WO1994018005A1 - Heat mode recording material and method for making a lithographic printing plate therewith - Google Patents

Heat mode recording material and method for making a lithographic printing plate therewith Download PDF

Info

Publication number
WO1994018005A1
WO1994018005A1 PCT/EP1994/000118 EP9400118W WO9418005A1 WO 1994018005 A1 WO1994018005 A1 WO 1994018005A1 EP 9400118 W EP9400118 W EP 9400118W WO 9418005 A1 WO9418005 A1 WO 9418005A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
recording material
heat mode
hydrophilic surface
surface layer
Prior art date
Application number
PCT/EP1994/000118
Other languages
French (fr)
Inventor
Yves Verburgh
Rudolf Van Den Bergh
Stefaan Karel De Meutter
Joan Triphon Vermeersch
Original Assignee
Agfa-Gevaert Naamloze Vennootschap
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 Naamloze Vennootschap filed Critical Agfa-Gevaert Naamloze Vennootschap
Priority to DE69402537T priority Critical patent/DE69402537D1/en
Priority to JP6517570A priority patent/JP2592225B2/en
Priority to EP94905082A priority patent/EP0683728B1/en
Publication of WO1994018005A1 publication Critical patent/WO1994018005A1/en

Links

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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
    • 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
    • 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
    • B41C2210/08—Developable by water or the fountain 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
    • B41C2210/24—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
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/24—Ablative recording, e.g. by burning marks; Spark recording

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 (hydrophobic areas) whereas other areas will not accept ink (hydrophilic areas) .
  • both water or an aqueous dampening liquid and ink are applied to the plate surface that contains hydrophilic and hydrophobic areas.
  • the hydrophilic areas will be soaked with water or the dampening liquid and are thereby rendered oleophobic while the hydrophobic areas will accept the ink.
  • DE-A-2448325 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 hydrophobic.
  • 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.
  • 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 li-quid during printing exposing the hydrophilic support.
  • Such plates can be used directly on the press without processing.
  • DD-A-155407 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.
  • this lithographic printing plate of high quality preferably can be obtained by development under essential dry conditions or with plain water or by using the imaged non processed plate directly on the press, these processing methods are referred to as 'ecological processing'.
  • a heat mode recording material comprising on a support having a 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.
  • a method for making a lithographic printing plate comprising the steps of:
  • a heat mode recording material comprising on a support having a 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 and
  • the thickness of the hydrophilic surface layer is not more than 3 ⁇ m preferably not more than l ⁇ m.
  • the minimum thickness of the surface layer is not particularly critical but is preferably more than 0.05
  • a particularly interesting range for the thickness of the hydrophilic surface layer is between 0.05 ⁇ m and 0.5 ⁇ m.
  • the heat mode recording material is image-wise exposed using a laser.
  • lasers are e.g. semiconductor lasers, YAG lasers e.g. Nd-YAG lasers, Argon lasers, ect.
  • the laser may have a power output between 40 mW and 10000 mW and preferably operates in the infrared part of the spectrum.
  • the hydrophilic surface layer is removed at the exposed imaged areas. Removing can be done by e.g. rubbing using e.g. a brush or a cotton pad. Such rubbing may be carried out during image-wise exposure as described in US-P-5.148.746.
  • Rubbing of the heat mode recording material is preferably carried out in absence of a liquid in essentially dry conditions.
  • plain water or a water based developer may be used also.
  • Removing the hydrophilic surface layer on the imaged areas can further be done by ultrasonic treatment of the imaged recording material immersed in plain water or a water based developer, by means of a pressure jet of plain water or a water based developer. Removal of the exposed areas may also be done by directly mounting the plate on a printing machine so that the dampening liquid dissolves and removes the hydrophilic surface layer at the exposed areas during startup of the printing machine.
  • the substance capable of converting light into heat may be present in the support and/or in a separate recording layer provided between the support and the hardened hydrophilic surface layer.
  • the thickness of such a separate recording layer may be varied over a wide range. However when the thickness of such recording layer becomes more than 3 ⁇ m image—wise exposure should then be carried out through the hardened hydrophilic surface layer. In this case it also preferred not to include an additional layer between such recording layer and the hardened hydrophilic surface layer or to keep the thickness of such additional layer to a minimum preferably not more than 0.5 ⁇ m. Furthermore when using a recording layer having a thickness of more than 3 ⁇ m such layer should then be ink receptive.
  • the thickness of the recording layer is less than 3 ⁇ m exposure can take place through the support, when transparent, or through the hardened hydrophilic layer.
  • the recording layer will generaly not be required to be ink receptive as long as the underlying surface or layer is ink receptive and total removal of the recording layer together with the hydrophilic surface layer at the exposed areas is possible.
  • a recording layer having a thickness between O.Ol ⁇ and 30 ⁇ m.
  • substances capable of converting light into heat that may be used in connection with the present invention are e.g. carbon black, infrared or near infrared absorbing dyes or pigments, metals such as Bi, Sn, Te etc. or a combination thereof. Suitable infrared dyes are disclosed in e.g. US-4833124, EP-321923,
  • Suitable infrared pigments are e.g. HEUCODOR metal oxide pigments available from Heubach Langelsheim.
  • the recording layer is preferably a vacuum or vapour deposited metal layer.
  • the recording layer may be a vacuum deposited aluminium layer.
  • the thickness of such an aluminium layer however should be less than 250 A and more preferably between lOOA and 225A.
  • Polymeric binders for the recording layer are preferably hydrophobic such as e.g. cellulose esters e.g. cellulose acetate, cellulose nitrate, a copolymer of vinylidene chloride and acrylonitrile, poly (meth) acrylates, polyvinyl chloride, etc..
  • 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-1316398 and DE-A-2512038) ; e.g. a polymer containing carbonate groups (e.g. polyalkylene carbonate); e.g. a polymer containing covalently bound chlorine (e.g. polyvinylidene chloride) .
  • Suitable supports for a heat mode recording material used in connection with the present invention are preferably non-metallic supports having a hydrophobic (ink receptive) surface e.g. a polyester film support, paper coated with a polyolefin such as polyethylene, polycarbonate film, polystyrene film etc..
  • metallic support such as e.g. aluminium can also used in connection with the present invention.
  • the surface of the support is not or insufficiently hydrophobic it may be provided with an intermediate hydrophobic primer coating whereon a recording layer may be deposited.
  • the recording layer can be the hydrophobic layer at the same time.
  • the recording layer may comprise additional substances such as plasticizers, crosslinking agents and resins, particulate materials such as e.g. polyethylene or fluorinated polymer dispersions, etc.. to impart toughness, print durability and oleophilic surface characteristics of the ablated image portions of the recording layer, wetting agents, matting agents, anti-oxidizing agents etc..
  • the recording layer will be hardened when it includes a binder.
  • any polymeric binder is suitable provided the adherance between the recording layer and the support is thereby improved. It has also been found that when the undercoat layer contains a polymer with heat labile groups (e.g. covalently bound chloride) adjacent to the recording layer the speed of the recording material can be improved as disclosed in EP 92201633.2.
  • a polymer with heat labile groups e.g. covalently bound chloride
  • imaging of the heat mode recording material takes place through the hydrophilic surface layer.
  • excellent image quality high sharpness, good contrast, excellent resolution
  • increased sensitivity are obtained.
  • hydrophilic coatings are preferably cast from aqueous compositions containing hydrophilic binders having free reactive groups including e.g. hydroxyl, carboxyl, hydroxyethyl, hydroxy-propyl, amino, aminoethyl, a inopropyl, carboxymethy1, etc.. along with suitable crosslinking or modifying agents including e.g. hydrophilic organotitanium reagents, ali.aminofo.rmyl acetate, dimethylol urea, melamines, aldehydes, hydrolyzed tetraalkyl orthosilicate, etc..
  • hydrophilic organotitanium reagents e.g. hydrophilic organotitanium reagents, ali.aminofo.rmyl 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, hydroxy-ethylene 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-3476937 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 91201227.5.
  • 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. a ino modified dextrane) and aldehyde.
  • the hardened hydrophilic surface layer may comprise additional substances such as e.g. plasticizers, pigments, dyes etc..
  • the hardened hydrophilic surface layer may also comprise particulate materials such as e.g. Ti ⁇ 2 or colloidal silica to increase the strength and/or hydrophilic character of the hydrophilic layer.
  • a polyethylene terephthalate support provided with a layer of a copolymer of vinylidene chloride (88 mol%) , methylacrylate (10 mol%) and itaconic acid (2mol%) in an amount of 170mg/m was vacuum deposited a bismuth layer as a recording layer such that the optical density thereof was 4.5 (thickness of about 0.30 ⁇ m) .
  • the thus prepared heat mode recording material was image-wise exposed through the hydrophilic surface layer with a Nd-YLF laser (1053 nm) at a linear writing speed of 32.8 m/s, with a spot diameter of 18 ⁇ m (l/e2) and a power output at the surface of the heat recording material of 1600 mW.
  • a Nd-YLF laser (1053 nm) at a linear writing speed of 32.8 m/s, with a spot diameter of 18 ⁇ m (l/e2) and a power output at the surface of the heat recording material of 1600 mW.
  • After imaging the hydrophilic surface layer was image—wise removed by rubbing with a dry cotton pad to expose the hydrophobic image portions of the support .
  • the optical density of the imaged image portions was decreased to about 0.05 compared to the non imaged areas having an optical density of 4.5. This difference in optical density between imaged and non imaged portions allows visual inspection of the recorded image on the plate.
  • the printing plate thus prepared was mounted on a printing press .ABDick 360 and was used to print with a commonly employed ink and dampening solution. The achieved image-wise hydrophobic-hydrophilic differentiation was satisfactory and print copies of good quality were obtained.
  • the imaged heat mode recording material as described in example 1 was image-wise exposed as described in example 1 and subjected to ultrasonic treatment in plain water during 2 minutes.
  • the printing plate thus prepared was mounted on a printing press ABDick 360 and was used to print with a commonly employed ink and dampening solution.
  • the image-wise achieved hydrophobic-hydrophilic differential was satisfactory and print copies of good quality were obtained.
  • the imaged heat mode recording material as described in example 1 was image-wise exposed as described in example 1 and was then mounted without further processing on a printing press .ABDick 360.
  • the recording material was used to print with a commonly employed ink and dampening solution.
  • the image-wise achieved hydrophobic- hydrophilic differential was satisfactory and print copies of good quality were obtained.
  • a dispersion for the recording layer having the following composition: 9.5 grams of low molecular weight nitrocellulose E330 (1), 9.5 grams of carbon black Special Schwarz 250, 0.2 grams of Solsperse 5000 (2), 0.8 grams of Solsperse 24000 (3), 80 grams of n-butanone.
  • the recording layer was applied to a dry coating thickness of about 0.5 ⁇ corresponding to an optical density of about 2.
  • E330 is a low molecular nitrocellulose, supplier Wolff Walsrode.
  • Solsperse 5000 is a dispersing agent from ICI .
  • Solsperse 24000 is a dispersing agent from ICI.
  • the thus prepared heat mode recording material was image-wise exposed through the hydrophilic layer with a Nd-YLF laser (1053nm) at a linear writing speed of 32.8 m/s, with a spot diameter of 18 ⁇ (l/e2) and a power output at the surface of the heat mode recording material of 1600 mW.
  • a Nd-YLF laser (1053nm) at a linear writing speed of 32.8 m/s, with a spot diameter of 18 ⁇ (l/e2) and a power output at the surface of the heat mode recording material of 1600 mW.
  • After imaging the hydrophilic surface layer was image—wise removed by rubbing with a dry cotton pad to expose the hydrophobic image portions of the remaining recording layer.
  • the optical density of the imaged image portions was decreased to about 1 compared to the non imaged areas having an optical density of 2. This difference in optical density between imaged and non imaged portions allows visual inspection of the recorded image on the plate.
  • the printing plate thus prepared was mounted on a printing press ABDick 360 and was used to print with a commonly employed ink and dampening solution.
  • the achieved image—wise hydrophobic-hydrophilic differentiation was satisfactory and print copies of good quality were obtained.
  • the recording layer was applied to a dry coating thickness of about 6 ⁇ corresponding to an optical density of >5.
  • the thus prepared heat mode recording material was image-wise exposed through the hydrophilic surface layer with a Nd-YLF laser (1053 nm) at a linear writing speed of 32.8 m/s, with a spot diameter of 18 ⁇ (l/e2) and a power output at the surface of the heat mode recording material of 1600 mW.
  • a Nd-YLF laser (1053 nm) at a linear writing speed of 32.8 m/s, with a spot diameter of 18 ⁇ (l/e2) and a power output at the surface of the heat mode recording material of 1600 mW.
  • After imaging the hydrophilic surface layer was image-wise removed by rubbing with a dry cotton pad to expose the hydrophobic image portions of the remaining recording layer.
  • the image portions showed a decreased optical reflectance compared to the non imaged areas. The difference in optical reflectance between imaged and non imaged portions allows visual inspection of the recorded image on the plate.
  • the printing plate thus prepared was mounted on a printing press ABDick 360 and was used to print with a commonly employed ink and dampening solution.
  • the achieved image-wise hydrophobic-hydrophilic differentiation was satisfactory and print copies of good quality were obtained.
  • a dispersion for the recording layer according the composition of example 4.
  • the recording layer was applied to a dry coating thickness of 0.5 ⁇ m corresponding to an optical density of about 2.
  • the thus prepared heat mode recording material was image-wise exposed through the hydrophilic toplayer with a Nd-YLF laser (1053 nm) at a linear writing speed of 32.8 m/s, with a spot diameter of 18 ⁇ m (l/e2) and a power output at the surface of the heat mode recording material of 1600 mW.
  • a Nd-YLF laser (1053 nm)
  • a spot diameter 18 ⁇ m (l/e2)
  • a power output at the surface of the heat mode recording material 1600 mW.
  • After imaging the hydrophilic surface layer was image-wise removed by rubbing with a dry cotton pad to expose the hydrophobic image portions of the remaining recording layer.
  • the optical density of the imaged portions was about 1 compared to the on imaged areas showing an optical density of 2. This difference in optical density between imaged and non imaged portions allows visual inspection of the recorded image on the plate.
  • the printing plate thus prepared was mounted on a printing press .ABDick 360 and was used to print with a commonly imployed ink and dampening solution. The acchieved image-wise hydrophobic-hydrophilic differentiation was satisfactory and print copies of good quality were obtained.
  • the imaged heat mode recording materials prepared and exposed according to examples 4, 5 and 6 were subjected to ultrasonic treatment in plain water during 2 minutes.
  • the printing plates thus prepared were mounted on a printing press ABDick 360 and were used to print with a commonly used ink and dampening.
  • the image-wise achieved hydrophobic-hydrophilic differential was satisfactory and print copies of good quality were obtained.
  • the recording materials were used to print with a commonly employed ink and dampening solution.
  • the image—wise achieved hydrophobic-hydrophilic differential was satisfactory and copies of good quality were obtained.

Abstract

The present invention provides a heat mode recording material having a high recording speed 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 3νm. There is further provided a method for making a printing plate of high quality therewith.

Description

HEAT MODE RECORDING MATERIAL AND METHOD FOR MAKING A LITHOGRAPHIC PRINTING PLATE THEREWITH.
DESCRIPTION
1. Field of the invention.
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.
2. Background of the invention.
Lithographic printing is the process of printing from specially prepared surfaces, some areas of which are capable of accepting ink (hydrophobic areas) whereas other areas will not accept ink (hydrophilic areas) . According to the so called conventional or wet printing plates, both water or an aqueous dampening liquid and ink are applied to the plate surface that contains hydrophilic and hydrophobic areas. The hydrophilic areas will be soaked with water or the dampening liquid and are thereby rendered oleophobic while the hydrophobic areas will accept the ink.
When a laser heat mode recording material is to be used as a direct offset master for printing with greasy inks, it is necessary to have hydrophobic-hydrophilic mapping of the image and non-image areas. In the case of heat mode laser ablation it is also necessary to completely image wise remove a hydrophilic or hydrophobic topcoat to expose the underlying hydrophobic respectively hydrophilic surface of the laser sensitive recording material in order to obtain the necessary difference in ink-acceptance between the image and non-image areas.
For example DE-A-2448325 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 hydrophobic. 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.
Other disclosures in DE-A-2448325 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) . Further ex-amples about heat mode recording materials for preparing "direct negative" printing plates include e.g. US-A-40341183, DE-A-2607207, DD-A-213530, DD-A-217645 and DD-A-217914. 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 li-quid during printing exposing the hydrophilic support. Such plates can be used directly on the press without processing.
DD-A-155407 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.
From the above it can be seen that a number of proposals have been made for making a 'direct negative' offset printing plate by laser heat mode recording. They have such disadvantages as low recording speed and/or the obtained plates are of poor quality.
3. Summary of the invention
According to the present invention it is an object to provide an alternative heat mode recording material of high sensitivity for making a negative working lithographic printing plate of high quality.
For ecological reasons it is another object of the present invention that this lithographic printing plate of high quality preferably can be obtained by development under essential dry conditions or with plain water or by using the imaged non processed plate directly on the press, these processing methods are referred to as 'ecological processing'.
Still further objects of the present invention will become clear from the description hereinafter.
According to the present invention there is provided a heat mode recording material comprising on a support having a 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 3μm.
According to the present invention there is provided a method for making a lithographic printing plate comprising the steps of:
— image wise exposing a heat mode recording material comprising on a support having a 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 3μm and
- subsequently removing said hardened hydrophilic surface layer at the exposed areas by rubbing a thus obtained image-wise exposed heat mode recording material under essentially dry conditions or by using water or an aqueous solution.
4. Detailed description of the invention.
It has been found that in accordance with the present invention negative working lithographic printing plates can be obtained having a high recording speed, yielding a high printing endurance, high sharpness, good contrast and an excellent resolution in an ecologically more acceptable way.
To obtain the effects of the present invention it is important that the thickness of the hydrophilic surface layer is not more than 3μm preferably not more than lμm. When the thickness of the hydrophilic surface layer becomes more than 3|lm a heat mode recording material will be obtained having a low recording speed and yielding printing plates of poor quality. The minimum thickness of the surface layer is not particularly critical but is preferably more than 0.05|im. A particularly interesting range for the thickness of the hydrophilic surface layer is between 0.05μm and 0.5μm.
In order to obtain good lithographic printing properties, especially to obtain a good printing endurance, it is also a requirement that the hydrophilic surface layer be hardened.
According to a preferred method of the present invention the heat mode recording material is image-wise exposed using a laser. Preferably used lasers are e.g. semiconductor lasers, YAG lasers e.g. Nd-YAG lasers, Argon lasers, ect.. The laser may have a power output between 40 mW and 10000 mW and preferably operates in the infrared part of the spectrum. Subsequent to the image-wise exposure the hydrophilic surface layer is removed at the exposed imaged areas. Removing can be done by e.g. rubbing using e.g. a brush or a cotton pad. Such rubbing may be carried out during image-wise exposure as described in US-P-5.148.746. Rubbing of the heat mode recording material is preferably carried out in absence of a liquid in essentially dry conditions. However plain water or a water based developer may be used also. Removing the hydrophilic surface layer on the imaged areas can further be done by ultrasonic treatment of the imaged recording material immersed in plain water or a water based developer, by means of a pressure jet of plain water or a water based developer. Removal of the exposed areas may also be done by directly mounting the plate on a printing machine so that the dampening liquid dissolves and removes the hydrophilic surface layer at the exposed areas during startup of the printing machine.
The substance capable of converting light into heat may be present in the support and/or in a separate recording layer provided between the support and the hardened hydrophilic surface layer. The thickness of such a separate recording layer may be varied over a wide range. However when the thickness of such recording layer becomes more than 3μm image—wise exposure should then be carried out through the hardened hydrophilic surface layer. In this case it also preferred not to include an additional layer between such recording layer and the hardened hydrophilic surface layer or to keep the thickness of such additional layer to a minimum preferably not more than 0.5μm. Furthermore when using a recording layer having a thickness of more than 3μm such layer should then be ink receptive.
On the other hand when the thickness of the recording layer is less than 3μm exposure can take place through the support, when transparent, or through the hardened hydrophilic layer. Further in this case the recording layer will generaly not be required to be ink receptive as long as the underlying surface or layer is ink receptive and total removal of the recording layer together with the hydrophilic surface layer at the exposed areas is possible.
In any case, irrespective of the thickeness of the recording layer, exposure through the hardened hydrophilic surface layer is preferred since it has been found that the printing plates obtained in this way have a better resolution and sharpness.
According to a preferred embodiment of the present invention a recording layer is used having a thickness between O.Olμ and 30μm. Examples of substances capable of converting light into heat that may be used in connection with the present invention are e.g. carbon black, infrared or near infrared absorbing dyes or pigments, metals such as Bi, Sn, Te etc. or a combination thereof. Suitable infrared dyes are disclosed in e.g. US-4833124, EP-321923,
US-4774583, US-4942141, US-4948776, US-4948777, US-4948778, US-4950639, US-4950640, US-4912083, US-4958552, US-5024990, US-5023229 etc.. Suitable infrared pigments are e.g. HEUCODOR metal oxide pigments available from Heubach Langelsheim. When a metal such as e.g. bismuth is used as a heat converting substance the recording layer is preferably a vacuum or vapour deposited metal layer.
According to a particular embodiment of the present invention the recording layer may be a vacuum deposited aluminium layer. The thickness of such an aluminium layer however should be less than 250 A and more preferably between lOOA and 225A.
However the substance capable of converting light into heat may alos be dissolved or dispersed in a binder. Polymeric binders for the recording layer are preferably hydrophobic such as e.g. cellulose esters e.g. cellulose acetate, cellulose nitrate, a copolymer of vinylidene chloride and acrylonitrile, poly (meth) acrylates, polyvinyl chloride, etc.. Preferably 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-1316398 and DE-A-2512038) ; e.g. a polymer containing carbonate groups (e.g. polyalkylene carbonate); e.g. a polymer containing covalently bound chlorine (e.g. polyvinylidene chloride) .
Suitable supports for a heat mode recording material used in connection with the present invention are preferably non-metallic supports having a hydrophobic (ink receptive) surface e.g. a polyester film support, paper coated with a polyolefin such as polyethylene, polycarbonate film, polystyrene film etc.. However metallic support such as e.g. aluminium can also used in connection with the present invention. In case the surface of the support is not or insufficiently hydrophobic it may be provided with an intermediate hydrophobic primer coating whereon a recording layer may be deposited. Alternatively the recording layer can be the hydrophobic layer at the same time.
According to the present invention the recording layer may comprise additional substances such as plasticizers, crosslinking agents and resins, particulate materials such as e.g. polyethylene or fluorinated polymer dispersions, etc.. to impart toughness, print durability and oleophilic surface characteristics of the ablated image portions of the recording layer, wetting agents, matting agents, anti-oxidizing agents etc.. Preferably the recording layer will be hardened when it includes a binder.
Concerning the composition of an optional undercoat layer any polymeric binder is suitable provided the adherance between the recording layer and the support is thereby improved. It has also been found that when the undercoat layer contains a polymer with heat labile groups (e.g. covalently bound chloride) adjacent to the recording layer the speed of the recording material can be improved as disclosed in EP 92201633.2.
According to the most preferred embodiment of the present invention imaging of the heat mode recording material takes place through the hydrophilic surface layer. In this way excellent image quality (high sharpness, good contrast, excellent resolution) and increased sensitivity are obtained.
Different kinds of hardened hydrophilic surface layers are suitable in connection with the present invention. The hydrophilic coatings are preferably cast from aqueous compositions containing hydrophilic binders having free reactive groups including e.g. hydroxyl, carboxyl, hydroxyethyl, hydroxy-propyl, amino, aminoethyl, a inopropyl, carboxymethy1, etc.. along with suitable crosslinking or modifying agents including e.g. hydrophilic organotitanium reagents, ali.aminofo.rmyl 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, hydroxy-ethylene 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-3476937 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 91201227.5. 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. a ino modified dextrane) and aldehyde.
According to the present invention the hardened hydrophilic surface layer may comprise additional substances such as e.g. plasticizers, pigments, dyes etc.. The hardened hydrophilic surface layer may also comprise particulate materials such as e.g. Tiθ2 or colloidal silica to increase the strength and/or hydrophilic character of the hydrophilic layer.
The present invention will now be illustrated with the following examples without however limiting it thereto. All parts are by weight unless otherwise specified.
EXAJtfPLE 1
To a polyethylene terephthalate support provided with a layer of a copolymer of vinylidene chloride (88 mol%) , methylacrylate (10 mol%) and itaconic acid (2mol%) in an amount of 170mg/m was vacuum deposited a bismuth layer as a recording layer such that the optical density thereof was 4.5 (thickness of about 0.30 μm) .
To this recording layer was then coated the following coating dispersion for the hydrophilic layer: to 82 grams of a dispersion containing 21.5 % of Ti02 (average particle size 0.3 to 0.5 μm) and 2.5 % of polyvinylalcohol in deionized water were subsequently added, while stirring, 639 grams of a 5 % polyvinyl alcohol solution in water, 77 grams of a hydrolyzed 22 % tetramethyl orthosilicate emulsion in water and 22 grams of a 10 % solution of a wetting agent. To this mixture was then added 180 grams of deionized water and the pH was adjusted to pH=4. The coating dispersion was coated on the recording layer to a dry thickness of 0.5 μ to obtain a hydrophilic surface layer. After drying at 30°C the thus obtained element was subjected to a temperature of 80°C for several hours.
The thus prepared heat mode recording material was image-wise exposed through the hydrophilic surface layer with a Nd-YLF laser (1053 nm) at a linear writing speed of 32.8 m/s, with a spot diameter of 18 μm (l/e2) and a power output at the surface of the heat recording material of 1600 mW. After imaging the hydrophilic surface layer was image—wise removed by rubbing with a dry cotton pad to expose the hydrophobic image portions of the support . The optical density of the imaged image portions was decreased to about 0.05 compared to the non imaged areas having an optical density of 4.5. This difference in optical density between imaged and non imaged portions allows visual inspection of the recorded image on the plate.
The printing plate thus prepared was mounted on a printing press .ABDick 360 and was used to print with a commonly employed ink and dampening solution. The achieved image-wise hydrophobic-hydrophilic differentiation was satisfactory and print copies of good quality were obtained.
EXAMPLE 2
The imaged heat mode recording material as described in example 1 was image-wise exposed as described in example 1 and subjected to ultrasonic treatment in plain water during 2 minutes.
The printing plate thus prepared was mounted on a printing press ABDick 360 and was used to print with a commonly employed ink and dampening solution. The image-wise achieved hydrophobic-hydrophilic differential was satisfactory and print copies of good quality were obtained.
EX2*iMPLE 3
The imaged heat mode recording material as described in example 1 was image-wise exposed as described in example 1 and was then mounted without further processing on a printing press .ABDick 360. The recording material was used to print with a commonly employed ink and dampening solution. The image-wise achieved hydrophobic- hydrophilic differential was satisfactory and print copies of good quality were obtained.
EJCAMPLE 4
To a polyethylene terephthalate support was coated a dispersion for the recording layer having the following composition: 9.5 grams of low molecular weight nitrocellulose E330 (1), 9.5 grams of carbon black Special Schwarz 250, 0.2 grams of Solsperse 5000 (2), 0.8 grams of Solsperse 24000 (3), 80 grams of n-butanone. The recording layer was applied to a dry coating thickness of about 0.5 μ corresponding to an optical density of about 2.
(1) E330 is a low molecular nitrocellulose, supplier Wolff Walsrode.
(2) Solsperse 5000 is a dispersing agent from ICI .
(3) Solsperse 24000 is a dispersing agent from ICI.
To this recording layer was then coated the coating dispersion from example 1 for the hydrophilic layer to a dry thickness of 0.5 μ to obtain a hydrophilic surface layer. After drying at 30°C the thus obtained element was subjected to a temperature of 80°C for several hours .
The thus prepared heat mode recording material was image-wise exposed through the hydrophilic layer with a Nd-YLF laser (1053nm) at a linear writing speed of 32.8 m/s, with a spot diameter of 18 μ (l/e2) and a power output at the surface of the heat mode recording material of 1600 mW. After imaging the hydrophilic surface layer was image—wise removed by rubbing with a dry cotton pad to expose the hydrophobic image portions of the remaining recording layer. The optical density of the imaged image portions was decreased to about 1 compared to the non imaged areas having an optical density of 2. This difference in optical density between imaged and non imaged portions allows visual inspection of the recorded image on the plate.
The printing plate thus prepared was mounted on a printing press ABDick 360 and was used to print with a commonly employed ink and dampening solution. The achieved image—wise hydrophobic-hydrophilic differentiation was satisfactory and print copies of good quality were obtained.
EXA1YIPLE 5
To a polyethylene terephthalate support was coated a dispersion for the recording layer according the composition of example 4. The recording layer was applied to a dry coating thickness of about 6 μ corresponding to an optical density of >5.
To this recording layer was then coated the coating dispersion from example 1 for the hydrophilic layer to a dry thickness of 0.5 μm to obtain a hydrophilic surface layer. After drying at 30°C the thus obtained element was subjected to a temperature of 80°C for several hours .
The thus prepared heat mode recording material was image-wise exposed through the hydrophilic surface layer with a Nd-YLF laser (1053 nm) at a linear writing speed of 32.8 m/s, with a spot diameter of 18μ (l/e2) and a power output at the surface of the heat mode recording material of 1600 mW. After imaging the hydrophilic surface layer was image-wise removed by rubbing with a dry cotton pad to expose the hydrophobic image portions of the remaining recording layer. The image portions showed a decreased optical reflectance compared to the non imaged areas. The difference in optical reflectance between imaged and non imaged portions allows visual inspection of the recorded image on the plate.
The printing plate thus prepared was mounted on a printing press ABDick 360 and was used to print with a commonly employed ink and dampening solution. The achieved image-wise hydrophobic-hydrophilic differentiation was satisfactory and print copies of good quality were obtained.
EXAMPLE 6
To a polyethylene terephthalate support was coated a dispersion for the recording layer according the composition of example 4. The recording layer was applied to a dry coating thickness of 0.5 μm corresponding to an optical density of about 2.
To this recording layer was then coated following coating composition for the hydrophilic surface layer: prior to application was added to lOOg of a solution containing 2 % of carboxy- methylcellulose (CMC) 4.5 grams of a hydrolyzed 22 % tetramethyl orthosilicate emulsion in water and 2 grams of a 10 % solution of a wetting agent. The pH of the composition was adjusted to pH=4. The coating dispersion was coated on the recording layer to a thickness of 0.5 μm. After drying at 30°C the thus obtained element was subjected to a temperature of 130°c for 5 minutes. After polishing with a wet cotton pad a very though hydrophilic surface layer with a thickness of <0.5 μm was obtained on the hydrophobic nitrocellulose- carbon black based recording layer.
The thus prepared heat mode recording material was image-wise exposed through the hydrophilic toplayer with a Nd-YLF laser (1053 nm) at a linear writing speed of 32.8 m/s, with a spot diameter of 18 μm (l/e2) and a power output at the surface of the heat mode recording material of 1600 mW. After imaging the hydrophilic surface layer was image-wise removed by rubbing with a dry cotton pad to expose the hydrophobic image portions of the remaining recording layer. The optical density of the imaged portions was about 1 compared to the on imaged areas showing an optical density of 2. This difference in optical density between imaged and non imaged portions allows visual inspection of the recorded image on the plate.
The printing plate thus prepared was mounted on a printing press .ABDick 360 and was used to print with a commonly imployed ink and dampening solution. The acchieved image-wise hydrophobic-hydrophilic differentiation was satisfactory and print copies of good quality were obtained.
EXAMPLE 7
The imaged heat mode recording materials prepared and exposed according to examples 4, 5 and 6 were subjected to ultrasonic treatment in plain water during 2 minutes.
The printing plates thus prepared were mounted on a printing press ABDick 360 and were used to print with a commonly used ink and dampening. The image-wise achieved hydrophobic-hydrophilic differential was satisfactory and print copies of good quality were obtained.
EXAMPLE 8
The imaged heat mode recording materials prepared and exposed according to examples 4, 5 and 6 were mounted without further processing on a printing press .ABDick 360.
The recording materials were used to print with a commonly employed ink and dampening solution. The image—wise achieved hydrophobic-hydrophilic differential was satisfactory and copies of good quality were obtained.

Claims

1. 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 3μm.
2. A heat mode recording material according to claim 1 wherein said substance capable of converting light into heat is provided in a separate recording layer between said support and said hardened hydrophilic surface layer.
3. A heat mode recording material according to claim 2 wherein said recording layer has a thickness of more than 3μm and is ink receptive.
4. A heat mode recording material according to claim 3 wherein said recording layer is adjacent to said hardened hydrophilic surface layer or wherein there is provided an intermediate layer between said recording layer and said hardened hydrophilic surface layer having a thickness of not more than 0.5μm.
5. A heat mode recording material according to claim 2 wherein the thickness of said recording layer is not more than 3μm.
6. A heat mode recording material according to claim 5 wherein said recording layer is a vapour or vacuum deposited metal layer.
7. A heat mode recording material according to any of the above claims wherein said hardened hydrophilic surface layer comprises the reaction product of a hydrophilic polymer and a hydrolyzed tetraalkyl orthosilicate.
8. A method for making a lithographic printing plate comprising the steps of:
- image-wise exposing a heat mode recording material comprising on a support having a 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 3μm and - subsequently removing said hardened hydrophilic surface layer at the exposed areas by rubbing a thus obtained image-wise exposed heat mode recording material under essentially dry conditions or by using water or an aqueous solution.
9. A method according to claim 8 wherein said substance capable of converting light into heat is provided in a separate recording layer between said support and said hardened hydrophilic surface layer.
10. A method according to claim 9 wherein said recording layer has a thickness of more than 3μm and is ink receptive and wherein image- wise exposure proceeds through said hardened hydrophilic surface layer.
PCT/EP1994/000118 1993-02-09 1994-01-14 Heat mode recording material and method for making a lithographic printing plate therewith WO1994018005A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE69402537T DE69402537D1 (en) 1993-02-09 1994-01-14 Heat sensitive recording material and method for producing a printing stream for planographic printing
JP6517570A JP2592225B2 (en) 1993-02-09 1994-01-14 Heat mode recording material and method for producing lithographic printing plate using the same
EP94905082A EP0683728B1 (en) 1993-02-09 1994-01-14 Heat mode recording material and method for making a lithographic printing plate therewith

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP93200342 1993-02-09
EP93200342.9 1993-02-09

Publications (1)

Publication Number Publication Date
WO1994018005A1 true WO1994018005A1 (en) 1994-08-18

Family

ID=8213618

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/000118 WO1994018005A1 (en) 1993-02-09 1994-01-14 Heat mode recording material and method for making a lithographic printing plate therewith

Country Status (4)

Country Link
EP (1) EP0683728B1 (en)
JP (1) JP2592225B2 (en)
DE (1) DE69402537D1 (en)
WO (1) WO1994018005A1 (en)

Cited By (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0727321A1 (en) * 1995-02-17 1996-08-21 Konica Corporation Image forming material, method of preparing the same and image forming method employing the same
EP0770496A1 (en) * 1995-10-24 1997-05-02 Agfa-Gevaert N.V. Printing apparatus for making a lithographic printing plate involving on press development
EP0770494A2 (en) * 1995-10-24 1997-05-02 Agfa-Gevaert N.V. A method for making a lithographic printing plate involving on press development
EP0770497A1 (en) * 1995-10-24 1997-05-02 Agfa-Gevaert N.V. A method for making a lithographic printing plate involving development by plain water
EP0770495A1 (en) * 1995-10-24 1997-05-02 Agfa-Gevaert N.V. A method for making a lithographic printing plate involving on press development
EP0795998A1 (en) * 1996-03-14 1997-09-17 Agfa-Gevaert N.V. Producing a lithographic printing plate by sequentially exposing a thermo-sensitive imaging element by a set of radiation beams
EP0816070A1 (en) * 1996-06-24 1998-01-07 Agfa-Gevaert N.V. A heat sensitive imaging element and a method for producing lithographic plates therewith
EP0839647A1 (en) * 1996-10-29 1998-05-06 Agfa-Gevaert N.V. Method for making a lithographic printing plate with improved ink-uptake
WO1998034796A1 (en) * 1997-02-07 1998-08-13 Kodak Polychrome Graphics Company Ltd. Planographic printing member and process for its manufacture
WO1998040213A1 (en) * 1997-03-13 1998-09-17 Kodak Polychrome Graphics, L.L.C. Method of imaging lithographic printing plates with high intensity laser
WO1998040212A1 (en) * 1997-03-13 1998-09-17 Kodak Polychrome Graphics, L.L.C. Lithographic printing plates with a sol-gel layer
WO1998055311A1 (en) * 1997-06-03 1998-12-10 Agfa-Gevaert Naamloze Vennootschap Heat sensitive printing plate precursors
WO1998058801A1 (en) * 1997-06-24 1998-12-30 Kodak Polychrome Graphics, L.L.C. Direct write lithographic printing plates
WO1999004974A1 (en) * 1997-07-25 1999-02-04 Kodak Polychrome Graphics Single layer direct write lithographic printing plates
WO1999019143A1 (en) * 1997-10-14 1999-04-22 Kodak Polychrome Graphics Improved lithographic printing plates comprising a photothermal conversion material
WO1999019144A1 (en) * 1997-10-14 1999-04-22 Kodak Polychrome Graphics Dimensionally stable lithographic printing plates with a sol-gel layer
WO1999038688A1 (en) * 1998-01-29 1999-08-05 Kodak Polychrome Graphics, Llc Direct write waterless imaging member with improved ablation properties and methods of imaging and printing
EP0953441A1 (en) * 1998-04-30 1999-11-03 Eastman Kodak Company Antireflection direct write lithographic printing plates
US6001536A (en) * 1995-10-24 1999-12-14 Agfa-Gevaert, N.V. Method for making a lithographic printing plate involving development by plain water
EP0967077A1 (en) * 1998-06-26 1999-12-29 Agfa-Gevaert N.V. A heat sensitive imaging element and a method for producing lithographic plates therewith
US6022668A (en) * 1998-01-19 2000-02-08 Kodak Polychrome Graphics Llc Positive-working direct write waterless lithographic printing members and methods of imaging and printing using same
US6040115A (en) * 1996-11-14 2000-03-21 Kodak Polychrome Graphics Llc Processless planographic printing plate
US6110645A (en) * 1997-03-13 2000-08-29 Kodak Polychrome Graphics Llc Method of imaging lithographic printing plates with high intensity laser
US6110644A (en) * 1995-10-24 2000-08-29 Agfa-Gevaert, N.V. Method for making a lithographic printing plate involving on press development
US6136508A (en) * 1997-03-13 2000-10-24 Kodak Polychrome Graphics Llc Lithographic printing plates with a sol-gel layer
EP1084826A1 (en) * 1999-09-17 2001-03-21 Fuji Photo Film Co., Ltd. Heat-sensitive lithographic printing plate precursor
US6210857B1 (en) 1998-06-26 2001-04-03 Agfa-Gevaert Heat sensitive imaging element for providing a lithographic printing plate
US6238843B1 (en) 1998-02-28 2001-05-29 Kodak Polychrome Graphics, Llc Planographic printing member and method for its preparation
EP1110719A2 (en) * 1999-12-22 2001-06-27 Fuji Photo Film Co., Ltd. Heat-sensitive lithographic printing plate precursor
EP1208974A2 (en) * 2000-11-21 2002-05-29 Agfa-Gevaert Processless lithographic printing plate
US6397749B1 (en) * 1999-07-26 2002-06-04 Fuji Photo Film Co., Ltd. Heat-sensitive lithographic printing plate precursor
EP1226976A1 (en) * 2001-01-24 2002-07-31 Fuji Photo Film Co., Ltd. Hydrophilic polymer having silane coupling group terminal and lithographic printing plate base
US6427595B1 (en) * 1996-12-19 2002-08-06 Agfa-Gevaert Heat-sensitive imaging element for making lithographic printing plates comprising polymer particles with a specific particle size
US6447884B1 (en) 2000-03-20 2002-09-10 Kodak Polychrome Graphics Llc Low volume ablatable processless imaging member and method of use
US6455222B1 (en) 1999-03-24 2002-09-24 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor
US6458507B1 (en) 2000-03-20 2002-10-01 Kodak Polychrome Graphics Llc Planographic thermal imaging member and methods of use
EP1260361A2 (en) 2001-05-22 2002-11-27 Fuji Photo Film Co., Ltd. Method for making lithographic printing plate
EP0983149B1 (en) * 1997-05-23 2003-01-08 Kodak Polychrome Graphics Company Ltd. Planographic printing
EP1354720A2 (en) 2002-04-15 2003-10-22 Fuji Photo Film Co., Ltd. Heat-sensitive lithographic printing plate precursor
US6653042B1 (en) 1999-06-04 2003-11-25 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor, method for producing the same, and method of lithographic printing
US6790595B2 (en) 2000-11-21 2004-09-14 Agfa-Gevaert Processless lithographic printing plate
US6878503B2 (en) 2001-10-10 2005-04-12 Fuji Photo Film Co., Ltd. Heat-sensitive lithographic printing plate precursor
EP1609617A1 (en) * 2004-06-21 2005-12-28 Konica Minolta Medical & Graphic Inc. Printing plate material and image formation process
WO2006026229A1 (en) * 2004-08-25 2006-03-09 Eastman Kodak Company Method and apparatus for development of lithographic printing plate precursor
WO2009061995A1 (en) * 2007-11-09 2009-05-14 Presstek, Inc. Lithographic imaging with printing members having hydrophilic, surfactant-containing top layers
EP2109000A1 (en) 2004-09-10 2009-10-14 FUJIFILM Corporation Polymer having polymerizable group, polymerizable composition, planographic printing plate precursor, and planographic printing method using the same
US7608388B2 (en) * 2004-10-12 2009-10-27 Presstek, Inc. Inkjet-imageable lithographic printing members and methods of preparing and imaging them

Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4130030B2 (en) 1999-03-09 2008-08-06 富士フイルム株式会社 Photosensitive composition and 1,3-dihydro-1-oxo-2H-indene derivative compound
US6479207B1 (en) 1999-04-22 2002-11-12 Konica Corporation Printing plate element and production method thereof
CA2441802C (en) * 2001-03-26 2008-01-22 Fuji Photo Film Co., Ltd. Thermosensitive plate material for lithographic plate formation, process for producing the same, coating liquid, and lithographic plate
EP1249342B1 (en) 2001-04-09 2006-10-18 Fuji Photo Film Co., Ltd. Planographic printing plate precursor
DE60214472T2 (en) 2001-06-11 2007-05-16 Fuji Photo Film Co., Ltd., Minami-Ashigara Planographic printing plate precursor, substrate therefor and hydrophilic surface material
JP2002370465A (en) 2001-06-14 2002-12-24 Konica Corp Printing plate material, method for forming image on printing plate material and method for printing
US6911295B2 (en) 2001-08-03 2005-06-28 Fuji Photo Film Co., Ltd. Planographic printing plate precursor
US6936399B2 (en) 2001-10-22 2005-08-30 Fuji Photo Film Co., Ltd. Hydrophilic member, hydrophilic graft polymer, and support of planographic printing plate
US6977132B2 (en) 2001-12-07 2005-12-20 Fuji Photo Film Co., Ltd. Planographic printing plate precursor
JP3780958B2 (en) 2002-02-12 2006-05-31 コニカミノルタホールディングス株式会社 Printing plate material and printing plate
DE60315772T2 (en) 2002-09-05 2008-06-05 Fujifilm Corp. Lithographic printing plate precursor
US7056642B2 (en) 2002-09-18 2006-06-06 Fuji Photo Film Co., Ltd. Method of graft polymerization and variety of materials utilizing the same as well as producing method thereof
JP4100112B2 (en) 2002-09-20 2008-06-11 コニカミノルタホールディングス株式会社 Printing plate material and printing method
JP2005037881A (en) 2003-04-21 2005-02-10 Fuji Photo Film Co Ltd Pattern forming method, image forming method, fine particle adsorption pattern forming method, conductive pattern forming method, pattern forming material, and planographic printing plate
JP2005178013A (en) 2003-12-16 2005-07-07 Konica Minolta Medical & Graphic Inc Printing plate material and printing method
DE602005000382T2 (en) 2004-01-20 2007-11-08 Konica Minolta Medical & Graphic Inc. Printing plate material and its development process
JP2005225023A (en) 2004-02-12 2005-08-25 Konica Minolta Medical & Graphic Inc Printing plate material
JP2005305690A (en) 2004-04-19 2005-11-04 Konica Minolta Medical & Graphic Inc Printing plate material, printing method of printing plate material and offset press
JP2005305689A (en) 2004-04-19 2005-11-04 Konica Minolta Medical & Graphic Inc Printing plate material and printing method
JP4452572B2 (en) 2004-07-06 2010-04-21 富士フイルム株式会社 Photosensitive composition and image recording method using the same
JP2006056184A (en) 2004-08-23 2006-03-02 Konica Minolta Medical & Graphic Inc Printing plate material and printing plate
JP2006065074A (en) 2004-08-27 2006-03-09 Fuji Photo Film Co Ltd Photosensitive lithographic printing plate
JP4411168B2 (en) 2004-09-24 2010-02-10 富士フイルム株式会社 Photosensitive planographic printing plate
EP1701213A3 (en) 2005-03-08 2006-11-22 Fuji Photo Film Co., Ltd. Photosensitive composition
JP4538350B2 (en) 2005-03-18 2010-09-08 富士フイルム株式会社 Photosensitive composition, image recording material, and image recording method
JP4368323B2 (en) 2005-03-25 2009-11-18 富士フイルム株式会社 Photosensitive planographic printing plate
JP4457034B2 (en) 2005-03-28 2010-04-28 富士フイルム株式会社 Photosensitive planographic printing plate
JP2006272782A (en) 2005-03-29 2006-10-12 Fuji Photo Film Co Ltd Planographic printing plate
JP4701042B2 (en) 2005-08-22 2011-06-15 富士フイルム株式会社 Photosensitive planographic printing plate
JP4694324B2 (en) 2005-09-09 2011-06-08 富士フイルム株式会社 Method for producing photosensitive lithographic printing plate
US20090186201A1 (en) 2006-07-14 2009-07-23 Konica Minolta Holdings, Inc. Plate making method and planographic printing plate
JP5238292B2 (en) 2007-03-23 2013-07-17 三菱製紙株式会社 Water-developable photosensitive lithographic printing plate material
TWI436163B (en) 2007-07-17 2014-05-01 Fujifilm Corp Photosensitive compositions, curable compositions, novel compounds, photopolymerizable compositions, color filters, and planographic printing plate precursors
JP2009086373A (en) 2007-09-28 2009-04-23 Fujifilm Corp Method of developing negative planographic printing plate
JP5305704B2 (en) 2008-03-24 2013-10-02 富士フイルム株式会社 Novel compound, photopolymerizable composition, photopolymerizable composition for color filter, color filter and method for producing the same, solid-state imaging device, and lithographic printing plate precursor
JP5171506B2 (en) 2008-06-30 2013-03-27 富士フイルム株式会社 NOVEL COMPOUND, POLYMERIZABLE COMPOSITION, COLOR FILTER, PROCESS FOR PRODUCING THE SAME, SOLID-STATE IMAGING ELEMENT, AND lithographic printing plate
EP2899034B1 (en) 2012-09-20 2019-07-03 FUJIFILM Corporation Original planographic printing plate, and plate making method
EP2905144B1 (en) 2012-09-26 2017-07-19 Fujifilm Corporation Lithographic printing original plate and plate making method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2258649A1 (en) * 1974-01-17 1975-08-18 Scott Paper Co
EP0160396A2 (en) * 1984-04-25 1985-11-06 Imperial Chemical Industries Plc Laser-imageable assembly and process for production thereof
EP0164128A2 (en) * 1984-06-08 1985-12-11 Howard A. Fromson Process for making lithographic printing plates, and printing plates made by the process

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1489308A (en) * 1974-03-18 1977-10-19 Scott Paper Co Laser imagable dry planographic printing plate blank
JPS597090B2 (en) * 1976-07-30 1984-02-16 関西ペイント株式会社 Plate making method for lithographic printing plates
JPS55105560A (en) * 1979-02-07 1980-08-13 Tomoegawa Paper Co Ltd Photoengraving by laser
JPS6490748A (en) * 1987-10-01 1989-04-07 Tomoegawa Paper Co Ltd Thermal processing method in plate making
EP0573091B1 (en) * 1992-06-05 1996-03-20 Agfa-Gevaert N.V. A heat mode recording material and method for producing driographic printing plates
EP0573092A1 (en) * 1992-06-05 1993-12-08 Agfa-Gevaert N.V. A method for obtaining an image using a heat mode recording material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2258649A1 (en) * 1974-01-17 1975-08-18 Scott Paper Co
EP0160396A2 (en) * 1984-04-25 1985-11-06 Imperial Chemical Industries Plc Laser-imageable assembly and process for production thereof
EP0164128A2 (en) * 1984-06-08 1985-12-11 Howard A. Fromson Process for making lithographic printing plates, and printing plates made by the process

Cited By (65)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5691103A (en) * 1995-02-17 1997-11-25 Konica Corporation Image forming material, method of preparing the same and image forming method employing the same
EP0727321A1 (en) * 1995-02-17 1996-08-21 Konica Corporation Image forming material, method of preparing the same and image forming method employing the same
US6001536A (en) * 1995-10-24 1999-12-14 Agfa-Gevaert, N.V. Method for making a lithographic printing plate involving development by plain water
EP0770495A1 (en) * 1995-10-24 1997-05-02 Agfa-Gevaert N.V. A method for making a lithographic printing plate involving on press development
US6110644A (en) * 1995-10-24 2000-08-29 Agfa-Gevaert, N.V. Method for making a lithographic printing plate involving on press development
EP0770496A1 (en) * 1995-10-24 1997-05-02 Agfa-Gevaert N.V. Printing apparatus for making a lithographic printing plate involving on press development
EP0770494A2 (en) * 1995-10-24 1997-05-02 Agfa-Gevaert N.V. A method for making a lithographic printing plate involving on press development
EP0770497A1 (en) * 1995-10-24 1997-05-02 Agfa-Gevaert N.V. A method for making a lithographic printing plate involving development by plain water
EP1092555A1 (en) * 1995-10-24 2001-04-18 Agfa-Gevaert N.V. A method for making a lithographic printing plate involving on-press development
EP0770494A3 (en) * 1995-10-24 1997-05-07 Agfa-Gevaert N.V. A method for making a lithographic printing plate involving on press development
EP0795998A1 (en) * 1996-03-14 1997-09-17 Agfa-Gevaert N.V. Producing a lithographic printing plate by sequentially exposing a thermo-sensitive imaging element by a set of radiation beams
EP0816070A1 (en) * 1996-06-24 1998-01-07 Agfa-Gevaert N.V. A heat sensitive imaging element and a method for producing lithographic plates therewith
EP0839647A1 (en) * 1996-10-29 1998-05-06 Agfa-Gevaert N.V. Method for making a lithographic printing plate with improved ink-uptake
US6040115A (en) * 1996-11-14 2000-03-21 Kodak Polychrome Graphics Llc Processless planographic printing plate
US6427595B1 (en) * 1996-12-19 2002-08-06 Agfa-Gevaert Heat-sensitive imaging element for making lithographic printing plates comprising polymer particles with a specific particle size
US6138568A (en) * 1997-02-07 2000-10-31 Kodak Polcyhrome Graphics Llc Planographic printing member and process for its manufacture
WO1998034796A1 (en) * 1997-02-07 1998-08-13 Kodak Polychrome Graphics Company Ltd. Planographic printing member and process for its manufacture
WO1998040213A1 (en) * 1997-03-13 1998-09-17 Kodak Polychrome Graphics, L.L.C. Method of imaging lithographic printing plates with high intensity laser
US6110645A (en) * 1997-03-13 2000-08-29 Kodak Polychrome Graphics Llc Method of imaging lithographic printing plates with high intensity laser
WO1998040212A1 (en) * 1997-03-13 1998-09-17 Kodak Polychrome Graphics, L.L.C. Lithographic printing plates with a sol-gel layer
US6136508A (en) * 1997-03-13 2000-10-24 Kodak Polychrome Graphics Llc Lithographic printing plates with a sol-gel layer
US6090524A (en) * 1997-03-13 2000-07-18 Kodak Polychrome Graphics Llc Lithographic printing plates comprising a photothermal conversion material
EP0983149B1 (en) * 1997-05-23 2003-01-08 Kodak Polychrome Graphics Company Ltd. Planographic printing
WO1998055311A1 (en) * 1997-06-03 1998-12-10 Agfa-Gevaert Naamloze Vennootschap Heat sensitive printing plate precursors
US5962188A (en) * 1997-06-24 1999-10-05 Kodak Polychrome Graphics Llc Direct write lithographic printing plates
WO1998058801A1 (en) * 1997-06-24 1998-12-30 Kodak Polychrome Graphics, L.L.C. Direct write lithographic printing plates
US6014930A (en) * 1997-07-25 2000-01-18 Kodak Polychrome Graphics Llc Single layer direct write lithographic printing plates
WO1999004974A1 (en) * 1997-07-25 1999-02-04 Kodak Polychrome Graphics Single layer direct write lithographic printing plates
US6207348B1 (en) 1997-10-14 2001-03-27 Kodak Polychrome Graphics Llc Dimensionally stable lithographic printing plates with a sol-gel layer
WO1999019144A1 (en) * 1997-10-14 1999-04-22 Kodak Polychrome Graphics Dimensionally stable lithographic printing plates with a sol-gel layer
WO1999019143A1 (en) * 1997-10-14 1999-04-22 Kodak Polychrome Graphics Improved lithographic printing plates comprising a photothermal conversion material
US6022668A (en) * 1998-01-19 2000-02-08 Kodak Polychrome Graphics Llc Positive-working direct write waterless lithographic printing members and methods of imaging and printing using same
US6085655A (en) * 1998-01-29 2000-07-11 Kodak Polychrome Graphics Llc Direct write waterless imaging member with improved ablation properties and methods of imaging and printing
WO1999038688A1 (en) * 1998-01-29 1999-08-05 Kodak Polychrome Graphics, Llc Direct write waterless imaging member with improved ablation properties and methods of imaging and printing
US6238843B1 (en) 1998-02-28 2001-05-29 Kodak Polychrome Graphics, Llc Planographic printing member and method for its preparation
US6268113B1 (en) * 1998-04-30 2001-07-31 Eastman Kodak Company Antireflection direct write lithographic printing plates
EP0953441A1 (en) * 1998-04-30 1999-11-03 Eastman Kodak Company Antireflection direct write lithographic printing plates
EP0967077A1 (en) * 1998-06-26 1999-12-29 Agfa-Gevaert N.V. A heat sensitive imaging element and a method for producing lithographic plates therewith
US6210857B1 (en) 1998-06-26 2001-04-03 Agfa-Gevaert Heat sensitive imaging element for providing a lithographic printing plate
US6455222B1 (en) 1999-03-24 2002-09-24 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor
US6653042B1 (en) 1999-06-04 2003-11-25 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor, method for producing the same, and method of lithographic printing
US6397749B1 (en) * 1999-07-26 2002-06-04 Fuji Photo Film Co., Ltd. Heat-sensitive lithographic printing plate precursor
EP1084826A1 (en) * 1999-09-17 2001-03-21 Fuji Photo Film Co., Ltd. Heat-sensitive lithographic printing plate precursor
US6852470B1 (en) 1999-09-17 2005-02-08 Fuji Photo Film Co., Ltd. Heat-sensitive lithographic printing plate precursor
US6808863B2 (en) 1999-12-12 2004-10-26 Fuji Photo Film Co., Ltd. Heat-sensitive lithographic printing plate precursor
EP1110719A3 (en) * 1999-12-22 2001-08-08 Fuji Photo Film Co., Ltd. Heat-sensitive lithographic printing plate precursor
EP1110719A2 (en) * 1999-12-22 2001-06-27 Fuji Photo Film Co., Ltd. Heat-sensitive lithographic printing plate precursor
US6447884B1 (en) 2000-03-20 2002-09-10 Kodak Polychrome Graphics Llc Low volume ablatable processless imaging member and method of use
US6458507B1 (en) 2000-03-20 2002-10-01 Kodak Polychrome Graphics Llc Planographic thermal imaging member and methods of use
US6790595B2 (en) 2000-11-21 2004-09-14 Agfa-Gevaert Processless lithographic printing plate
EP1208974A3 (en) * 2000-11-21 2003-02-12 Agfa-Gevaert Processless lithographic printing plate
EP1208974A2 (en) * 2000-11-21 2002-05-29 Agfa-Gevaert Processless lithographic printing plate
EP1226976A1 (en) * 2001-01-24 2002-07-31 Fuji Photo Film Co., Ltd. Hydrophilic polymer having silane coupling group terminal and lithographic printing plate base
EP1260361A2 (en) 2001-05-22 2002-11-27 Fuji Photo Film Co., Ltd. Method for making lithographic printing plate
EP1260361A3 (en) * 2001-05-22 2004-03-24 Fuji Photo Film Co., Ltd. Method for making lithographic printing plate
US6878503B2 (en) 2001-10-10 2005-04-12 Fuji Photo Film Co., Ltd. Heat-sensitive lithographic printing plate precursor
EP1354720A2 (en) 2002-04-15 2003-10-22 Fuji Photo Film Co., Ltd. Heat-sensitive lithographic printing plate precursor
EP1609617A1 (en) * 2004-06-21 2005-12-28 Konica Minolta Medical & Graphic Inc. Printing plate material and image formation process
WO2006026229A1 (en) * 2004-08-25 2006-03-09 Eastman Kodak Company Method and apparatus for development of lithographic printing plate precursor
US7807333B2 (en) 2004-08-25 2010-10-05 Eastman Kodak Company Method and apparatus for development of lithographic printing plate precursor
EP2109000A1 (en) 2004-09-10 2009-10-14 FUJIFILM Corporation Polymer having polymerizable group, polymerizable composition, planographic printing plate precursor, and planographic printing method using the same
EP3182204A1 (en) 2004-09-10 2017-06-21 FUJIFILM Corporation Planographic printing plate precursor using a polymerizable composition
US7608388B2 (en) * 2004-10-12 2009-10-27 Presstek, Inc. Inkjet-imageable lithographic printing members and methods of preparing and imaging them
WO2009061995A1 (en) * 2007-11-09 2009-05-14 Presstek, Inc. Lithographic imaging with printing members having hydrophilic, surfactant-containing top layers
US8198010B2 (en) 2007-11-09 2012-06-12 Presstek, Inc. Lithographic imaging with printing members having hydrophilic, surfactant-containing top layers

Also Published As

Publication number Publication date
EP0683728B1 (en) 1997-04-09
EP0683728A1 (en) 1995-11-29
JP2592225B2 (en) 1997-03-19
JPH08507727A (en) 1996-08-20
DE69402537D1 (en) 1997-05-15

Similar Documents

Publication Publication Date Title
EP0683728B1 (en) Heat mode recording material and method for making a lithographic printing plate therewith
JP3515836B2 (en) Plate material for lithographic printing and a method of making a lithographic printing plate using the same
JP2000335131A (en) Lithographic printing master plate
US6196129B1 (en) Wet lithographic printing plates
WO2007123031A1 (en) Printing plate material
JPH10193824A (en) Heat-sensitive image forming element for manufacturing lithographic printing plate having improved transfer characteristic
JP4244757B2 (en) On-press development type printing plate material distributed in the market in the form of a roll.
US6210857B1 (en) Heat sensitive imaging element for providing a lithographic printing plate
EP0960729B1 (en) A heat sensitive imaging element for providing a lithographic printing plate
US6399276B1 (en) Processless printing plate with cover layer containing compounds with cationic groups
JP2002225452A (en) Original plate for lithographic printing plate
EP1065051B1 (en) Processless printing plate with cover layer containing compounds with cationic groups
US6620573B2 (en) Processless lithographic printing plate
EP0967077B1 (en) A heat sensitive imaging element and a method for producing lithographic plates therewith
EP1065049B1 (en) Heat-sensitive imaging element with cover layer for providing a lithographic printing plate
US6555285B1 (en) Processless printing plate with low ratio of an inorganic pigment over hardener
EP1065052B1 (en) Processless printing plate with high ratio of anorganic pigment over hardener
EP1065053B1 (en) Processless printing plate with low ratio of anorganic pigment over hardener
US6576395B1 (en) Processless printing plate with high ratio of inorganic pigment over hardener in a hydrophilic layer
JP2000355178A (en) Original plate for lithographic printing
EP1208973B1 (en) Processless lithographic printing plate
JP2001039047A (en) Processless thermal printing plate having cover layer containing compound having cationic group
JP2002307855A (en) Original plat for lithographic printing plate
JP2000301846A (en) Heat sensitive recording lithographic printing plate original plate and manufacture of lithographic printing plate
EP0934824A1 (en) Heat-sensitive imaging material and method for making on-press lithographic plates requiring no separate processing

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

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

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1994905082

Country of ref document: EP

ENP Entry into the national phase

Ref country code: US

Ref document number: 1995 448583

Date of ref document: 19950606

Kind code of ref document: A

Format of ref document f/p: F

WWP Wipo information: published in national office

Ref document number: 1994905082

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1994905082

Country of ref document: EP