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
  • B41C1/1041—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by modification of the lithographic properties without removal or addition of material, e.g. by the mere generation of a lithographic pattern
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
  • B41N3/00—Preparing for use and conserving printing surfaces
  • B41N3/03—Chemical or electrical pretreatment
  • B41N3/034—Chemical or electrical pretreatment characterised by the electrochemical treatment of the aluminum support, e.g. anodisation, electro-graining; Sealing of the anodised layer; Treatment of the anodic layer with inorganic compounds; Colouring of the anodic layer

Definitions

• This invention relates to the formation of images directly from electronically composed digital sources and is particularly concerned with the formation of images on lithographic printing plate precursors. More particularly, the invention relates to lithographic printing plate precursors which incorporate an imaging layer comprising metallic silver, and a method of preparing lithographic printing plates which does not require the use of chemical treatments.
• Lithographic printing is a process of printing from surfaces which have been prepared in such a way that certain areas are capable of accepting ink (oleophilic areas), whereas other areas will not accept ink (oleophobic areas).
• the oleophilic areas form the printing areas while the oleophobic areas form the background areas.
• Plates for use in lithographic printing processes may be prepared using a photographic material that is made imagewise receptive or repellent to ink upon photo-exposure of the photographic material and subsequent chemical treatment.
• this method of preparation which is based on photographic processing techniques, involves several steps, and therefore requires a considerable amount of time, effort and expense.
• Imaging systems are also available which involve a sandwich structure which, on exposure to a heat generating infra-red laser beam, undergoes selective (imagewise) delamination and subsequent transfer of materials.
• peel-apart systems are generally used as replacements for silver halide films.
• a digital imaging technique has been described in US Patent No 4911075 whereby a so-called driographic plate which does not require dampening with an aqueous fountain solution to wet the non-image areas during printing is produced by means of a spark discharge.
• a plate precursor comprising an ink-repellent coating containing electrically conductive particles coated on a conductive substrate is used and the coating is ablatively removed from the substrate.
• the ablative spark discharge provides images having relatively poor resolution.
• Coatings which may be imaged by means of ablation with infra-red radiation have previously been proposed.
• a proofing film in which an image is formed by imagewise ablation of a coloured layer on to a receiver sheet is described in PCT Application No 90/12342.
• This system is, however, disadvantageous in requiring a physical transfer of material in the imaging step, and such methods tend to give rise to inferior image resolution.
• a driographic printing plate precursor is imaged digitally by means of an infra-red diode laser or a YAG laser, and the image is formed directly through the elimination of unwanted material.
• the technique involves exposing a plate precursor, incorporating an infra-red radiation ablatable coating covered with a transparent cover sheet, by directing the beam from an infra-red laser at sequential areas of the coating so that the coating ablates and loses its ink repellency in those areas to form an image, removing the cover sheet and ablation products, and inking the image.
• a heat mode recording material is disclosed in US Patent No 4034183 which comprises an anodised aluminium support coated with a hydrophilic layer. On imagewise exposure using a laser, the exposed areas are rendered hydrophobic, and thereby accept ink.
• Japanese patent application laid open to public inspection No 49-117102 (1974) discloses a method for producing printing plates wherein a metal is incorporated in the imaging layer of a printing plate precursor which is imaged by irradiation with a laser beam modulated by electric signals.
• the plate precursor comprises a metal base, such as aluminium, coated with a resin film, which is typically nitrocellulose, and on top of which has been provided a thin layer of copper.
• the resin and metal layers are removed in the laser-struck areas, thereby producing a printing plate.
• the disadvantage of this system is that two types of laser beam irradiation are required in order to remove firstly the copper (e.g. by means of an argon-ion laser) and then the resin (e.g. with a carbon dioxide laser); hence, the necessary equipment is expensive.
• a printing plate precursor comprising a support, typically aluminium, an anodic aluminium oxide layer, and a layer of brass, silver, graphite or, preferably, copper is exposed to a laser beam of high energy density in order to render the exposed areas hydrophilic to yield a printing plate.
• the printing plate precursor is, however, of rather low sensitivity and requires the use of a high energy laser for exposure.
• An alternative heat mode recording material for making a lithographic printing plate is disclosed in European Patent No 609941, which comprises a support having a hydrophilic surface, or provided with a hydrophilic layer, on which is coated a metallic layer, on top of which is a hydrophobic layer having a thickness of less than 50 nm.
• a lithographic printing plate may be produced from the said material by imagewise exposing to actinic radiation, thereby rendering the exposed areas hydrophilic and repellent to greasy ink.
• European Patent No 628409 discloses a heat mode recording material for making a lithographic printing plate which comprises a support and a metallic layer, on top of which is provided a hydrophilic layer having a thickness of less than 50 nm.
• a lithographic printing plate is produced by imagewise exposing the material to actinic radiation in order to render the exposed areas hydrophobic and receptive to greasy ink.
• the metallic layer functions as the hydrophobic surface in one case, and as the hydrophilic surface in the alternative case, it would be expected that such differences in hydrophilicity and oleophilicity would not be sufficiently clearly defined so as to provide a satisfactory printing surface.
• a hydrophilic layer is present, and the metallic surface functions as the oleophilic areas of the plate, image areas will necessarily be printed from the metallic surface; such an arrangement is known to be unsatisfactory, and to result in difficulties in achieving acceptable printing quality.
• WO 98/55311 teaches the presence of a transparent cover sheet or layer of material to collect ablated debris
• WO98/55308 describes a hydrophobising layer comprising a proteolytic enzyme and an oleophilising agent, this layer improving the ink-accepting properties of image areas and thereby increasing the degree of differentiation between hydrophilic and oleophilic areas.
• Laser devices for the exposure of thermally sensitive printing plates may be conveniently divided into two types:
• the printing plate is mounted on the inside of a stationary drum.
• the modulated beam from a high power IR laser usually a YAG laser
• a galvanometer mirror or rotating prism and the laser head traverses across the plate.
• the dwell time of the laser spot on the plate is typically of the order of 0.02 microseconds. Examples of such exposure devices are a Gerber Crescent C42T platesetter and an Agfa Galileo Talant platesetter.
• the printing plate is mounted on the outside of a rotating drum.
• the modulated laser beam is typically from a diode laser; a diode laser array may be used.
• the laser head traverses across the rotating drum to expose the plate, but the dwell time of the laser spot on the plate is much longer than that for the internal drum and is usually 0.5 to 20 microseconds, typically 5 microseconds.
• One example of such an exposure device is a Creo Trendsetter.
• the present inventors have found that by providing a plate precursor having a grained and anodised aluminium substrate with an anodic weight which lies within a certain specific range, it is possible to obtain a plate which does not suffer from these expected problems, thereby overcoming the prejudices resulting from the teachings of the prior art and allowing for the efficient exposure of such a recording material by means of an imaging device of the external drum type.
• a method of preparing a lithographic printing plate comprising:
• the aluminium substrate is brush grained or electrochemically grained with an alternating electric current in a bath containing mineral or organic acids, or their mixtures, to give a roughened surface with a Centre Line Average (CLA) of between 0.2 ⁇ m and 1.5 ⁇ m, preferably between 0.4 ⁇ m and 1.0 ⁇ m.
• CLA Centre Line Average
• the aluminium is electrochemically grained in a mixture of acetic acid and hydrochloric acid according to the process disclosed in British Patent No. 1598701.
• the grained aluminium is then chemically cleaned in either mineral acid or aqueous alkali to remove smut that may be present in the form of metal, metal oxides and metal hydroxides.
• Phosphoric acid, sulphuric acid or sodium hydroxide may suitably be used for this purpose.
• phosphoric acid is employed at a concentration of 50 to 250 g/l and a temperature of 40 to 50°C.
• the aluminium is electrochemically anodised with a direct electric current in a bath containing mineral or organic acids, or their mixtures, to provide an aluminium oxide film with an anodic weight of between 6.0 g/m 2 and 20.0 g/m 2 , preferably between 6.0 g/m 2 and 15.0 g/m 2 .
• the preferred anodising medium is sulphuric acid. Typical conditions involve treatment of the aluminium in 100 to 150 g/l sulphuric acid for 10 to 60 seconds at 40 to 50°C and an applied potential of 10 to 30 V.
• the said aluminium oxide film should be substantially porous, and that the pores should extend substantially from the aluminium/aluminium oxide interface to the surface of the substrate, such that in excess of 95% of the pores have a diameter which lies in the range between 5 nm and 100 nm.
• the surface of the pores may be chemically treated in order to partly or completely seal the substrate. Examples of such treatments are described in PCT patent application No. PCT/EP98/03474, a preferred means of treatment being with a solution comprising potassium hexafluorozirconate.
• an anodic layer having the specific thickness required by the present invention results in a significant reduction in the efficiency of heat dissipation from the ablatable metal layer into the aluminium substrate, without compromising the printing properties of the resulting plate. It is the ability to provide a balance between satisfying commercial requirements in terms of the exposure of heat mode recording materials of the type described, and their subsequent performance during lithographic printing operations that lies at the heart of the present invention.
• the aluminium substrate material may be laminated to other materials, such as paper or various plastics materials, in order to enhance its flexibility, whilst retaining the good dimensional stability associated with aluminium.
• the metallic layer which is applied to the grained and anodised surface of the aluminium, may comprise one or a combination of several metals, specific examples of which include copper, bismuth and brass. Most preferably, however, the metallic layer comprises a silver layer.
• the thickness of the metallic layer is preferably from 1 nm to 100 nm, most preferably from 10 nm to 50 nm.
• the metallic layer comprises a silver layer
• the most preferred method for applying the layer involves the treatment of a silver halide material according to the silver salt diffusion transfer process.
• a silver halide emulsion layer is transformed by treatment with a so-called silver halide solvent, into soluble silver complex compounds which are then allowed to diffuse into an image receiving layer and are reduced therein by means of a developing agent, generally in the presence of physical development nuclei, to form a metallic silver layer.
• Two such systems are available: a two sheet system in which a silver halide emulsion layer is provided on one element, and a physical development nuclei layer is provided on a second element, the two elements are placed in contact in the presence of developing agent(s) and silver halide solvent(s) in the presence of an alkaline processing liquid, and subsequently peeled apart to provide a metallic silver layer on the second element; and a single sheet system wherein the element is provided with a physical development nuclei layer, a silver halide emulsion layer is provided on top thereof, the element is treated with developing agent(s) and silver halide solvent(s) in the presence of an alkaline processing liquid, and the element is washed to remove spent emulsion layer and leave a metallic silver layer which is formed in the layer containing physical development nuclei.
• the diffusion transfer process may be used to apply a metallic silver layer by overall exposing a positive working silver halide emulsion layer to form a latent negative image which is then developed in contact with a physical development nuclei layer to form a metallic silver layer.
• the process may be carried out using either a single sheet or a double sheet system.
• a transparent cover sheet or a layer of material is present on the metallic layer before exposure.
• this top layer of material is water soluble and contains thermal sensitising agents as described in European patent application No. 00204272, stain-reducing agents as taught by European patent application No. 01000002, proteolytic enzymes, silver oleophilising agents, and desensitising compounds.
• Suitable enzymes for use in the above composition may include, for example, trypsin, pepsin, ficin, papain or the bacterial proteases or proteinases.
• Oleophilising compounds may be chosen from those disclosed on pages 105 to 106 of "Photographic Silver Halide Diffusion Processes" by Andre Rott and Edith Weyde, but mercapto compounds and cationic surfactants such as quaternary ammonium compounds are of particular value.
• Carbohydrates such as gum arabic, dextrin and inorganic polyphosphates such as sodium hexametaphosphate provide useful desensitising compounds in these compositions.
• the plate may be directly transferred to a printing press following exposure, without the requirement for any intermediate treatment, since the hydrophilic materials are readily removable from the silver image in the printing areas by means of aqueous washing; such washing is effectively achieved by the action of the typical aqueous fount solutions and fount-ink mixtures commonly used on printing presses, and the hydrophilic material is thereby replaced by a film of ink in image areas and fount in background, non-image areas.
• the plate may be subjected to a manual or automatic scrubbing and/or soaking treatment with an aqueous solution in order to remove any top layer; this procedure, which is described in WO 98/55309, additionally facilitates removal of any silver particles remaining in exposed areas, and enables the cosmetic appearance of the plate to be improved prior to press operations.
• the plate can be prepared for printing operations by further treatment with an aqueous composition comprising at least one oleophilising agent for the image areas and at least one compound capable of desensitising the non-image areas to ink. In this way, it is possible to ensure good ink acceptance in image areas and a high degree of hydrophilicity in background areas, thus enabling a good start-up on press to be achieved.
• the method of the present invention provides press ready plates showing high image quality, good press properties and high durability on press without the requirement for the use of costly intermediate film and developer chemistry, and the attendant inconvenience resulting from the use of these materials.
• a sheet of aluminium was degreased in a 5% w/w aqueous solution of sodium hydroxide, electrochemically grained with an alternating electric current in a mixture of acetic and hydrochloric acids according to the method disclosed in British Patent No. 1598701, cleaned with an aqueous solution of phosphoric acid and then anodised for various times with a direct electric current in 100 g/l sulphuric acid solution at 45°C.
• the sheet was rinsed with water to remove residual acid and a Carey Lea colloidal dispersion of silver stabilised with ammonium polyacrylate was applied to the grained and anodised surface to give a coating weight of 2.5 mg/m 2 of silver, and this was then further coated with a gelatino-silver chlorobromide dispersion to give a coating weight of 2 g/m 2 and a silver coating weight of 0.8 g/m 2 .
• a diffusion transfer developer comprising an aqueous solution containing 11% w/w sodium sulphite, 2% w/w hydroquinone, 0.6% w/w Phenidone (1-phenyl-3-pyrazolidone), 1% w/w sodium thiosulphate and 3% w/w 2-methylaminoethanol.
• the pH of the developer solution was adjusted to 12.8 by the addition of sodium hydroxide.
• the above plate precursor was dipped into the developer at 20 °C for 20 seconds, and then rinsed with warm water containing proteolytic enzyme to remove residual coating and leave a physically developed silver layer, with 0.5 g/m 2 silver, on the grained and anodised aluminium substrate.
• the silver layer was then coated with a solution containing sodium 1-octyl-5-mercaptotetrazole plus desensitisers as in example 2 of European patent application No. 00204272 to give a dry coat weight of 0.1 g/m 2 .
• the plate was exposed at different energies on a Creo Trendsetter external drum imagesetter.
• the exposed areas were qualitatively assessed as detailed in Table 1.
• Score Observation 0 No image visible 1 Exposed areas darker than non exposed areas 2 Exposed areas starting to turn gold in colour 3 Exposed areas gold in colour 4 Some ablation of silver in exposed areas 5 Silver completely removed in exposed areas
• the exposed plate was then wiped over with a damp cloth and the plate re-assessed.

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• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Printing Plates And Materials Therefor (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)

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Citations (3)

• 2001
  • 2001-06-22 EP EP01000249A patent/EP1270216A1/fr not_active Withdrawn
• 2002
  • 2002-06-19 JP JP2002178407A patent/JP2003034895A/ja active Pending

Patent Citations (3)

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