PLANOGRAPHIC PRINTING

Abstract: There is described a method of rendering non-ink accepting a selected ink-accepting area of a printing member of a type comprising a support, a hydrophilic layer derived from a silicate liquid in which particulate material is dispersed and an image layer, the method comprising treating the area to be rendered non-ink accepting with a hydrophilising means, suitably selected from one or more of acids and/or alkalis and/or oxidising formulations or, alternatively, said area may be rendered non-ink accepting by covering it with a non-ink accepting formulation.

Description: PLANOGRAPHIC PRINTING This invention relates to planographic , especially lithographic, printing and particularly, although not exclusively, relates to the correction of mistakes or other imperfections on printing members, for example printing plates, by rendering ink accepting areas non-ink accepting. Our co-pending patent application No. PCT/GB96/02883 describes a printing plate which comprises a support provided with a hydrophilic layer comprising a binder based on a material having Si-0 bonds in which particulate material is dispersed and an image layer over the hydrophilic layer. The Applicant has shown such a hydrophilic layer can advantageously be applied to a wide range of different support materials, for example metals such as aluminium, plastics, such as polyester and also paper. Printing plates including a hydrophilic layer as described have excellent printing properties. However, a problem has now been noted in relation to the rendering of ink accepting areas non-ink accepting as may be required to correct mistakes or other imperfections on the printing plates . It is well-known in the printing industry to remove or delete unwanted image material utilising a deletion fluid which may be applied to areas to be removed using a brush, a pen or other means. Known deletion fluids for negative plates commonly utilise a hydrogen fluoride solution in combination with an organic solvent and other additives. Hydrogen fluoride based deletion fluids generally remove image material very well. However, the applicant has noted, in relation to plastics plates comprising a hydrophilic layer of the type described above, that although most or all of an unwanted image area to which a known deletion fluid is applied is rendered non-ink accepting, there is often an area associated with and/or close to the unwanted image area which should be non-ink accepting but is found to be ink accepting. Consequently, such an area accepts ink during printing and leads to imperfections in printed material. The inadequacies of hydrogen fluoride based deletion fluids in relation to hydrophilic layers of the type described have, to the applicant's knowledge, been unappreciated in the past and, furthermore, the reasons for the apparent inadequate deletion of unwanted image areas using hydrogen fluoride based deletion fluids have not been investigated. This invention is based on an appreciation of the existence of a problem with commercially-available hydrogen fluoride based deletion fluids and, additionally, on the discovery of the reasons for the problem. More particularly, it has been discovered that commercially- available hydrogen fluoride deletion fluids attack the aforesaid hydrophilic layer at a greater rate than that at which they attack the image layer and, consequently, the hydrophilic layer is removed in localised regions contacted by the deletion fluid. Such localized regions may be cosmetically undesirable (since they imply a defective hydrophilic layer); and they may be undesirable from a performance perspective since they may be less hydrophilic and/or have a different ink-water balance compared to other regions of the plate and/or they may be more prone to wear. According to the invention, there is provided a method of rendering non-ink accepting a selected ink accepting area of a printing member of a type comprising a support, a hydrophilic layer which includes a material having Si-0 bonds and an image layer, the method comprising contacting said area with a means (hereinafter "said hydrophilising means") which renders said area non- ink accepting at a greater rate than that at which it can remove said hydrophilic layer. Said hydrophilic layer may be removed by said hydrophilising means at a rate of less than 0.15 μm.s '1 , suitably less than 0.1 μm.s "1 , preferably less than 0.05 μm.s "1 , more preferably less than 0.02 μm.s "1 . Said ink-accepting area may be rendered non-ink accepting within 3 minutes, suitably 2 minutes, preferably lh minutes, more preferably within 1 minute, especially within 30 seconds or less of the first contact with said hydrophilising means. The rate of rendering of said ink-accepting area non- ink accepting may be at least 5 times, preferably at least 10 times, more preferably at least 20 times, especially at least 30 times the rate of removal of said hydrophilic layer. In a first embodiment, contact with said hydrophilising means renders said ink accepting area non- ink accepting by removing said area. Said ink-accepting area may be removed at a rate of greater than 0.005 gm "2 s " ', preferably greater than 0.01 gm "2 s " 'more preferably greater than 0.05 gm "2 s " '. The thickness of said ink-accepting area may be at least 0.4 μm, preferably at least 0.8 μm, more preferably at least about 1 μm. Said thickness of said ink-accepting area may be less than 10 μm, suitably less than 8 μm, preferably less than 6 μm, more preferably less than 4 μm, especially less than 2 μm or less. Preferably, in the method, substantially the whole thickness of said ink-accepting area is removed, thereby to reveal an underlying layer which is non-ink accepting and which is suitably said hydrophilic layer. Said hydrophilising means may include one or more of acids and/or alkalis and/or oxidising formulations. Preferred acids include strong acids, for example inorganic acids such as sulphuric or nitric; weak inorganic acids, for example phospho-acids such as orthophosphoric; and organic acids for example carboxylic acids such as acetic and acrylic. Solutions comprising greater than 60%, preferably 70%, more preferably 80%, especially 90% of a said acid may be used. An especially preferred acid is sulphuric acid. Preferred alkalis include sodium hydroxide, potassium hydroxide and silicates such as sodium silicate. Preferred oxidizing formulations may include nitrites such as sodium nitrite; nitrates such as aluminium or potassium nitrate; halogen-based oxidizers for example per acids such as perchloric acid, perhalates such as periodates and perchlorates ; hydrogen peroxide; transition metal oxidizing agents such as potassium permanganate, ferric chloride and chromium VI oxide. Said hydrophilising means may include means for softening said hydrophilic layer. Said hydrophilising means may include one or more solvents . Suitable solvents may include one or more of water; acids, suitably of the type described above; and organic solvents, especially alcohols such as C,- 3 alcohols and/or alkoxyalcohols , such as 2-butoxyethanol , cyclohexanone, N-methylpyrrolidone, gamma butyrolactone, DMSO and benzylalcohol. Said hydrophilising means may include a thickener. Components of said hydrophilising means may be applied together or may be applied one after the other. Especially preferred hydrophilising means may include one or more of sulphuric acid, hydrogen peroxide, nitrates, transition metal oxidising agents, potassium hydroxide and a silicate especially sodium silicate. In a second embodiment, contact with said hydrophilising means renders said ink-accepting area non- ink accepting by covering said area. In this case, said hydrophilising means may comprise any material or materials which can be bonded to said image layer and which is/are non-ink accepting. Said hydrophilising means may comprise a first material which is applied directly to said ink-accepting area and a second material which is arranged over said first material. For example, said first material may be provided to aid adhesion of said second material to the ink-accepting area. Said hydrophilising means of said second embodiment may include one or more materials selected from a silicate material; a silicone based material; a hydrophilic polymeric material, especially an organic material such as gelatin, PVA or PVP; or a sol or a gel material. The aforesaid hydrophilising means are collectively referred to hereinafter as "binder means". Said hydrophilising means preferably comprises a fluid which is transformed to a non-fluid state after contact with said area. For example, said fluid may be transformed into a film after contact. Said hydrophilising means may include a plurality of layers of material. Said hydrophilic layer of said printing plate which includes Si-0 bonds may have an average thickness of less than 100 μm, suitably less than 50 μm, preferably less than 20 μm, more preferably less than 10 μm, especially less than 5 μm. In some cases said hydrophilic layer may have an average thickness of less than 3 μm. Said hydrophilic layer may have an average thickness of greater than 0.1 μm, suitably greater than 0.3 μm, preferably greater than 0.5 μm, more preferably greater than 1 μm. The Ra of the hydrophilic layer may be measured using a Talysurf Plus fitted with a 112/2564-430 head, supplied by Rank Taylor Hobson Inc. of Leicester, U.K. The Ra may be at least 0.2 μm, suitably at least 0.25 μm, preferably at least 0.3 μm, more preferably at least 0.35 μm, especially at least 0.4 μm. The Ra may be less than 1.5 μm, suitably less than 1 μm, preferably less than 0.8 μm, more preferably less than 0.7 μm, especially less than 0.6 μm, most preferably less than 0.5 μm. Said hydrophilic layer may include 1 to 20 g of material per metre squared of substrate. Preferably said layer includes 3 to 20 g, more preferably 5 to 18 g, of material per metre squared of substrate. Most preferably, said layer includes 8 to 16 g of material per metre squared. Said hydrophilic layer may include a binder material. Said binder material preferably includes said material having Si-0 bonds. Said binder material may be a component of a polymeric material which includes Si-0 bonds. Said polymeric material may include -Si-O-Si-, especially -Si-O-Si-0-, moieties. At least 50 wt%, suitably at least 60 wt%, preferably at least 70 wt%, more preferably at least 80 wt%, especially at least 90 wt% of said binder material is made up of a polymeric material having Si-0 bonds as described. Preferably, said binder material consists essentially of a polymeric material having Si-0 bonds as described. Said binder material may make up at least 5 wt%, preferably at least 10 wt%, more preferably at least 15 wt%, especially at least 20 wt% of said hydrophilic layer. Said binder material may make up less than 50 wt%, preferably less than 40 wt%, more preferably less than 30 wt%, especially less than 25 wt%, of said hydrophilic layer. Said binder material may be derived or derivable from a silicate material for example water glasses, metasilicates , orthosilicates , sesquisilicates and modified silicates such as borosilicate and phosphosilicate . Said binder material is preferably derived or derivable from a silicate solution. Said binder material preferably includes less than 10 wt%, preferably less than 5 wt%, more preferably less than 1 wt%, especially substantially no, organic material, for example polymeric organic material. Preferably, particulate material is provided in said hydrophilic layer, for example by being dispersed in the binder material thereof. Suitably 30 to 85 wt%, preferably 40 to 80 wt%, more preferably 50 to 80 wt%, especially 60 to 80 wt%, of said hydrophilic layer is composed of said particulate material. Said particulate material may be organic or inorganic. Organic particulate materials may be provided by latexes. Inorganic particulate materials may be selected from alumina, silica, silicon carbide, zinc sulphide, zirconia, barium sulphate, talcs, clays (e.g. kaolin), lithopone and titanium oxide. Said particulate material may comprise a first particulate material. Said first material may have a hardness of greater than 8 Modified Mohs (on a scale of 0 to 15), preferably greater than 9 and, more preferably, greater than 10 Modified Mohs. Said first material may comprise generally spherical particles. Alternatively, said material may comprise flattened particles or platelets. Said first material may have a mean particle size of at least 0.1 μm, preferably at least 0.5 μm and, more preferably, at least 1.0 μm. Said first material may have a mean particle size of less than 200 μm, suitably less than 100 μm, preferably less than 45 μm, more preferably less than 20 μm, especially less than 10 μm, and, most preferably, less than 5 μm. The particle size distribution for 95% of particles of the first material may be in the range 0.01 to 150 μm, preferably in the range 0.05 to 75 μm, more preferably in the range 0.05 to 30 μm. Said first material preferably comprises an inorganic material. Said first material preferably comprises alumina which term includes Al 2 0-f and hydrates thereof, for example Al 2 0 3 .3H 2 0. Preferably, said material is A1 2 0 3 . Said hydrophilic layer may include at least 10 wt%, suitably at least 20 wt%, preferably at least 25 wt%, more preferably at least 30 wt%, especially at least 35 wt% of said first particulate material. Said hydrophilic layer may include less than 80 wt%, suitably less than 70 wt%, preferably less than 60 wt%, more preferably less than 50 wt%, especially less than 40 wt% of said first particulate material. The ratio of the wt% of said first particulate material to binder material may be in the range 0.5 to 2 , preferably in the range 1 to 2 , more preferably in the range 1.4 to 1.8. Said particulate material may comprise a second particulate material. Said second material may have a mean particle size of at least 0.001 μm, suitably at least 0.005 μm, preferably at least 0.01 μm, more preferably at least 0.05 μm, especially at least 0.1 μm. Said second material may have a mean particle size of less than 200 μm, suitably less than 100 μm, preferably less than 50 μm, more preferably less than 10 μm, especially less than 1 μm, most preferably less than 0.5 μm. Said second material is preferably a pigment. Said second material is preferably inorganic. Said second material is preferably titanium dioxide. Said first and second particulate materials preferably define a multimodal, for example a bimodal particle size distribution. The ratio of the wt% of said first particulate material to said second particulate material may be in the range 0.3 to 3, preferably 0.5 to 2, more preferably 0.75 to 1.33, especially about 1 to 1. Said hydrophilic layer may include at least 10 wt%, suitably at least 20 wt%, preferably at least 25 wt%, more preferably at least 30 wt%, especially at least 35 wt% of said second particulate material. Said hydrophilic layer may include less than 80 wt%, suitably less than 70 wt%, preferably less than 60 wt%, more preferably less than 50 wt%, especially less than 40 wt % of said second particulate material. The ratio of the wt% of said second particulate material to binder material may be in the range 0.5 to 2, preferably in the range 1 to 2 , more preferably in the range 1.4 to 1.8. Said hydrophilic layer may include one or more additional materials for improving its adhesion to a support, especially a plastics support. A preferred additional material is organic and is preferably polymeric. Resins are preferred. The hydrophilising means of said second embodiment described above may include additives to adjust its properties. For example, it may include materials for aiding deposition and/or abrasion resistance and/or for aiding the masking of the selected ink-accepting area and/or for aiding the hardening or curing or drying of the binder means. Said hydrophilising means may include first and/or second particulate materials which may be as described in any statement herein. Preferably, said binder material of said hydrophilic layer and said binder means of said hydrophilising means include some or all of the same components. In a preferred embodiment, said binder material of said hydrophilic layer is derived from a silicate material and said binder means of said hydrophilising means is also derived from the same silicate material. At least 50 wt%, suitably at least 60 wt%, preferably at least 70 wt%, more preferably at least 80 wt%, especially at least 90 wt% of the composition of the hydrophilic layer is the same as that of the hydrophilising means. Said support may comprise a metal layer. Preferred metals include aluminium, zinc and titanium, with aluminium being especially preferred. Said support may comprise an alloy of the aforesaid metals. Other alloys that may be used include brass and steel, for example stainless steel. Said support may comprise a non-metal layer. Preferred non-metal layers include layers of plastics, paper or the like. Preferred plastics include polyester, especially polyethylene terephthlate. Said support may include one or a plurality of layers. Where the support comprises a plurality of layers, it may comprise a plastics, paper or textile layer and another layer. Said other layer may be a metal layer, suitably of a type described above. In this case, said support may comprise a metal to plastics or paper laminate; or metal may be applied by other means to plastics or paper, for example by sputtering or the like. The image layer may comprise any known photosensitive material whether arranged to form a positive or negative plate. Examples of photosensitive materials include diazonium materials, polymers which undergo depolymerisation or addition photopolymerisation and silver halide gelatin assemblies. Examples of suitable materials are disclosed in GB 1 592 281, GB 2 031 442, GB 2 069 164, GB 2 080 964, GB 2 109 573, EP 0 377 589, US 4 268 609 and US 4 567 131. Said image layer is preferably arranged to form a negative plate. According to a second aspect of the present invention, there is provided a method of preparing a printing member for printing, the method comprising rendering non-ink accepting selected ink accepting areas of the member. The method preferably includes the step of causing printable information to become associated with a substrate, for example by information-wise exposing a non- exposed printing member, and inspecting said member to determine said selected ink-accepting areas to be rendered non-ink accepting. Said printing member preferably includes a hydrophilic layer prepared by contacting a support with a fluid comprising a silicate liquid in which particulate material is dispersed. Said silicate liquid may comprise a solution of any soluble silicate including compounds often referred to as water glasses, metasilicates , orthosilicates and sesquisilicates. Said silicate liquid may comprise a solution of a modified silicate for example a borosilicate or phosphosilicate. Said silicate liquid may comprise one or, more preferably only one, metal or non-metal silicate. A metal silicate may be an alkali metal silicate. A non-metal silicate may be quaternary ammonium silicate. Said silicate liquid may be formed from silicate wherein the ratio of the number of moles of Si species, for example Si0 2 , to the number of moles of cationic, for example metal species is in the range 0.25 to 10, preferably in the range 0.25 to about 6, more preferably in the range 0.5 to 4. Said silicate liquid is preferably alkali metal silicate. In this case, the ratio of the number of moles of Si0 2 to the number of moles of M 2 0 in said silicate, where M represents an alkali metal may be at least 0.25, suitably at least 0.5, preferably at least 1, more preferably at least 1.5. Especially preferred is the case wherein said ratio is at least 2.5. Said ratio may be less than 6, preferably less than 5 and more preferably less than 4. Preferred alkali metal silicates include lithium, sodium and potassium silicates, with lithium and/or sodium silicate being especially preferred. A silicate liquid comprising only sodium silicate is most preferred. Said fluid may comprise 2 to 30 wt% of silicate (e.g. dissolved sodium silicate solid), preferably 5 to 20 wt%, more preferably 8 to 16 wt%. The liquid may be prepared using 10 to 60 wt%, preferably 30 to 50 wt%, more preferably 35 to 45 wt% of a silicate solution which comprises 30 to 40 wt% silicate. Said fluid may include 5 to 60 wt% of particulate material. Preferably, the fluid includes 10 to 50 wt%, more preferably 15 to 45 wt%, especially 20 to 40 wt% of particulate material. The ratio of the weight of silicate to the weight of particulate material in the fluid is preferably in the range 0.1 to 2 and, more preferably, in the range 0.1 to 1. Especially preferred is the case wherein the ratio is in the range 0.2 to 0.6. Said fluid may include more than 20 wt%, preferably more than 30 wt%, more preferably more than 40 wt%, especially more than 45 wt% water (including water included in said silicate liquid) . Said fluid may include less than 80 wt%, preferably less than 70 wt%, more preferably less than 65 wt%, especially less than about 60 wt% water. Where the fluid comprises a silicate and said particulate material comprises a first material and a second material as described, the ratio of the wt% of silicate (e.g. dissolved sodium silicate solid) to the wt% of said first material may be in the range 0.25 to 4, preferably in the range 0.5 to 1.5 and more preferably about 1. Similarly, the ratio of the wt% of silicate to the wt% of said second material may be in the range 0.25 to 4, preferably in the range 0.5 to 1.5 and more preferably about 1. The ratio of the wt% of first material to the wt% of second material may be in the range 0.5 to 2, preferably in the range 0.75 to 1.5, more preferably about 1 to 1. Said particulate material may include a third material which is preferably adapted to lower the pH of the fluid. Said third material may be a colloid, suitably colloidal silica or an inorganic salt, suitably a phosphate, with aluminium phosphate being preferred. Preferably less than 30wt%, more preferably less than 20wt%, especially less than 10wt% of the total particulate material in said fluid is comprised by said third material . The pH of said fluid may be greater than 9.0, is preferably greater than 9.5 and, more preferably, greater than 10.0. Especially preferred is the case wherein the pH is greater than 10.5. The pH is suitably controlled so that the silicate remains in solution and does not form a gel. A gel is generally formed when the pH of a silicate solution falls below pH9. The pH of said fluid is preferably less than 14, more preferably less than 13. The fluid may include other compounds for adjusting its properties. For example, the fluid may include one or more surfactants. Said fluid may include 0 to 1 wt% of surfactant(s) . A suitable class of surfactants comprises anionic sulphates or sulphonates. The fluid may include viscosity builders for adjusting the viscosity of the liquid. Said fluid may include 0 to 10 wt%, preferably 0 to 5 wt% of viscosity builder(s). Also, the fluid may include dispersants for dispersing the inorganic particulate material throughout the fluid. Said fluid may include 0 to 2 wt% of dispersant ( s ) . A suitable dispersant may be sodium hexametaphosphate. Said fluid may have a viscosity of less than 100 centipoise when measured at 20°C and a shear rate of 200s " ' using a Mettler Rheomat 180 Viscometer incorporating a double gap measuring geometry. Preferably, said viscosity is less than 50 centipoise, more preferably less than 30 centipoise when measured as aforesaid. Especially preferred is the case wherein the viscosity is less than 20 centipoise. Said fluid may be applied to said support by any suitable means which is preferably non-electrochemical. Said fluid may be applied to both sides of said support in order to form hydrophilic layers on both sides. A support with such a layer on both sides may be used to prepare a double-sided lithographic plate. Alternatively, if such a support is used for a single-sided plate, the side of the plate which does not carry an image layer may be protected by the hydrophilic layer. Said fluid is preferably applied to only one surface of said support. In the method, water is suitably removed from the fluid after application. It is believed that, when a silicate liquid is used, this results in the silicate polymerising, and thereby binding said particulate materials in position. According to a third aspect of the present invention, there is provided a printing member including non-ink accepting areas prepared according to said first aspect. According to a fourth aspect, there is provided any novel hydrophilising means for rendering non-ink accepting a selected ink-accepting area of a printing member per se. According to a fifth aspect, there is provided the use of a hydrophilising means as described herein for rendering non-ink accepting a selected ink-accepting area of a printing member. According to a sixth aspect, there is provided a method of printing using a printing member as described herein. According to a seventh aspect, there is provided a method of rendering non-ink accepting a selected ink- accepting area of a printing member, the method comprising contacting said selected area with a means (herein "said hydrophilising means") which renders said area non-ink accepting by covering said area. Any feature of any aspect of any invention or embodiment described herein may be combined with any feature of any other aspect of any invention or embodiment described herein. The invention will now be described by way of example . A Preparation of lithographic printing plate. Example 1 Step 1 Preparation of Aluminium A 0.2 mm gauge aluminium alloy sheet of designation AA1050 was cut to a size of 459 mm by 525 mm. The sheet was then immersed face up in a solution of sodium hydroxide dissolved in distilled water (lOOg/l) at ambient temperature for 60 seconds and thoroughly rinsed with water. Step 2 Preparation of coating formulation The following reagents are used in the preparation: - Sodium silicate solution having a ratio Si0 2 : Na 2 0 in the range 3.17 to 3.45 (average about 3.3); a composition of 27.1 - 28.1 wt% Si0 2 , 8.4 - 8.8 wt% Na 2 0, with the balance being water; and a density of about 75 Twaddel (°Tw) , equivalent to 39.5 Baume (°Be) and a specific gravity of 1.375. - Deionised water having a resistivity of 5 Mohm.cm - Al 2 0 3 powder comprising alumina (99.6%) in the shape of hexagonal platelets. The mean particle size is 3 μm. The powder has a hardness of 9 Moh (on a 0 - 10 hardness scale). - Anatase titanium dioxide having a mean primary particle size of 0.2 μm. Deionised water (150g; 40 wt%) was added to a 250ml beaker and sheared using a Silverson high shear mixer. Titanium dioxide powder (53.29g; 14.21 wt%) was then added in portions over a period of four minutes with the shearing continuing. Then, alumina powder (53.29g; 14.21wt%) was added in portions over a period of four minutes with the shearing continuing. On completion of the addition, sodium silicate solution (118.43g; 31.58 wt%) was added with shearing for a further three minutes. The viscosity of the liquid was found to be about 10 centipoise when measured at 20°C and a shear rate of 200s' using a Mettler Rheomat 180 Viscometer incorporating a double gap measuring geometry. Step 3 Application of coating formulation The coating formulation prepared in Step 2 was coated onto the aluminium sheet prepared in Step 1 using a rotating Meyer bar coater (designation K303) to give a 12 μm wet film thickness. Step 4 Drying the formulation The coated sheet prepared in Step 3 was placed in an oven at 130°C for 80 seconds. The plate was then removed from the oven and allowed to cool to ambient temperature. The Ra of the sheet was 0.45 μm measured using a Hommelmeter T2000 having an LV-50 measuring head. Step 5 Post-drying treatment The dried sheet prepared in Step 4 was immersed in aluminium sulphate (0.1M) for thirty seconds. The sheet was then spray rinsed for about twenty seconds using tap water and fan dried. Step 6 Application of light sensitive coating A printing plate was produced from the sheet prepared in Step 5 by coating to a dry coating weight of lgm "2 using a Meyer bar, a negative light sensitive material comprising Ronacoat RO300 photopolymer (89 wt%) and Ronacoat RO301 sensitizer (9 wt%) as major components. The light sensitive material was dried at 100°C for 60 seconds . B Exposure and development of lithographic plate Example 2 The plate of Example 1, step 6 was exposed to 190 exposure units (equivalent to 80 mJcm "1 ) and developed using a developer comprising sodium metasilicate as main active ingredient sold under the Trade Mark GOLDSTAR by Horsell Anitec. C Post-development deletion of unwanted image areas using deletion fluids The ability of various fluids or combinations of fluids described below in Examples 3 to 10 and comparative Examples Cl and C2 to remove (or delete) a small (1.5 cm by 1.5 cm) image area from plates prepared as described in Example 2 was assessed by applying the fluids to the area of image to be removed using suitable means, optionally agitating the area, wiping the area with cotton wool, rinsing the area with tap water, assessing the area, inking in the area using RAPIDINK (Trade Mark) applied using damp cotton wool, and visually assessing whether the area inked in or not thereby to indicate whether the particular fluids successfully removed the image area. Example 3 12.5 wt% of a sodium silicate solution comprising Si0 2 (27 wt%) and sodium oxide (14 wt%) was mixed with alcoholic potassium hydroxide which comprises potassium hydroxide (25 wt%) in methanol. 3-4 drops of the solution were applied to an area of a plate to be deleted and then the plate was placed in an oven at 130°C for 80 seconds. On removal from the oven, the plate was rinsed with water. Example 4 A thin layer of a solvent comprising water/2- butoxyethanol (50/50) was brushed onto the surface of the image area and allowed to penetrate the image area so that it softened. Thereafter, a few drops of concentrated sulphuric acid (98%) were applied using a pipette, followed by mixing using the pipette. After 60 seconds, the area was washed as described above. Example 5 A solution (green in colour) comprising potassium permanganate (5 wt%) in concentrated sulphuric acid (98% concentrated) was applied as a thin layer. Example 7 Hydrogen peroxide (30% w/v) was applied to the image area and then concentrated sulphuric acid (98%) was added dropwise. Example 8 Ammonium nitrate (5 wt%) in concentrated sulphuric acid (98%) was applied to the area. Example 9 Ammonium fluoride (5 wt%) in methanol was applied to the area. Then, concentrated sulphuric acid (98%) was added dropwise to the area with mixing. Example 10 Hydrogen peroxide at a temperature of about 70°C was applied to the area. Example Cl A commercially available deletion fluid for negative plates was applied to the area, the fluid including 40% hydrofluoric acid (23.5 wt%), a PVP thickener (15.2 wt%) and water (28.3 wt%) and tetrahydrofuran (33 wt%) as solvents. Example C2 A commercially available deletion fluid for negative plates was applied to the area, the fluid including 40 % hydrofluoric acid (8.8 wt%), a PVP thickener (44.5 wt%), a dye and water (2.2 wt%) and cyclohexanone (44.5 wt%) as solvents. Results Table 1 below lists, for each example, the results of a visual assessment of the image area after application of the fluid but before inking; a visual assessment of an area around the image area after application of the fluid; and whether or not the image area inks in after application of the fluid. Discussion Whereas each of Examples 3 to 10 and Cl and C2 were capable of deleting the image area to greater or lesser extents to render them less ink-accepting, the fluid of examples Cl and C2 also severely attacked the hydrophilic layer of the substrate around the image area so that it was removed. This resulted in the exposure of bare aluminium which was cosmetically unacceptable and/or was ink-accepting and/or has an ink-water balance which is different from the rest of the plate and/or is expected to have reduced wear resistance. Thus, the fluids of examples Cl and C2 cannot be used for deletion from plates having a hydrophilic layer of the type described. D Post-development covering of unwanted image areas Example 11 The coating formulation described in Example 1, Step 2 was applied using a brush to a small (1.5 cm by 1.5 cm) image area on a plate prepared as described in Example 2. In one example, the coating formulation was cured in an oven at 130°C for 80 seconds; in another example, the coating was fan dried for 50 seconds at 50°C. Results The coating formulation covered the image area and rendered it non-ink accepting. The reader's attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps -are mutually exclusive. Each feature disclosed in this specification (including any accompanying claims, abstract and drawings), may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features. The invention is not restricted to the details of the foregoing embodiment ( s ) . The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

Claims: CLAIMS 1. A method of rendering non-ink accepting a selected ink accepting area of a printing member of a type comprising a support, a hydrophilic layer which includes a material having Si-0 bonds and an image layer, the method comprising contacting said area with a means (hereinafter "said hydrophilising means") which renders said area non-ink accepting at a greater rate than that at which it can remove said hydrophilic layer. 2. A method according to Claim 1, wherein said hydrophilic layer is removed by said hydrophilising means at a rate of less than 0.15 μm.s "1 . 3. A method according to Claim 1 to Claim 2, wherein said ink accepting area is rendered non-ink accepting within three minutes . 4. A method according to any preceding claim, wherein the rate of rendering of said ink-accepting area non-ink accepting is at least 5 times the rate of removal of said hydrophilic layer. 5. A method according to any preceding claim, wherein contact with said hydrophilising means renders said ink- accepting area non-ink accepting by removing said area at a rate of greater than 0.005 gm "2 s " ' . 6. A method according to any preceding claim, wherein said hydrophilising means is selected from one or more of acids, alkalis and oxidising formulations. 7. A method according to any preceding claim, wherein said hydrophilising means is selected from strong inorganic acids, weak inorganic acids, organic acids, hydroxides, silicates, nitrites, nitrates, per acids, per halates, hydrogen peroxide and transition metal oxidising agents. 8. A method according to any preceding claim, wherein said hydrophilising means includes means for softening said hydrophilic layer. 9. A method according to any preceding claim, wherein said hydrophilising means includes one or more solvents. 10. A method according to any of Claims 1 to 4, wherein contact with said hydrophilising means renders said ink accepting area non-ink accepting by covering said area. 11. A method according to any preceding claim, wherein said material having Si-0 bonds is a component of a binder material which is polymeric. 12. A method according to Claim 11, wherein said binder material makes up at least 5 wt% of said hydrophilic layer. 13. A method according to Claim 11 or Claim 12, wherein said binder material is derived or derivable from a silicate material. 14. A method according to any preceding claim, wherein particulate material is provided in said hydrophilic layer. 15. A method according to Claim 14, wherein said particulate material comprises a first particulate material having a mean particle size of at least 0.1 μm and less than 200 μm and a second particulate material having a mean particle size of at least 0.001 μm and less than 200 μm. 16. A method of preparing a printing member for printing wherein the printing member preferably includes a hydrophilic layer prepared by contacting a support with a fluid comprising a silicate liquid in which particulate material is dispersed, the method comprising rendering non-ink accepting selected ink accepting areas of the member. 17. A printing member including non-ink accepting areas prepared according to any of Claims 1 to 15. 18. A novel hydrophilising means for rendering non-ink accepting a selected ink accepting area of a printing member of the type comprising a support, a hydrophilic layer which includes a material having Si-0 bonds and an image layer. 19. The use of a hydrophilising means as described in any of Claims 1 to 15 for rendering non-ink accepting a selected ink-accepting area of a printing member. 20. A method of printing using a printing member as described in any of Claims 1 to 16. 21. A method of rendering non-ink accepting a selected ink-accepting area of a printing member, the method comprising contacting said selected area with a means (herein "said hydrophilising means") which renders said area non-ink accepting by covering said area.

Inventors: BHAMBRA HARJIT SINGH, DICKINSON KELVIN, ORGAN ROBERT MICHAEL, BHAMBRA, HARJIT, SINGH, DICKINSON, KELVIN, ORGAN, ROBERT, MICHAEL
Applicants: BHAMBRA HARJIT SINGH, DICKINSON KELVIN, HORSELL GRAPHIC IND LTD, ORGAN ROBERT MICHAEL, BHAMBRA, HARJIT, SINGH, DICKINSON, KELVIN, HORSELL GRAPHIC INDUSTRIES LIMITED, ORGAN, ROBERT, MICHAEL
Application year: 1998
Main classification: B41N3
IPC codes: B41N3, G03F7