EP0595179B1 - Verfahren zur Herstellung einer Aluminiumfolie zur Verwendung als Träger in lithographischen Druckplatten - Google Patents

Verfahren zur Herstellung einer Aluminiumfolie zur Verwendung als Träger in lithographischen Druckplatten Download PDF

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Publication number
EP0595179B1
EP0595179B1 EP19930116973 EP93116973A EP0595179B1 EP 0595179 B1 EP0595179 B1 EP 0595179B1 EP 19930116973 EP19930116973 EP 19930116973 EP 93116973 A EP93116973 A EP 93116973A EP 0595179 B1 EP0595179 B1 EP 0595179B1
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Prior art keywords
brush
acid
bristles
light
sho
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EP19930116973
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French (fr)
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EP0595179A1 (de
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Kazushige c/o FUJI PHOTO FILM CO. LTD. Takizawa
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • 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
    • B41N3/04—Graining or abrasion by mechanical means

Definitions

  • the present invention relates to a method for preparing an aluminum substrate for lithographic printing plate comprising a brush graining step which comprises surface roughening an aluminium plate with at least two kinds of brushes whose bristles have different diameters.
  • the lithographic printing method is a printing method which makes use of the fact that water is not substantially miscible with oils.
  • a region which receives water and repels an oil-based ink hereunder referred to as "non-image portion”
  • image portion a region which repels water and receives am oil-based ink
  • the aluminum substrate is used, in the lithographic printing plate, for carrying non-image portions on the surface thereof and, therefore, must satisfy various requirements of properties which are in conflict with one another, such as excellent hydrophilicity and water retention characteristics as well as excellent adhesion to a light-sensitive layer subsequently applied thereto. If the substrate has low hydrophilicity, an ink is adhered to non-image portions of the resulting lithographic printing plate during printing operations and this results in the so-called background contamination. On the other hand, the use of a substrate having poor water retention characteristics leads to the phenomenon of ink-spreading in shadowed portions unless a large amount of dampening water is used. Thus, so-called water tolerance of the resulting lithographic printing plate becomes narrow.
  • fine irregularities are in general formed on the surface of an aluminum plate by a surface-graining treatment.
  • surface-graining treatments these have been known, for instance, mechanical surface-graining methods such as ball-graining, brush-graining, wire-graining and blast-graining; electrolytic surface-graining methods such as a method comprising electrolytically etching an aluminum plate in an electrolyte containing hydrochloric acid and/or nitric acid; and combined surface-roughening methods comprising combinations of mechanical surface-roughening treatments and electrolytic surface-roughening treatments as disclosed in U.S. Patent No. 4,476,006.
  • the irregularities of the roughened surface should be shallow and smooth to some extent to improve the hydrophilicity thereof to a preferred level, but this results in a decrease in the amount of water retained and impairs the adhesion to a light-sensitive layer subsequently applied, while if deeper irregularities are formed on the aluminum substrate, the water retention characteristics thereof is increased, or the water tolerance becomes wider and the adhesion to a light-sensitive layer is improved, but this results in background contamination during printing operations.
  • Document US-A-2 637 929 discloses a method as indicated above wherein two kinds of brushes are utilised which have bristles having diameters ranging from 0.20 to 0.23 mm and a second bristle diameter of 0.13 mm, in order to perform a brush graining step during preparing aluminium substrates for lithographic printing plates.
  • the brushes disclosed therein are of a rolled type.
  • an object of the present invention is to provide a substrate for presensitized plate for use in making a lithographic printing plate (hereinafter referred to as "PS plate") which has high water retention characteristics and accordingly, does not cause any collapse of shadowed portions even when the amount of dampening water is reduced, which is hardly contaminated and which is excellent in the adhesion to a light-sensitive layer subsequently applied thereto.
  • PS plate lithographic printing plate
  • the above object is achieved by a method of preparing an aluminium substrate for lithographic printing plate as indicated above wherein the two kinds of brushes comprise a first brush whose bristles have a diameter of not less than 0.57 mm and not more than 1.20 mm and a second brush whose bristles have a diameter of not less than 0.10 mm and not more than 0.34 mm and wherein the brush used in the final brush graining processes is the second brush.
  • Fig. 1 is a schematic diagram for explaining an embodiment of the method of the present invention.
  • the aluminum plate used in the invention is selected from the group consisting of pure aluminum plate, aluminum alloy plates comprising aluminum as main component and trace amounts of other elements as well as plastic films laminated with an aluminum film or on which aluminum is vapor-deposited.
  • the trace elements included in the aluminum alloys are silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth. nickel and/or titanium.
  • the amount of these trace elements present in the aluminum alloy is not more than 10% by weight.
  • Preferred aluminum plate used in the invention is a pure aluminum plate, but it is presently difficult to obtain completely pure aluminum plate from the viewpoint of refining techniques. Therefore, an aluminum plate containing other elements in a trace amount may be used.
  • the aluminum plates usable in the invention are not restricted to those having specific compositions, may be those commonly known and used in this art and thus may appropriately be selected from, for instance, JIS A 1050, JIS A 1100, JIS A 3103 and JIS A 3005.
  • the aluminum plate used in the invention has a thickness in the order of about 0.1 to 0.6 mm.
  • the aluminum plate is, if desired, degreased by treating with, for instance, a surfactant solution, an organic solvent or an alkaline aqueous solution for the removal of the rolling oils present on the surface thereof prior to the brush-graining treatment, but the degreasing treatment may be omitted. Subsequently, the aluminum plate is subjected to the brush-graining using at least two kinds of brushes having different bristle-diameters while supplying a slurry of an abrasive to the surface of the plate.
  • a brush initially used in the process is called a first brush and a brush used in the final brush-graining process is called a second brush.
  • an aluminum plate 1 is sandwiched between a roll-like brush (2 or 4) and two support rolls (5 and 6; or 7 and 8) as will be seen from Fig. 1.
  • these two support rolls in each set are arranged in such a manner that the shortest distance between the outer surfaces of the support rolls is smaller than the outer diameter of each corresponding roll-like brush.
  • the brush preferably used in the invention may be those each comprising a roll-like base and bristles of a brush material such as nylon, polypropylene, animal hairs or steel wire having a uniform length which are implanted in and uniformly distributed on the base; those each comprising a base having small holes and bundles of bristles implanted in the holes of the base; or channel roll type ones.
  • a brush material such as nylon, polypropylene, animal hairs or steel wire having a uniform length which are implanted in and uniformly distributed on the base
  • those each comprising a base having small holes and bundles of bristles implanted in the holes of the base or channel roll type ones.
  • particularly preferred are those comprising nylon bristles having a bristle length preferably ranging from 10 to 200 mm as determined after the implantation.
  • the diameter of the roll-like base preferably ranges from 20 to 60 cm, and more preferably from 30 to 50 cm.
  • the density of bristles to be implanted in a brush roll preferably ranges from 30 to 1000 bristles/cm 2 and more preferably 50 to 300 bristles/cm 2 .
  • the preferred diameter of the bristles is not less than 0.57 mm and not more than 1.20 mm, more preferably not less than 0.64 mm and not more than 1.00 mm for the first brush; and not less than 0.10 mm and not more than 0.34 mm, more preferably not less than 0.20 mm and not more than 0.30 mm for the second brush.
  • the resulting aluminum substrate does not ensure water retention characteristics sufficient for preventing any collapse of shadowed portions when the amount of dampening water is reduced during printing operations.
  • the second brush comprising fine bristles having a diameter of not more than 0.34 mm is used for smoothening the sharp convexes on the grained surface formed through the graining by the first brush comprising thick bristles having a diameter of not less than 0.57 mm and for preventing the occurrence of background contamination during printing. For this reason, if the bristles of the second brush have a diameter of greater than 0.34 mm, a desired effect of sufficiently preventing background contamination cannot be ensured.
  • the number of the first brushes used in the invention is not restricted to a specific number, but preferably 1 to 10 and more preferably 1 to 6 brushes.
  • the number of the second brushes to be used in the invention is not likewise be limited to a specific number, but preferably 1 to 3 and more preferably 1 to 2 brushes.
  • the rotational number of the brush roll can arbitrarily be selected so that it falls within the range of from 200 rpm to 2000 rpm.
  • the support rolls used have rubbery or metallic surfaces and excellent straightness.
  • the brush rolls are preferably rotated in the direction along the conveying direction of the aluminum plate as shown in Fig. 1, but some of the brush rolls may be rotated in the direction opposite to the conveying direction of the aluminum plate if a plurality of brush rolls are used.
  • a substrate having all of the desired properties such as hydrophilicity, water retention characteristics and adhesion to a light-sensitive layer subsequently applied thereto to form a light-sensitive material such as a PS plate can be obtained by first surface-roughening the plate with the foregoing brush having thick bristles and then treating it with a brush having fine bristles according to the present invention.
  • the present invention can ensure various effects.
  • the aluminum substrate prepared by the invention shows wide water tolerance and can provide a lithographic printing plate which hardly causes background contamination since the plate does not cause any collapse of shadowed portions when the amount of dampening water used is reduced.
  • the plate never suffers from any deterioration of the adhesion to the subsequently applied light-sensitive layer.
  • the present invention ensures a dot gain-reducing effect during printing operations, although the mechanism thereof has not yet been clearly elucidated.
  • the slurry of an abrasive herein used preferably comprises an abrasive having a particle size ranging from 15 to 35 ⁇ m such as quartz sand, alumina powder, volcanic ash, carborundum and emery dispersed in water in a concentration preferably ranging from 10 to 70% by weight.
  • the substrate is preferably treated in such a manner that the center line average roughness (Ra: surface roughness) of the substrate prepared by the method of the invention falls within the range of from 0.5 to 1.0 ⁇ m (the tracer 10 ⁇ mR).
  • the aluminum plate After brush-graining the aluminum plate in the foregoing manner, it is preferred to chemically etch the surface of the plate.
  • the chemical etching serves to remove the abrasive particles and aluminum scraps cutting into the surface of the brush-grained aluminum plate.
  • the aluminum plate After the etching, the aluminum plate is electrochemically surface-roughened and, as a result, these treatments ensures the formation of a uniformly and effectively surface-roughened aluminum plate.
  • the method comprises immersing an aluminum plate in a solution capable of dissolving aluminum, such as an aqueous solution of an acid or a base.
  • a solution capable of dissolving aluminum such as an aqueous solution of an acid or a base.
  • the acids usable in this etching treatment are sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid and hydrochloric acid
  • the bases include sodium hydroxide, potassium hydroxide, sodium tertiary phosphate, potassium tertiary phosphate, sodium aluminate, sodium metasilicate and sodium carbonate.
  • preferred are aqueous solutions of bases because of high etching rates.
  • the chemical etching treatment is generally carried out in an aqueous solution having an acid or alkali concentration ranging from 0.05 to 40% by weight at an etching temperature ranging from 40 to 100°C for 5 to 300 seconds.
  • the aluminum plate is preferably subjected to the so-called desmutting treatment in which the plate is treated with phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixture thereof.
  • the aluminum plate is, if desired, electrochemically surface-roughened.
  • the concentration of hydrochloric acid or nitric acid in an electrolyte used preferably ranges from 0.01 to 3% by weight and more preferably 0.05 to 2.5% by weight.
  • the electrolyte may further comprise anticorrosive agents (or stabilizers) and/or grain-uniformizing agents such as nitrates, chlorides, monoamines, diamines, aldehydes, phosphoric acid, chromic acid, boric acid and aluminum oxalate. Further the electrolyte may comprise a proper amount (1 to 10 g/l) of aluminum ions.
  • the electrochemical surface-roughening treatment is in general performed at an electrolyte temperature ranging from 10 to 60°C.
  • the alternating current used in this treatment may be those having rectangular waveform, trapezoidal wave form or sinusoidal wave form so far as the polarity thereof is alternatively exchanged.
  • the alternating current may be single phase and three phase alternating currents which are usually used as commercial alternating currents.
  • the electrochemical surface-roughening treatment is desirably carried out at a current density ranging from 5 to 100 A/dm 2 for 10 to 300 seconds.
  • the aluminum plate thus surface-roughened is, if desired, desmutted by treating with a 10 to 50% hot sulfuric acid solution (40 to 60 °C) or a dilute alkali solution (such as an aqueous solution of sodium hydroxide). If the desmutting treatment is carried out with an alkali solution, the plate is subsequently immersed in an acid solution (such as nitric acid or sulfuric acid) for washing and neutralizing the plate.
  • a 10 to 50% hot sulfuric acid solution 40 to 60 °C
  • a dilute alkali solution such as an aqueous solution of sodium hydroxide
  • Electrolytes used in the anodization of the aluminum plate is not restricted to specific ones so far as they can form porous anodized layers and in general may be, for instance, sulfuric acid, phosphoric acid, oxalic acid, chromic acid or mixture thereof. The concentrations of these electrolyte can appropriately be determined depending on the kinds thereof.
  • the conditions for the anodization vary depending on the kinds of electrolytes selected and, therefore, cannot unconditionally be determined, but in general the anodization is suitably carried out at an electrolyte concentration ranging from 1 to 80% by weight, an anodization temperature ranging from 5 to 70 °C, a current density ranging from 1 to 60 A/dm 2 , an electric voltage ranging from 1 to 100 V for an electrolyzation time ranging from 10 seconds to 5 minutes.
  • the aluminum plate is usually treated by a direct current, but an alternating current may likewise be used in this anodization method.
  • This electrolyzation treatment is performed at a sulfuric acid concentration ranging from 5 to 30% and a temperature ranging from 20 to 60 °C for 5 to 250 seconds.
  • the electrolyte preferably comprises aluminum ions.
  • the current density used in this treatment preferably ranges from 1 to 20 A/dm 2 .
  • the aluminum plate is treated at a phosphoric acid concentration ranging from 5 to 50%, a temperature ranging from 30 to 60 °C, a current density ranging from 1 to 15 A/dm 2 for an anodization time ranging from 10 to 300 seconds.
  • the amount of the anodized layer thus formed is preferably not less than 1.0 g/m 2 and more preferably 2.0 to 6.0 g/m 2 . This is because if it is less than 1.0 g/m 2 , the resulting aluminum substrate provides a lithographic printing plate having insufficient printing durability, the non-image portions of the lithographic printing plate are easily damaged and this often leads to so-called "contamination due to defects", i.e., adhesion of an ink to these defects during printing operations.
  • the surface of the aluminum plate is, if necessary, subjected to a hydrophilization treatment.
  • the hydrophilization used in the invention may be treatments with alkali metal silicates (such as aqueous sodium silicate solution) as disclosed in U.S. Patent Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734. According to these methods, the aluminum substrate is treated by immersing or electrolyzing in an aqueous sodium silicate solution.
  • Preferred aluminum substrates further include those subjected to a sealing treatment after surface-graining and anodization treatments.
  • the sealing treatment comprises immersing the aluminum plate in hot water or a hot aqueous solution containing an inorganic salt or organic salt or exposing the plate to water vapor.
  • Organic compounds used in the organic underlying layer are, for instance, carboxymethyl cellulose, dextrin, gum arabic, phosphonic acids carrying amino groups such as 2-aminoethyl phosphonic acid, organic phosphonic acids which may have substituents such as phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, organic phosphoric acids which may have substituents such as phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid, organic phosphinic acids which may have substituents such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and ⁇
  • the organic layer can be formed by a method comprising the steps of applying a solution of the foregoing organic compound dissolved in a solvent selected from water, an organic solvent such as methanol, ethanol, methyl ethyl ketone or a mixture thereof to the hydrophilized aluminum plate and then drying or a method comprising the steps of dipping the hydrophilized aluminum plate in a solution of the foregoing organic compound dissolved in a solvent selected from water, an organic solvent such as methanol, ethanol, methyl ethyl ketone or a mixture thereof to adsorb the compound on the plate, then washing with, for instance, water and drying.
  • a coating solution containing the organic compound in a concentration ranging from 0.005 to 10% by weight can be applied by a variety of methods such as coating with a bar coater, a whirler and a spray device or curtain coating, while in the latter method, the concentration of the solution ranges from 0.01 to 20% by weight, preferably 0.05 to 5% by weight and the dipping temperature ranges from 20 to 90 °C, preferably 25 to 50 °C and the dipping time ranges from 0.1 second to 20 minutes, preferably 2 seconds to one minute.
  • the pH value of the solutions herein used may be adjusted to 1 to 12 with a basic substance such as ammonia, triethylamine or potassium hydroxide, or an acidic substance such as hydrochloric acid or phosphoric acid.
  • a yellow dye can be added for the improvement of tone reproduction of the resulting PS plates.
  • the coated amount (weighed after drying) of the organic underlying layer suitably ranges from 2 to 200 mg/m 2 , preferably 5 to 100 mg/m 2 . This is because, if the coated amount is less than 2 mg/m 2 , the printing durability of the resulting lithographic printing plate is insufficient, while if it exceeds 200 mg/m 2 , sufficient printing durability cannot likewise be obtained.
  • a coating layer of an organic polymer (hereinafter referred to as "back coat layer”) may be applied onto the back face of the PS plate which makes use of the substrate prepared according to the present invention to prevent the formation of defects observed when the PS plates are put in stack.
  • the principal component for the back coat layer is at least one member selected from the group consisting of saturated copolymerized polyester resins, phenoxy resins, polyvinyl acetal resins and copolymerized vinylidene chloride resins, having glass transition points of not less than 20 °C.
  • the saturated copolymerized polyester resin comprises repeating units derived from a dicarboxylic acid and a diol.
  • the dicarboxylic acid units of the polyesters used in the invention are, for instance, those derived from aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, tetrabromophthalic acid and tetrachlorophthalic acid; and saturated aliphatic dicarboxylic acids such as adipic acid, azelaic acid, succinic acid, oxalic acid, suberic acid, sebacic acid, malonic acid and 1,4-cyclohexanedicarboxylic acid.
  • the back coat layers may, if desired, comprise dyes and/or pigments for coloring the layer; agents for improving the adhesion to an aluminum substrate such as silane coupling agents, diazo resins comprising diazonium salts, organic phosphonic acids, organic phosphoric acids and cationic polymers; and agents usually used as labricating agents such as waxes, higher fatty acids, higher fatty acid amides, silicone compounds derived from dimethylsiloxane, modified dimethylsiloxanes and polyethylene powder.
  • agents for improving the adhesion to an aluminum substrate such as silane coupling agents, diazo resins comprising diazonium salts, organic phosphonic acids, organic phosphoric acids and cationic polymers
  • agents usually used as labricating agents such as waxes, higher fatty acids, higher fatty acid amides, silicone compounds derived from dimethylsiloxane, modified dimethylsiloxanes and polyethylene powder.
  • the thickness of the back coat layer is basically selected such that a light-sensitive layer subsequently applied thereto is not damaged even if any interleaf is not used and preferably ranges from 0.01 to 8 ⁇ m. If it is less than 0.01 ⁇ m, the formation of scratch marks cannot be prevented when the resulting PS plates are handled while putting them in stack. On the other hand, if the thickness thereof exceeds 8 ⁇ m, the back coat layer gets swollen through the action of agents used in the environment surrounding the resulting printing plate during printing operation and thus suffers from change in the thickness thereof. This sometimes leads to change in the printing pressure depending on the position and hence deterioration of printing properties of the plate.
  • the back coat layer may be applied onto the back face of an aluminum substrate by a variety of methods.
  • the back coat layer may be prepared by a method comprising applying, onto the aluminum substrate, the foregoing components for the back coat layer in the form of a solution or an emulsion dissolved or dispersed in a proper solvent and then drying; a method comprising forming the foregoing components into a film and adhering the film, to the aluminum substrate, through the use of an adhesive or application of heat; and a method comprising extruding the components into a molten film through a melt extruder and then adhering the molten film to the substrate with the method comprising applying the components in the form of a solution and then drying being most preferred since it can ensure the coated amount (thickness) defined above.
  • a light-sensitive layer of a known light-sensitive composition is applied onto the aluminum plate which is prepared by the method detailed above and has a hydrophilized surface to give a PS plate.
  • light-sensitive compositions usable herein include positive-working light-sensitive compositions mainly comprising o-quinonediazide compounds; and negative-working light-sensitive compositions mainly comprising photopolymerizable compounds which mainly comprise diazonium salts, alkali-soluble diazonium salts and/or unsaturated double bond-containing monomers and cinnamic acid or dimethylmaleimido group-containing photocrosslinkable compounds as light-sensitive substances.
  • examples of the photopolymerizable compositions mainly comprising unsaturated double bond-containing monomers are those comprising addition polymerizable unsaturated compounds each having at least two terminal ethylene groups and photopolymerization initiators as disclosed in U.S. Patent Nos. 2,760,863 and 3,060,023 and J.P. KOKAI No. Sho 59-53836.
  • Examples of negative-working light-sensitive compositions comprising dimethylmaleimido group-containing photocrosslinkable compounds are light-sensitive substances as disclosed in J.P. KOKAI Nos. Sho 52-988, Hei 3-288853 and Hei 4-25845 and European Patent No. 0410654.
  • o-naphthoquinonediazide compounds used in positive-working light-sensitive compositions are preferably esters of 1,2-diazonaphthoquinone sulfonic acid with pyrogallol ⁇ acetone resins as disclosed in J.P. KOKOKU No. Sho 43-28403.
  • Other preferred examples of o-quinonediazide compounds are esters of 1,2-diazonaphthoquinone-5-sulfonic acid with phenol-formaldehyde resins as disclosed in U.S. Patent Nos.
  • Particularly preferred o-naphthoquinonediazide compounds are those obtained through the reaction of polyhydroxy compounds having molecular weight of not more than 1,000 with 1,2-diazonaphthoquinonesulfonic acid.
  • Specific examples thereof are those disclosed in, for instance, J.P. KOKAI Nos. Sho 51-139402, Sho 58-150948, Sho 58-203434, Sho 59-165053, Sho 60-121445, Sho 60-134235, Sho 60-163043, Sho 61-118744, Sho 62-10645, Sho 62-10646, Sho 62-153950, Sho 62-178562 and Sho 64-76047; and U.S. Patent Nos. 3,102,809; 3,126,281; 3,130,047; 3,148,983; 3,184,310; 3,188,210 and 4,639,406.
  • o-naphthoquinonediazide compounds are preferably obtained through reactions of polyhydroxy compounds with 1,2-diazonaphthoquinonesulfonic acid chloride in an amount ranging from 0.2 to 1.2 eq, more preferably 0.3 to 1.0 eq per unit equivalent of hydroxyl group of the former.
  • the 1,2-diazonaphthoquinonesulfonic acid chloride may be either 1,2-diazonaphthoquinone-5-sulfonic acid chloride or 1,2-diazonaphthoquinone-4-sulfonic acid chloride.
  • the resulting o-naphthoquinonediazide compound is a mixture of products variously differing in the positions of 1,2-diazonaphthoquinonesulfonate groups and the amounts thereof introduced, but preferred are those having a rate of the compound whose hydroxyl groups are all converted into 1,2-diazonaphthoquinonesulfonic acid esters (content of the completely esterified compound) of not less than 5 mole%, more preferably 20 to 99 mole%.
  • the light-sensitive composition used in the invention preferably comprises the positive-working light-sensitive compounds (inclusive of the foregoing combination) in an amount ranging from 10 to 50% by weight and more preferably 15 to 40% by weight.
  • the positive-working light-sensitive composition may comprise only o-quinonediazide compounds such as those listed above, but preferebly the o-quinonediazide compounds are used in combination with an alkaline water-soluble resin as a binder.
  • alkaline water-soluble novolak resins such as phenol-formaldehyde resins and cresol-formaldehyde resins, for instance, o-, m- and p-cresol-formaldehyde resins, m-/p- mixed cresol-formaldehyde resins and phenol-mixed cresol (m-/p-/o- or m-/p- or m-/o-)-formaldehyde resins.
  • Suitable binders may further include copolymers generally having a molecular weight of 10,000 to 200,000 and having structural units derived from the following monomers (1) to (13).
  • the foregoing monomers may likewise be copolymerized with other monomers copolymerizable therewith and the copolymers of the monomers listed above can be modified with, for instance, glycidyl (meth)acrylate.
  • the copolymers usable in the invention are not limited to these specific examples.
  • the foregoing copolymers preferably comprises moieties derived from the unsaturated carboxylic acids (3) listed above and the acid value thereof preferably ranges from 0 to 10 meq/g, more preferably 0.2 to 5.0 meq/g.
  • preferred molecular weight of these copolymers ranges from 10,000 to 100,000.
  • copolymers may be used, in the light-sensitive composition, in combination with polyvinyl butyral resin, polyurethane resin, polyamide resin and/or epoxy resin.
  • alkali-soluble polymers may be used alone or in combination and the amount thereof is not more than 80% by weight on the basis of the total weight of the light-sensitive composition.
  • alkali-soluble polymers may preferably be used in combination with a condensate of a phenol having an alkyl group carrying 3 to 8 carbon atoms as a substituent with formaldehyde such as t-butylphenol-formaldehyde resin or octylphenol-formaldehyde resin for the improvement of the ink receptivity of the resulting images.
  • formaldehyde such as t-butylphenol-formaldehyde resin or octylphenol-formaldehyde resin
  • the light-sensitive composition used in the invention preferably comprises, for the improvement of sensitivity, cyclic acid anhydrides, phenols and/or organic acids.
  • cyclic acid anhydrides examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endoxy- ⁇ 4 -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, ⁇ -phenylmaleic anhydride, succinic anhydride and pyromellitic anhydride.
  • phenols include, for instance, bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,3,4-trihydroxybenzophenone, 4-hydroxy-benzophenone, 2,4,4'-trihydroxybenzophenone, 4,4',4''-trihydroxytriphenylmethane and 4,4',3'',4''-tetrahydroxy-3,5,3',5'-tetramethyltriphenylmethane.
  • organic acids are, for instance, sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphinic acid, phosphoric acid esters and carboxylic acids as disclosed in J.P. KOKAI Nos.
  • Sho 60-88942 and Hei 2-96755 and specific examples thereof are p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethylsulfuric acid, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluylic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4-cyclohexene-2,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid and ascorbic acid.
  • the content of the foregoing cyclic acid anhydrides, phenols and/or organic acid in the light-sensitive composition preferably ranges from 0.05 to 15% by weight and more preferably 0.1 to 5% by weight on the basis of the total weight of the composition.
  • the light-sensitive composition used in the invention may further comprise, for extending the development latitude, non-ionic surfactants as disclosed in J.P. KOKAI No. Sho 62-251740 and/or amphoteric surfactants as disclosed in J.P. KOKAI No. Sho 59-121044 and Hei 4-13149.
  • non-ionic surfactants are sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearyl monoglyceride, polyoxyethylene sorbitan monooleate and polyoxyethylene nonylphenyl ether.
  • amphoteric surfactants are alkyl di(aminoethyl)glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethyl imidazolinium betaine and Amorgen K (trade name of an N-tetradecyl-N,N-betaine type surfactant, available from Dai-Ichi Kogyo Seiyaku Co., Ltd.) and Rebon 15 (trade name of an alkyl imidazoline type one available from Sanyo Chemical Industries, Ltd.).
  • the content of the foregoing non-ionic and/or amphoteric surfactants in the light-sensitive composition preferably ranges from 0.05 to 15% by weight and more preferably 0.1 to 5% by weight on the basis of the total weight of the composition.
  • the light-sensitive composition used in the invention may comprise a printing out agent for obtaining a visible image immediately after exposure to light and/or a dye or pigment for coloring images.
  • a representative example of the printing out agent is a combination of a compound capable of releasing an acid through exposure to light (photolytically acid-releasing agent) with a salt-forming organic dye, for instance, a combination of o-naphthoquinonediazide-4-sulfonic acid halide with a salt-forming organic dye as disclosed in J.P. KOKAI Nos. Sho 50-36209 and Sho 53-8128; and a combination of a trihalomethyl compound with a salt-forming organic dye as disclosed in J.P. KOKAI Nos. Sho 53-36223, Sho 54-74728, Sho 60-3626, Sho 61-143748, Sho 61-151644 and Sho 63-58440.
  • Such trihalomethyl compounds include oxadiazole and triazine type compounds and both of these are excellent in stability with time and can provide clear printed out images.
  • dyes may also be used instead of or together with the foregoing salt-forming organic dyes as the agents for coloring images.
  • Preferred dyes inclusive of the salt-forming organic dyes are, for instance, oil-soluble and basic dyes. Specific examples thereof are Oil Yellow #101 and #103, Oil Pink #312, Oil Green BG, Oil Blue BOS and #603, Oil Black BY, BS and T-505 (they are all available from Orient Chemical Industries, Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI 42555), Methyl Violet (CI 42535), Ethyl Violet, Rhodamine B (CI 145170B), Malachite Green (CI 42000) and Methylene Blue (CI 52015). Particularly preferred are those disclosed in J.P. KOKAI No. Sho 62-293247.
  • the light-sensitive composition used in the invention is dissolved in a solvent in which the foregoing components are soluble and then applied onto the aluminum substrate treated by the method of the invention.
  • the light-sensitive composition is dissolved and dispersed in the solvent in a concentration ranging from 2 to 50% by weight (solid content), applied to the substrate and then dried to give a light-sensitive material.
  • the coated amount of the light-sensitive composition layer (light-sensitive layer) applied onto the substrate varies depending on the applications of the resulting plate, but preferably ranges from 0.3 to 4.0 g/m 2 (weighed after drying). As the coated amount decreases, the quantity of light required for imagewise exposure is reduced, but the strength of the film is lowered. On the other hand, as it is increased, the quantity of light required for imagewise exposure is increased, but the strength of the light-sensitive film is increased and if the product is used as a PS plate, it can provide a lithographic printing plate capable of providing a large number of acceptable copies (i.e., high printing durability).
  • the light-sensitive composition may comprise a surfactant such as a fluorine atom-containing surfactant as disclosed in J.P. KOKAI No. Sho 62-170950 for improving the coating properties thereof.
  • the amount thereof to be added preferably ranges from 0.001 to 1.0% by weight, more preferably 0.005 to 0.5% by weight on the basis of the total weight of the composition.
  • Light-sensitive layers for negative-working PS plates usable in the invention are, for instance, those prepared from light-sensitive compositions comprising light-sensitive diazo compounds, photopolymerizable light-sensitive compositions and photocrosslinkable light-sensitive compositions.
  • photohardenable light-sensitive copying materials comprising light-sensitive diazo compounds will be detailed below by way of example.
  • the light-sensitive diazo compounds used herein are, for instance, diazo resins obtained through condensation of aromatic diazonium salts with reactive carbonyl group-containing organic condensation agents, in particular, aldehydes such as formaldehyde and acetaldehyde or acetals in acidic mediums, with a condensate of p-diazodiphenylamine with formaldehyde being most typical example thereof.
  • aldehydes such as formaldehyde and acetaldehyde or acetals in acidic mediums
  • a condensate of p-diazodiphenylamine with formaldehyde being most typical example thereof.
  • Preferably used light-sensitive diazo compounds further include, for instance, co-condensed diazo compounds of aromatic diazonium salts with substituted aromatic compounds free of diazonium groups as disclosed in J.P. KOKOKU No. Sho 49-48001, with co-condensed diazo compounds of aromatic diazonium salts with aromatic compounds substituted with alkali-soluble groups such as carboxyl and/or hydroxyl groups being particularly preferred.
  • Preferably used examples thereof further include light-sensitive diazo compounds obtained through condensation of alkali-soluble group-containing reactive carbonyl compounds with aromatic diazonium salts as disclosed in J.P. KOKAI Nos. Hei 4-18559, Hei 4-190361 and Hei 4-172353.
  • diazo resins in which the counter anions of the diazonium salts are those derived from inorganic anions such as mineral acids, e.g., hydrochloric acid, hydrobromic acid, sulfuric acid and phosphoric acid or complex salts thereof with zinc chloride.
  • mineral acids e.g., hydrochloric acid, hydrobromic acid, sulfuric acid and phosphoric acid or complex salts thereof with zinc chloride.
  • diazo resins which are substantially insoluble in water and soluble in organic solvents.
  • Such preferred diazo resins are detailed in J.P. KOKOKU No. Sho 47-1167 and U.S. Patent No. 3,300,309.
  • preferred diazo resins further include, for instance, those having counter anions derived from halogenated Lewis acids such as tetrafluoroboric acid, hexafluorophosphoric acid and perhalogenic acids such as perchloric acid and periodic acid as disclosed in J.P. KOKAI Nos. Sho 54-98613 and Sho 56-121031.
  • halogenated Lewis acids such as tetrafluoroboric acid, hexafluorophosphoric acid and perhalogenic acids such as perchloric acid and periodic acid as disclosed in J.P. KOKAI Nos. Sho 54-98613 and Sho 56-121031.
  • the amount of the light-sensitive diazo compounds usually ranges from 5 to 50% by weight and preferably 8 to 20% by weight on the basis of the total weight of the light-sensitive layer.
  • the light-sensitive diazo compounds used in the invention are preferably used in combination with alkaline water-soluble or swellable lipophilic polymeric materials as binders.
  • lipophilic polymeric compounds are the same copolymers listed above in connection with the positive-working light-sensitive compositions and having repeating units derived from the monomers (1) to (13) and molecular weights generally ranging from 10,000 to 200,000 as well as those having repeating units derived from the following monomers (14) and (15):
  • binders also include copolymers obtained by copolymerization of the foregoing monomers which are further modified with glycidyl (meth)acrylate.
  • the present invention is not restricted to these specific binders.
  • the foregoing copolymers preferably comprises moieties derived from the unsaturated carboxylic acids (3) listed above and the acid value thereof preferably ranges from 0 to 10 meq/g, more preferably 0.2 to 5.0 meq/g.
  • preferred molecular weight of these copolymers ranges from 10,000 to 100,000.
  • copolymers may be used, in the light-sensitive composition, in combination with polyvinyl butyral resin, polyurethane resin, polyamide resin and/or epoxy resin.
  • polyvinyl butyral resin polyurethane resin
  • polyamide resin polyamide resin
  • epoxy resin polyamide resin
  • binders are novolak type resins, phenol-modified xylene resins, polyhydroxystyrene, halogenated polyhydroxystyrene and alkali-soluble resins having phenolic hydroxyl groups as disclosed in J.P. KOKAI No. Sho 51-43711.
  • alkali-soluble polymers may be used alone or in combination and the amount thereof ranges from 40 to 95% by weight based on the total weight of the solid content of the light-sensitive composition.
  • the light-sensitive composition used in the invention may optionally comprise a plasticizer for improving the flexibility and wear resistance of the coated light-sensitive layer.
  • a plasticizer for improving the flexibility and wear resistance of the coated light-sensitive layer.
  • Specific examples thereof are butyl phthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate and oligomers and polymers of (meth)acrylic acid, with tricresyl phosphate being particularly preferred.
  • the light-sensitive composition used in the invention may comprise, for the improvement of stability with time, additives such as phosphoric acid, phosphonic acid, citric acid, oxalic acid, dipicolinic acid, benzenesulfonic acid, naphthalenesulfonic acid, sulfosalicylic acid, 4-methoxy-2-hydroxybenzo-phenone-5-sulfonic acid and tartric acid.
  • additives such as phosphoric acid, phosphonic acid, citric acid, oxalic acid, dipicolinic acid, benzenesulfonic acid, naphthalenesulfonic acid, sulfosalicylic acid, 4-methoxy-2-hydroxybenzo-phenone-5-sulfonic acid and tartric acid.
  • the light-sensitive composition used in the invention may comprise a dyestuff as a printing out agent for obtaining a visible image immediately after imagewise exposure to light and/or as an agent for coloring images such as a dye or pigment.
  • the dyestuffs are preferably those which change color tone through the reaction with free radicals or acids.
  • Specific examples thereof which are initially colored and converted into colorless ones, or which cause color change are triphenylmethane, diphenylmethane, oxazine, xanthene, iminonaphthoquinone, azomethine or anthraquinone type dyes such as Victoria Pure Blue (available from Hodogaya Chemical Co., Ltd.), Oil Yellow #101 and #103, Oil Pink #312, Oil Red, Oil Green BG, Oil Blue BOS and #603, Oil Black BY, BS and T-505 (they are all available from Orient Chemical Industries, Co., Ltd.), Patent Pure Blue (available from Sumitomo Mikuni Chemical Co., Ltd.), Crystal Violet (CI 42555), Methyl Violet (CI 42535), Ethyl Violet, Rhodamine B (CI 145170B), Malachite Green (CI 42000), Methylene Blue (CI 52015
  • dyestuffs which are initially colorless and converted into colored ones are leuco dyes and primary and secondary arylamine type dyes such as triphenylamine, diphenylamine, o-chloroaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p,p'-bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p,p',p''-tris-dimethylaminotriphenylmethane, p,p'-bis-dimethylaminodiphenylmethylimine, p,p',p''-triamino-o-me thyltriphenylmethane, p,p'-bis-dimethylaminodiphenyl-4-anilinonaphthylmethane and p,p',p''-triaminotriphenylmethane
  • Particularly preferred dyestuffs are triphenylmethane and diphenylmethane type ones, with triphenylmethane type dyestuffs being more preferred and Victoria Pure Blue BOH being particularly preferred.
  • the foregoing dyestuffs are in general used in the light-sensitive composition in an amount ranging from about 0.5 to 10% by weight and preferably about 1 to 5% by weight on the basis of the total weight of the composition.
  • the light-sensitive compositions may further comprise cyclic acid anhydrides, phenols, organic acids and/or higher alcohols for the improvement of developability thereof. These additives are the same as those listed above in connection with the positive-working light-sensitive composition and used in the same amount defined above.
  • the light-sensitive composition used in the invention is dissolved in a solvent in which the foregoing components are soluble and then applied onto the aluminum substrate treated above according to the method of the present invention.
  • the light-sensitive composition is dissolved and dispersed in the solvent in a concentration ranging from 2 to 50% by weight (solid content), applied to the aluminum substrate and then dried to give a negative-working light-sensitive material.
  • the coated amount of the light-sensitive composition layer (light-sensitive layer) applied onto the substrate varies depending on the applications of the resulting plate, but preferably ranges from 0.3 to 4.0 g/m 2 (weighed after drying). As the coated amount decreases, the quantity of light required for imagewise exposure is reduced, but the strength of the film is lowered. On the other hand, as it is increased, the quantity of light required for imagewise exposure is increased, but the strength of the light-sensitive film is increased and if the product is used as a PS plate, it can provide a lithographic printing plate capable of providing a large number of acceptable copies (i.e., high printing durability).
  • the light-sensitive composition may comprise a surfactant for improving the coating properties thereof like the positive-working light-sensitive composition discussed above.
  • the back coat layer to be applied onto the back face of a substrate may be formed prior to the formation of the light-sensitive layer on the surface thereof, or vice versa, or they can simultaneously be applied to the substrate.
  • a mat layer is applied onto the surface of the light-sensitive layer thus formed on the substrate to reduce the time required for evacuation during contact exposure using a vacuum printing frame and to prevent the formation of an indistinct image during printing.
  • the average diameter of projections formed on the mat layer is preferably not more than 100 ⁇ m. This is because if it exceeds the upper limit, the contact area between the light-sensitive layer and the back coat layer excessively increases when the PS plates are stored while putting them in stack increases, the slipping properties thereof is thus reduced and accordingly, scratch marks are easily formed on both surfaces of the light-sensitive and mat layers.
  • the average height of the projections is preferably not more than 10 ⁇ m and more preferably 2 to 8 ⁇ m. If the average height thereof exceeds the upper limit, the formation of fineline images becomes difficult, the dot density in highlight portions decreases and the tone reproduction is also impaired.
  • the resulting PS plate is in sufficient in the adhesion, under vacuum, to an original film and suffers from a problem of the formation of an indistinct image during printing.
  • the amount of the coated mat layer preferably ranges from 5 to 200 mg/m 2 and more preferably 20 to 150 mg/m 2 . If the amount thereof exceeds the upper limit, scratch marks are easily formed on the surfaces of the light-sensitive layer and the mat layer since the contact area between the light-sensitive layer and the back coat layer increases upon putting them in stack, while if it is less than the lower limit, the resulting PS plate is insufficient in the adhesion, under vacuum, to an original transparency during printing.
  • the PS plate thus prepared is imagewise exposed, through an original transparency, to actinic light from a light source such as a carbon arc lamp, a mercury lamp, a metal halide lamp, a xenon lamp or a tungsten lamp and then developed.
  • a light source such as a carbon arc lamp, a mercury lamp, a metal halide lamp, a xenon lamp or a tungsten lamp and then developed.
  • Alkali aqueous solutions commonly known can be used as developers and replenishers for these PS plates.
  • the alkaline agents used in the developer and replenisher compositions include inorganic alkaline agents such as sodium silicate, potassium silicate, sodium tertiary phosphate, potassium tertiary phosphate, ammonium tertiary phosphate, sodium secondary phosphate, potassium secondary phosphate, ammonium secondary phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide; and organic alkaline agents such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanol
  • these alkaline agents may be employed alone or in combination.
  • those preferred as developers for, in particular, positive-working PS plates are aqueous solutions of silicates such as sodium silicate and potassium silicate. This is because the developing ability of the developer can be controlled by adjusting the ratio of the silicon oxide SiO 2 to the alkali metal oxide M 2 O which are components of the silicate (in general expressed in terms of the molar ratio:[SiO 2 ]/[M 2 O]) and the concentration of the silicate.
  • the activity of the replenisher increases and the amount thereof to be supplemented can be saved by reducing the molar ratio: [SiO 2 ]/[M 2 O] of the alkali metal silicate. Therefore, the alkali metal silicate solution is preferably used as a developer and this results in a reduction of the running cost and the amount of waste liquor.
  • the increase in the activity of the developer leads to dissolution of aluminum from the substrate of the PS plate and that insolubles are correspondingly formed in the developer.
  • a developer system having a high activity there can preferably be used, for instance, a combination of a developer having a high activity and comprising an aqueous solution of an alkali metal silicate which has a molar ratio: SiO 2 /M 2 O of 0.7 to 1.5 and an SiO 2 content of 1.0 to 4.0% by weight and a replenisher comprising an aqueous solution of an alkali metal silicate which has a molar ratio: SiO 2 /M 2 O of 0.3 to 1.0 and an SiO 2 content of 0.5 to 4.0% by weight.
  • the developer and replenisher used in the invention for the development of the positive-working and negative-working PS plates may optionally comprise various kinds of surfactants and/or organic solvents for promoting or suppressing development, for dispersing insoluble substances formed during development and for improving the ink receptivity of the image portions of the resulting lithographic printing plate.
  • surfactants preferably used herein are anionic, cationic, nonionic and amphoteric ones.
  • surfactants preferably used are nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polystyrylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol fatty acid monoesters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylene-modified castor oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N,N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters and trialkylamine oxides; anionic
  • Examples of other surfactants preferably used are fluorine atom-containing ones having, in the molecules, perfluoroalkyl groups.
  • Specific examples thereof include anionic type ones such as perfluoroalkylcarboxylic acid salts, perfluoroalkylsulfonic acid salts and perfluoroalkylphosphoric acid esters; amphoteric type ones such as perfluoroalkyl betaines; cationic type ones such as perfluoroalkyl trimethylammonium salts; and nonionic type ones such as perfluoroalkylamine oxides, perfluoroalkyl ethylene oxide adducts, oligomers carrying perfluoroalkyl groups and hydrophilic groups, oligomers carrying perfluoroalkyl groups and lipophilic groups, oligomers carrying perfluoroalkyl groups, hydrophilic groups and lipophilic groups and urethanes carrying perfluoroalkyl groups and lipophilic groups.
  • the foregoing surfactants may be used alone or in combination and the amount thereof added to the developer preferably ranges from 0.001 to 10% by weight and more preferably 0.01 to 5% by weight.
  • the organic solvents which may be added to the developer are preferably selected from those having solubility in water of not more than about 10% by weight, in particular not more than 5% by weight.
  • the organic solvent include 1-phenylethanol, 2-phenylethanol 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, N-phenyl ethanolamine and N-phenyl diethanolamine.
  • the amount of the organic solvents preferably ranges from 0.1 to 5% by weight with respect to the total weight of the developer practically employed.
  • the amount of the organic solvent is closely related to that of the surfactant. More specifically, the amount of the surfactant should be increased with the increase in that of the organic solvent. This is because if the amount of the anionic surfactant is low and that of the organic solvent is great, the organic solvent is not completely solubilized in water and as a result, good developing properties of the composition cannot be ensured.
  • the developer and replenisher used in the invention for developing the PS plates may further comprise reducing agent for preventing the contamination of the resulting lithographic printing plate and this is particularly effective in the development of negative-working PS plates comprising light-sensitive diazonium salts.
  • reducing agents preferably used are organic reducing agents, for instance, phenolic compounds such as thiosalicylic acid, hydroquinone, menthol, methoxyquinone, resorcin and 2-methylresorcin; amine compounds such as phenylenediamine and phenyl hydrazine; and inorganic reducing agents such as sodium, potassium and ammonium salts of inorganic acids such as sulfinic acid, hydrosulfurous acid, phosphorous acid, hydrogenphosphorous acid, dihydrogenphosphorous acid, thiosulfuric acid and dithionous acid.
  • reducing agents are preferably used in an amount ranging from 0.05 to
  • the developer and replenisher may also comprise organic carboxylic acids.
  • Preferred are aliphatic and aromatic carboxylic acids having 6 to 20 carbon atoms.
  • Specific examples of the aliphatic carboxylic acids are caproic acid, enanthylic acid, caprilic acid, lauric acid, myristic acid, palmitic acid and stearic acid with the alkanoic acids having 8 to 12 carbon atoms being particularly preferred.
  • These aliphatic acids may be unsaturated ones having, in the carbon chain, double bonds or those having branched carbon chains.
  • aromatic carboxylic acids are compounds having carboxyl groups on the aromatic rings such as benzene, naphthalene and anthracene rings, for instance, o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-naphthoic acid and 2-naphthoic acid, with the hydroxynaphthoic acids being particularly effective.
  • the foregoing aliphatic and aromatic carboxylic acids are preferably used in the form of sodium, potassium or ammonium salt for improving the solubility thereof in water.
  • the amount of the organic carboxylic acids used in the developer is not restricted to a particular range. However, if they are used in an amount of less than 0.1% by weight, the desired effect thereof is not anticipated, while if they are used in an amount of more than 10% by weight, any further effect thereof is not anticipated and if other additives are simultaneously used, they interrupt the dissolution thereof. Therefore, the amount of the carboxylic acids preferably ranges from 0.1 to 10% by weight and more preferably 0.5 to 4% by weight on the basis of the total weight of the developer practically used.
  • water softeners include polyphosphoric acids and sodium, potassium and ammonium salts thereof; polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid and 1,3-diamino-2-propanoltetraacetic acid, and ammonium, potassium and sodium salts thereof; aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), triethylenetetraminehexa(methylenephosphonic acid), hydroxyethylethylenediaminetri(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, and ammonium, potassium and sodium salts thereof.
  • the optimum amount of the water softener varies depending on the chelating ability of a specific softener, the hardness and the amount of hard water used, but the amount thereof in general ranges from 0.01 to 5% by weight and preferably 0.01 to 0.5% by weight on the basis of the total weight of the developer practically used. If the amount of the softener is less than the lower limit, the desired effect cannot be anticipated, while if it exceeds the upper limit, images are adversely affected and cause color blinding or the like.
  • the balance of the developer and replenisher used in the invention is water, but they may optionally comprise other various additives currently known in the art.
  • the developer and replenisher in the form of stock solutions having contents of the components higher than those practically used and diluted prior to use from the viewpoint of transportation.
  • the degree of concentration is preferably selected such that each component does not cause separation and precipitation.
  • the PS plate thus developed is then subjected to post-treatments with, for instance, washing water, a rinsing solution containing, for instance, a surfactant and/or a desensitization solution containing, for instance, gum arabic or a starch derivative. Any combination of these treatments can be used as the post-treatment for the PS plate thus prepared.
  • the automatic developing machine of this type generally comprises a developing zone and a post-treatment zone and more specifically it comprises a device for conveying PS plates to be processed, baths filled with various processing solutions and spray devices, wherein an imagewise exposed PS plate is developed by spraying each processing solution, sent up by a pump, thereon through a spray nozzle while the PS plate is horizontally conveyed.
  • the PS plate can be processed while supplementing replenishers to the corresponding processing baths in proportion to the amount of the processed PS plates and the operation time.
  • the lithographic printing plate prepared from a PS plate which makes use of the aluminum substrate brush-grained by the method of the present invention hardly causes, on a printing press, background contamination and narrowing and/or collapse of the shadowed portion thereof even when only a small amount of dampening water is used. Therefore, the printing plate can easily be handled even by an inexperienced person and can stably provide high quality copies as compared with conventional lithographic printing plates.
  • An aluminum plate of JIS A 1050 having a thickness of 0.24 mm was subjected to a brush-graining treatment using two kinds of rotary nylon brushes detailed below while supplying, to the surface of the plate, a suspension comprising particles of pumice stone having an average particle size of about 21 ⁇ m dispersed in water.
  • the first brush had a bristle length of 100 mm, a bristle diameter of 0.95 mm and a bristle-implantation density of 70 bristles/cm 2
  • the second brush had a bristle length of 80 mm, a bristle diameter of 0.295 mm and a bristle-implantation density of 670 bristles/cm 2 .
  • the diameter of the first and second brushes was 40 cm. These two brushes were both rotated at 250 rpm.
  • the plate was etched by immersing in a 10% sodium hydroxide solution at 60 °C for 25 seconds, followed by washing with running water, neutralization and washing with a 20% nitric acid solution and water-washing.
  • the aluminum plate was then electrolytically surface-roughened in a 1% aqueous nitric acid solution at an anodic voltage, V A , of 12.7 V such that the quantity of electricity at the anode time was 160 coulomb/dm 2 using a sinusoidal alternating waved current.
  • the surface roughness thereof was determined to be 0.79 ⁇ m (expressed in terms of the Ra unit). Thereafter, it was desmutted by immersing in a 1% aqueous sodium hydroxide solution at 40°C for 30 seconds and then in a 30% sulfuric acid aqueous solution at 60°C for 40 seconds and anodized in a 20% aqueous solution of sulfuric acid at a current density of 2 A/dm 2 so that the thickness of the resulting anodized layer was 1.6 g/m 2 to give an aluminum substrate.
  • An underlying coating solution having the following composition was applied onto the surface of the substrate thus treated and dried at 80°C for 30 seconds.
  • the coated amount of the underlying coating solution (weighed after drying) was found to be 30 mg/m 2 .
  • a mat layer was formed on the light-sensitive layer thus applied by electrostatically spraying an aqueous solution of methyl methacrylate/ethyl acrylate/sodium acrylate (68/20/12) copolymer according to the method disclosed in Example 1 of J.P. KOKOKU No. Sho 61-28986.
  • the PS plate thus formed was imagewise exposed, in a vacuum printing frame, to light from a 3 KW metal halide lamp at a distance of 1 m through a positive transparency for 50 seconds and then processed in an automatic developing machine STABLON 900D (available from Fuji Photo Film Co., Ltd.) which was supplied with a 5.26% aqueous solution (pH 12.7) of sodium silicate having a molar ratio SiO 2 /Na 2 O of 1.74 as a developer and FR-3 (diluted 8 times with water; available from Fuji Photo Film Co., Ltd. ) as a rinsing solution.
  • STABLON 900D available from Fuji Photo Film Co., Ltd.
  • the dampening water was decreased on the printing press and the lithographic printing plate was observed with naked eyes to determine the degree of contamination of the non-image area with the ink which was evaluated according to the following criteria: A ⁇ completely free of contamination; B ⁇ almost no contamination; C ⁇ slightly contaminated; and D ⁇ contaminated.
  • the narrowing of the distance between half tone dots in a shadowed portion was judged by determining whether 2% of the half tone dots in the Portion were opened or not when the dampening water was decreased and evaluated according to the following criteria: A ⁇ completely opened; B ⁇ approximately opened; C ⁇ slightly narrowed; and D ⁇ collapsed.
  • preferred acceptable copies can be obtained upon using a lithographic printing plate whose contamination of non-image area and narrowing of shadowed portions are both not less than the evaluation criterion B.
  • the lithographic printing plate which made use of the substrate prepared by the method of the present invention, hardly caused background contamination and narrowing or collapse of the shadowed portion thereof even when only a small amount of dampening water was used.
  • the lithographic printing plate could provide acceptable copies of more than 100,000.
  • Example 1 Combination of Brushes Surface Roughness Ra ( ⁇ m) Background Contaminattion Narrow ing of Shad. Port.
  • First Brush Second Brush Bristle Length (mm) 0.95 0.72 0.57 0.295 0.21 1 * * 0.79 B A 2 * * 0.78 B A 3 * * 0.74 B A 4 * * 0.71 B A 5 * * 0.69 A A 6 * * 0.63 A A Comp. Ex. 1 * 0.82 D A 2 * 0.76 C A 3 * 0.70 C A 4 * 0.43 A C 5 * 0.35 A D *: This indicates that each corresponding brush was used. 1): Narrowing of shadowed portions.
  • the surface roughness Ra was determined using a surface roughness-determining device (surface profilometer) SURFCOM 300B (available from Tokyo Seimitsu Co., Ltd.; tracer 10 ⁇ mR).
  • Example 2 Example Combination and No. of Brushes Surface Roughness ( ⁇ m) Background Contamination Narrowing in Shad. Port. First Brush Second Brush Bristle Length (mm) 0.72 0.57 0.295 5 -- 1 1 0.69 A A 7 -- 2 1 0.70 A A 8 -- 5 1 0.71 A A 9 1 1 1 0.73 A A Comp. Ex. 6 -- 2 -- 0.72 C A 7 -- -- 2 0.37 A C

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Claims (9)

  1. Verfahren zur Vorbereitung eines Aluminiumsubstrats für eine lithografische Druckplatte mit einem Bürst-Körnungs-Schritt, der ein Oberflächenaufrauhen einer Aluminiumplatte mit zumindest zwei Arten von Bürsten enthält, die Borsten von unterschiedlichen Durchmessern aufweisen, dadurch gekennzeichnet, daß die zwei Arten von Bürsten aufweisen eine erste Bürste, die Borsten mit einem Durchmesser von nicht weniger als 0,57 mm und nicht mehr als 1,20 mm aufweist, und eine zweite Bürste, die Borsten mit einem Durchmesser von nicht weniger als 0,10 mm und nicht mehr als 0,34 mm aufweist und daß die Bürste, die in dem abschließenden Bürst-Körnungs-Prozeß verwendet wird, die zweite Bürste ist.
  2. Verfahren nach Anspruch 1, bei dem die Bürsten jeweils aufweisen eine walzenartige Basis und Nylonborsten, die in die Basis implantiert sind; oder eine Basis aufweisen, die kleine Öffnungen aufweist, und wobei Bündel von Nylonborsten in die Öffnungen der Basis implantiert sind; oder eine Bürste vom Walzenrolltyp aufweisen.
  3. Verfahren nach Anspruch 2, bei dem die Bürste Nylonborsten aufweist, die eine Borstenlänge im Bereich von 10 bis 200 mm, bestimmt nach der Implantation, aufweisen.
  4. Verfahren nach Anspruch 2, bei dem die Bürste eine Dichte der implantierten Borsten im Bereich von 50 bis 300 Borsten/cm2 aufweist.
  5. Verfahren nach Anspruch 1, bei dem die zwei Arten von Bürsten sind: die erste Bürste, deren Borsten einen Durchmesser von nicht weniger als 0,64 mm und nicht mehr als 1,00 mm aufweisen und die zweite Bürste, deren Borsten einen Durchmesser von nicht weniger als 0,20 mm und nicht mehr als 0,30 mm aufweisen; und daß die Bürste, die in dem abschließenden Bürst-Körnungs-Prozeß verwendet wird, die zweite Bürste ist.
  6. Verfahren nach Anspruch 1, bei dem die Anzahl der verwendeten ersten Bürsten im Bereich von 1 bis 10 liegt und die Anzahl der zweiten Bürsten, die verwendet werden, im Bereich von 1 bis 3 liegt.
  7. Verfahren nach Anspruch 1, bei dem der Bürst-Körnungs-Prozeß unter Verwendung einer Schlämmung ausgeführt wird, die ein abrasives Material aufweist, mit einer durchschnittlichen Partikelgröße von 15 bis 35 µ, dispergiert in Wasser, in einer Konzentration im Bereich von 10 bis 70 Gew.-%.
  8. Verfahren nach Anspruch 1, bei dem der Bürst-Körnungs-Prozeß ausgeführt wird, bis der arithmetische Mittenrauhwert (Ra) der Aluminiumplatte in den Bereich von 0,5 bis 1,0 µ fällt.
  9. Verfahren nach Anspruch 1, bei dem es außerdem im Anschluß an den Bürst-Körnungs-Prozeß einen elektrolytischen Oberflächen-Aufrauhungsprozeß und einen anodischen Oxidationsprozeß aufweist.
EP19930116973 1992-10-28 1993-10-20 Verfahren zur Herstellung einer Aluminiumfolie zur Verwendung als Träger in lithographischen Druckplatten Expired - Lifetime EP0595179B1 (de)

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JP290527/92 1992-10-28
JP29052792A JP3276422B2 (ja) 1992-10-28 1992-10-28 平版印刷版用アルミニウム支持体の製造方法

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EP0595179B1 true EP0595179B1 (de) 1997-03-19

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JPH09207467A (ja) * 1996-02-02 1997-08-12 Fuji Photo Film Co Ltd 平版印刷版支持体の製造方法
EP0874068B1 (de) * 1997-04-25 2004-01-14 Fuji Photo Film Co., Ltd. Verfahren zur Herstellung eines Aluminiumträgers für lithographische Druckplatten
DE19809802A1 (de) * 1998-03-09 1999-09-16 Binder Hans Verfahren zur Oberflächenbehandlung von Aluminium oder dergleichen
CN1169680C (zh) 2000-05-15 2004-10-06 富士胶片株式会社 平版印刷印版的支持体和感光性树脂平版
US6780305B2 (en) 2001-02-20 2004-08-24 Fuji Photo Film Co., Ltd. Method for producing support for planographic printing plate, support for planographic printing plate, and planographic printing plate precursor
ATE541709T1 (de) 2001-10-05 2012-02-15 Fujifilm Corp Lithographisches druckplattensubstrat und vorsensibilisierte platte und herstellungsverfahren für eine lithographische druckplatte
ATE443616T1 (de) 2002-02-26 2009-10-15 Fujifilm Corp Aluminiumträger für eine flachdruckplatte und verfahren zu seiner herstellung sowie eine vorsensibilisierte druckplatte, die diesen verwendet
US7063935B2 (en) 2002-03-26 2006-06-20 Fuji Photo Film Co., Ltd. Support for lithographic printing plate and presensitized plate and method of producing lithographic printing plate
JP4152656B2 (ja) 2002-04-02 2008-09-17 富士フイルム株式会社 平版印刷版用原版
JP4410714B2 (ja) 2004-08-13 2010-02-03 富士フイルム株式会社 平版印刷版用支持体の製造方法
ATE395195T1 (de) 2005-04-13 2008-05-15 Fujifilm Corp Verfahren zur herstellung eines flachdruckplattenträgers
DE602007000242D1 (de) 2006-05-25 2008-12-24 Fujifilm Corp Flachdruckplattenvorläufer und Stapel daraus
WO2009041659A1 (ja) 2007-09-28 2009-04-02 Fujifilm Corporation 太陽電池
JP2009208140A (ja) 2008-03-06 2009-09-17 Fujifilm Corp 平版印刷版用アルミニウム合金板の製造方法、ならびに該製造方法により得られる平版印刷版用アルミニウム合金板および平版印刷版用支持体
EP2110261B1 (de) 2008-04-18 2018-03-28 FUJIFILM Corporation Aluminiumlegierungsplatte für eine lithographische Druckplatte, lithographische Druckplattenträger, Druckplattenvorläufer, Verfahren zur Herstellung einer Aluminiumlegierungsplatte für eine lithographische Druckplatte und Verfahren zur Herstellung eines lithographischen Druckplatteträgers
JP5296434B2 (ja) 2008-07-16 2013-09-25 富士フイルム株式会社 平版印刷版用原版
JP5405475B2 (ja) 2008-09-30 2014-02-05 富士フイルム株式会社 電解粗面化処理方法および電解粗面化処理装置
KR20120101290A (ko) 2009-06-26 2012-09-13 후지필름 가부시키가이샤 광반사 기판 및 그 제조 방법
JP2012033853A (ja) 2010-04-28 2012-02-16 Fujifilm Corp 絶縁性光反射基板
EP2586621B1 (de) 2011-10-28 2014-08-20 Fujifilm Corporation Herstellungsverfahren und Herstellungsvorrichtung einer Stütze für Flachdruckplatte
WO2018235659A1 (ja) 2017-06-21 2018-12-27 富士フイルム株式会社 アルミニウム複合材料
BR112019000016A2 (pt) 2017-10-31 2020-05-05 Fujifilm Corp precursor de placa de impressão litográfica, método para produção de placa de impressão litográfica, método de impressão e método para produção de suporte de alumínio
EP4269120A4 (de) 2020-12-25 2024-05-22 Fujifilm Corp Originalplatte für eine flachdruckplatte, verfahren zur herstellung einer flachdruckplatte, druckverfahren und verfahren zur herstellung eines aluminiumträgers
JPWO2023032992A1 (de) 2021-08-31 2023-03-09

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EP0595179A1 (de) 1994-05-04
JP3276422B2 (ja) 2002-04-22
JPH06135175A (ja) 1994-05-17
DE69308983T2 (de) 1997-06-26
DE69308983D1 (de) 1997-04-24

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