CA1103507A - Process for the preparation of planographic printing forms by means of laser beams - Google Patents
Process for the preparation of planographic printing forms by means of laser beamsInfo
- Publication number
- CA1103507A CA1103507A CA306,161A CA306161A CA1103507A CA 1103507 A CA1103507 A CA 1103507A CA 306161 A CA306161 A CA 306161A CA 1103507 A CA1103507 A CA 1103507A
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- CA
- Canada
- Prior art keywords
- recording layer
- layer
- irradiated
- oxide layer
- light
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
- G03F7/2055—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser for the production of printing plates; Exposure of liquid photohardening compositions
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/016—Diazonium salts or compounds
- G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
- G03F7/0212—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the diazo resins or the polymeric diazonium compounds
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Printing Plates And Materials Therefor (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Manufacture Or Reproduction Of Printing Formes (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
Abstract
PROCESS FOR THE PREPARATION OF PLANOGRAPHIC
PRINTING FORMS BY MEANS OF LASER BEAMS
Abstract of the Disclosure This invention relates to an improvement in the process for the preparation of a planographic printing form wherein a re-cording material comprising a support of anodically oxidized aluminum with an oxide layer weighing at least 3 grams per square meter and a light-sensitive recording layer on the oxide layer is imagewise irradiated with a laser beam, thus rendering the irradiated portions of the recording layer oleophilic and/or insoluble, and the non-irradiated areas of the recording layer are then removed with a developer liquid, the improvement comprising employing a recording layer which comprises a negative-working, light-hardenable, water-soluble diazo compound.
PRINTING FORMS BY MEANS OF LASER BEAMS
Abstract of the Disclosure This invention relates to an improvement in the process for the preparation of a planographic printing form wherein a re-cording material comprising a support of anodically oxidized aluminum with an oxide layer weighing at least 3 grams per square meter and a light-sensitive recording layer on the oxide layer is imagewise irradiated with a laser beam, thus rendering the irradiated portions of the recording layer oleophilic and/or insoluble, and the non-irradiated areas of the recording layer are then removed with a developer liquid, the improvement comprising employing a recording layer which comprises a negative-working, light-hardenable, water-soluble diazo compound.
Description
35;~7 Hoe 77/K 038 (K 2455b) The present invention relates to a process for the prepa-ratlon of planographic prlnting forms where1n an aluminum support covered by a recording layer comprising diazo compounds is image-wise lrradiated with a laser beam, thus producing in the recording layer oleophiLic or insoluble image areas, U. S. Patent No. 3,664,737, dlscloses a prlnting plate comprising a UV light-sensitive layer, preierably a diazo layer, on an aluminum support and which is irradiated wlth a laser beam.
German Patent No . 2, 448, 325, and German Offenlegungs-schrift No . 2, 543, 820, disclose the manufacture of printing plates by irradiating non-light~sensitive recording layers wlth laser beams, the irradiated a reas of the recording layer being rendered permanently oleophilic or, if an oleophllic layer is used, insol-uble in an appropriately selected developer liquid. Anodized aluminum is mentioned as a suitable support, inter alia.
In the earlier filed German Patent Application No. P
German Patent No . 2, 448, 325, and German Offenlegungs-schrift No . 2, 543, 820, disclose the manufacture of printing plates by irradiating non-light~sensitive recording layers wlth laser beams, the irradiated a reas of the recording layer being rendered permanently oleophilic or, if an oleophllic layer is used, insol-uble in an appropriately selected developer liquid. Anodized aluminum is mentioned as a suitable support, inter alia.
In the earlier filed German Patent Application No. P
2,725,308, lt has been suggested to use laser beams for imaging a presensitized printing plate which comprises a support of op-tionally anodized aluminum and a light-sensitive layer comprising a negative-working diazonium compound.
Further, it has been suggested, in the earlier German Patent Applicatlon No. P 2,725,307, to render a printing plate of the type just mentioned more sensitive to laser beams within the visible range of the spectrum by adding a sensltizing dyestuff to the light-sensitive layer.
The basic patent relates to a process for the preparation of planographic printlng forms wherein a recordlng material ~"~.d `` Hoe 77/K 038 (K 2455b) comprising a support of anodically oxidized aluminum and a re-cording layer on the oxide layer is imagewise irradlated with a laser beam, thus rendering the irradiated portions of the recording layer oleophilic and/or insoluble, and the non-irradiated portions of the recording layer are then removed, where necessary, by washing with a developer liquid. In the process a support is used which has an oxide layer weighing at least 3 grams per square meter.
It is the object of the present invention to improve the 10 - process according to the basic patent in a suitable rnanner.
In the process according to the present invention a record-ing layer is used which comprises a negative-working, light-hardenable ,- water-soluble diazo compound.
Negative-working, light-hardenable diazo compounds which may be used in the process according to the present invention are, in particular, polycondensation products of diazonium salts, also designated as diazo resins. Suitable polycondensation prod-ucts are obtained by condensation of aromatic diazonium salts, preferably of substituted or unsubstituted diphenylamine-4-diazonium salts, -with active carbonyl compounds, preferably formaLdehyde, ln a strongly acid medium.
Products of this type have been disclosed, for example, in German Patents No. 1,214,086 and No. 1,292 ,001. They advantageously may be employed in the form oi their water-soluble salts, for example the chlorozincates~ Particularly preferred are mixed condensation products containing diazonium salt units and units of non-light~sensitive second components capable of 311.~3S~'~ Hoe 77/K 038 (K 2455b) condensation, such as aromatic amines, phanols, thiophenols, phenol ethers, aromatic thioethers, aromatic hydrocarbons, aro-matic heterocyclic compounds, and organic acid amldes, ln the form of their water-soluble salts. Condensation products of ~his type are described in U. S. Patents Nos. 3,849,392, 3,867,147, and especiaLly 9,021,243.
Dyestuffs which absorb in the emitted wave length range and have a sensitizing action, and/or water-soluble metal salts, are advantageously added to the layers according to the invention.
Suitable dyestuffs are, e . g . rhodamines, triphenyl methane dye--~ l stuffs, such as crystal violet, astrazon orange, eosin, methylene blue, victoria pure blue and the like. The :following metal salts have proved particularly suitable: :
Cobaltous chloride - CoCl2 6 H20 ~ ~ uranyl nitrate - U02(N03)2 6 H2O
: ~ ~ cadmium chloride - CdC12 2 H2O
-~ ; ammonium iron-(III)-sulfate - NH4Fe(S04)2 12 H20 cadmlum nitrate - Cd(N03)2 4 H20 cerous~ chloride - CeCl3 7 :H20 . cadmium sulfate - CdS04 8/3 H20 ammonlum iron-~II)-sulfate -(NH4)2Fe(S04~2 2 ammonium cerous-IV-nitrate -: ~ (NH",)2Ce(N03)6 cadmium ac:etate - Ca(CH3C00)2 2 H20 cobalt-III-acetylacetonate ~ C15H210~jCo cobalt~ acetate - Co(CH3C00)2 4 H20 sodlum hexanitro cobaltate- (III) Na3[C(N2)~;1 Hoe 77/K 038 (K 2455b) ~3~;~7 nickel chloride - NiC12 6 H O, and manganous chloride - MnC12 4 H2O
For the preparation of the laser-sensitive printing plate according to the invention, the diazo compound and, where appli-cable, the dyestuff or dyestuffs, and/or metal salts, are applied to the support in an aqueous solution and then drled. For better application to the support, small quantities of wetting agants, e.g. non-ionogenic wetting agents, and/or lower alcohols, such as methanol, ethanol or propanol, may be added to the solution.
The solution may be applied by whirler coating, spraying, immer-sion, or by roller application.
The supports for the recording materials used according to the invention are prepared In known manner. Preferably, the aluminum is roughened by mechanical, chemLcal or electrochemical means before it is anodically oxidized. A combination of electro lytic roughening and anodic oxidation has been found to be par-ticularly advantageous for a continuous process. Roughening is effected in a bath containing a dilute aqueous mineral acid, e.g. hydrochloric acld or nitric acid, with direct or alternating current being used.
Anodization is preferably also effected in an aqueous acid bath, for example a sulfuric acid or phosphoric acid bath, prefer-ably using direct current. The current densities and anodization times are so selected that oxide layers of the thickness above mentioned result. The thickness of the layer should correspond to a weigh~ of at least 3 grams per square meter. The upper limit of the layer thickness 1s not critical, but normally no sub-stantial improvements are achleved by using layers whose weight ~3~ Hoe 77/K 038 (K 2455b) exceeds ~5 grams per square meter. If considerably thicker layers are used, for example, layers weighlng more than about 30 grams per square meter, there ls the additlonal risk of cracks forming in the oxide layer when the plate is bent. As a rule, oxide layers weighing between about 5 and 12 grams per square meter are preferred.
After irradiation with laser light, the UV-light-sensitive diazo layers accordlng to the invention are developed with aque-ous alkaline or acid solutions or, preferably, with water alone.
Lacquer emulsions ~or lacquers such as those known for use with planographic printing plates, also may be used. These lacquer emulsions and lacquers may be used, for developing and lacquer-ing the plates in one operation, or they may be applied after the plate has been developed with an aqueous solution.
Appropriately powered relatively short-wave lasers, e . g .
argon lasers and krypton lasers with a radiation output of between 0.5 and approximately 2.5 watts in the UV region or between and 25 watts in the visible region - depending on which type of mirror is used - are suitable for the pùrposes of the invention.
: ~ . .
The laser beam may be controlled by means of a given programmed llne and/or screen movement. Processes and devices for controlling laser beams by means ol computers and for bundl-ing, modulation, or deflection of laser beams are no part of the present invention; they are descrlbed in various publications, for example in German Offenlegungsschriften Nos. 2,318,133 (page 3 et seq.), 2,344,233 (page 8 et seq.), and in U. S. Patents Nos
Further, it has been suggested, in the earlier German Patent Applicatlon No. P 2,725,307, to render a printing plate of the type just mentioned more sensitive to laser beams within the visible range of the spectrum by adding a sensltizing dyestuff to the light-sensitive layer.
The basic patent relates to a process for the preparation of planographic printlng forms wherein a recordlng material ~"~.d `` Hoe 77/K 038 (K 2455b) comprising a support of anodically oxidized aluminum and a re-cording layer on the oxide layer is imagewise irradlated with a laser beam, thus rendering the irradiated portions of the recording layer oleophilic and/or insoluble, and the non-irradiated portions of the recording layer are then removed, where necessary, by washing with a developer liquid. In the process a support is used which has an oxide layer weighing at least 3 grams per square meter.
It is the object of the present invention to improve the 10 - process according to the basic patent in a suitable rnanner.
In the process according to the present invention a record-ing layer is used which comprises a negative-working, light-hardenable ,- water-soluble diazo compound.
Negative-working, light-hardenable diazo compounds which may be used in the process according to the present invention are, in particular, polycondensation products of diazonium salts, also designated as diazo resins. Suitable polycondensation prod-ucts are obtained by condensation of aromatic diazonium salts, preferably of substituted or unsubstituted diphenylamine-4-diazonium salts, -with active carbonyl compounds, preferably formaLdehyde, ln a strongly acid medium.
Products of this type have been disclosed, for example, in German Patents No. 1,214,086 and No. 1,292 ,001. They advantageously may be employed in the form oi their water-soluble salts, for example the chlorozincates~ Particularly preferred are mixed condensation products containing diazonium salt units and units of non-light~sensitive second components capable of 311.~3S~'~ Hoe 77/K 038 (K 2455b) condensation, such as aromatic amines, phanols, thiophenols, phenol ethers, aromatic thioethers, aromatic hydrocarbons, aro-matic heterocyclic compounds, and organic acid amldes, ln the form of their water-soluble salts. Condensation products of ~his type are described in U. S. Patents Nos. 3,849,392, 3,867,147, and especiaLly 9,021,243.
Dyestuffs which absorb in the emitted wave length range and have a sensitizing action, and/or water-soluble metal salts, are advantageously added to the layers according to the invention.
Suitable dyestuffs are, e . g . rhodamines, triphenyl methane dye--~ l stuffs, such as crystal violet, astrazon orange, eosin, methylene blue, victoria pure blue and the like. The :following metal salts have proved particularly suitable: :
Cobaltous chloride - CoCl2 6 H20 ~ ~ uranyl nitrate - U02(N03)2 6 H2O
: ~ ~ cadmium chloride - CdC12 2 H2O
-~ ; ammonium iron-(III)-sulfate - NH4Fe(S04)2 12 H20 cadmlum nitrate - Cd(N03)2 4 H20 cerous~ chloride - CeCl3 7 :H20 . cadmium sulfate - CdS04 8/3 H20 ammonlum iron-~II)-sulfate -(NH4)2Fe(S04~2 2 ammonium cerous-IV-nitrate -: ~ (NH",)2Ce(N03)6 cadmium ac:etate - Ca(CH3C00)2 2 H20 cobalt-III-acetylacetonate ~ C15H210~jCo cobalt~ acetate - Co(CH3C00)2 4 H20 sodlum hexanitro cobaltate- (III) Na3[C(N2)~;1 Hoe 77/K 038 (K 2455b) ~3~;~7 nickel chloride - NiC12 6 H O, and manganous chloride - MnC12 4 H2O
For the preparation of the laser-sensitive printing plate according to the invention, the diazo compound and, where appli-cable, the dyestuff or dyestuffs, and/or metal salts, are applied to the support in an aqueous solution and then drled. For better application to the support, small quantities of wetting agants, e.g. non-ionogenic wetting agents, and/or lower alcohols, such as methanol, ethanol or propanol, may be added to the solution.
The solution may be applied by whirler coating, spraying, immer-sion, or by roller application.
The supports for the recording materials used according to the invention are prepared In known manner. Preferably, the aluminum is roughened by mechanical, chemLcal or electrochemical means before it is anodically oxidized. A combination of electro lytic roughening and anodic oxidation has been found to be par-ticularly advantageous for a continuous process. Roughening is effected in a bath containing a dilute aqueous mineral acid, e.g. hydrochloric acld or nitric acid, with direct or alternating current being used.
Anodization is preferably also effected in an aqueous acid bath, for example a sulfuric acid or phosphoric acid bath, prefer-ably using direct current. The current densities and anodization times are so selected that oxide layers of the thickness above mentioned result. The thickness of the layer should correspond to a weigh~ of at least 3 grams per square meter. The upper limit of the layer thickness 1s not critical, but normally no sub-stantial improvements are achleved by using layers whose weight ~3~ Hoe 77/K 038 (K 2455b) exceeds ~5 grams per square meter. If considerably thicker layers are used, for example, layers weighlng more than about 30 grams per square meter, there ls the additlonal risk of cracks forming in the oxide layer when the plate is bent. As a rule, oxide layers weighing between about 5 and 12 grams per square meter are preferred.
After irradiation with laser light, the UV-light-sensitive diazo layers accordlng to the invention are developed with aque-ous alkaline or acid solutions or, preferably, with water alone.
Lacquer emulsions ~or lacquers such as those known for use with planographic printing plates, also may be used. These lacquer emulsions and lacquers may be used, for developing and lacquer-ing the plates in one operation, or they may be applied after the plate has been developed with an aqueous solution.
Appropriately powered relatively short-wave lasers, e . g .
argon lasers and krypton lasers with a radiation output of between 0.5 and approximately 2.5 watts in the UV region or between and 25 watts in the visible region - depending on which type of mirror is used - are suitable for the pùrposes of the invention.
: ~ . .
The laser beam may be controlled by means of a given programmed llne and/or screen movement. Processes and devices for controlling laser beams by means ol computers and for bundl-ing, modulation, or deflection of laser beams are no part of the present invention; they are descrlbed in various publications, for example in German Offenlegungsschriften Nos. 2,318,133 (page 3 et seq.), 2,344,233 (page 8 et seq.), and in U. S. Patents Nos
3,751,587, 3,745,586, 3,747,117, 3,~75,760, 3,506,779, and 3,664,737.
' - .
Hoe 77/K 038 (K 2455b) The invention will be further illustrated by reference to the following specific examples:
Example A roll of bright rolled alumlnum is electrolytically roughen-ed in a continuous process and then anodically oxidized for 75 seconds, at 40 C, with a 9 A/dm2 direct current in an aqueous bath containing 150 grams of H2SO4 per liter. The layer is then treated for 30 seconds, at 70 C, with a 0 . 25 per cent by weight aqueous solution of polyvinyl phosphonic acid and then dried.
The plate is then sensitized with an aqueous solution containing 5, 6 per cent by weight of a diazo polycondensate (obtained by condensing 1 mole of 3-methoxy-diphenylamine-4 diazonium sul-fate with 1 mole of 4,4' dimethoxymethyl-diphenyl ether in 85 per cent by weight phosphoric acid at 40 C and separating the reac-tion product in the form of the methane sulfonate) and 0 . 5 6 per cent by weight of cadmium chloride CdC12 2 1/2 H O which is applied by roller appllcation.
The sensitized plate is then irradiated wi~h an ar~on laser emitting within the visible range of the spectrum, mainly at wave lengths of 488 and 514 nm, the radiation output being 5 watts and the recording speed 40 meters per secondO The areas of the layer not struck by the laser beam are removed by washlng with water. The areas which were lrradiated by the laser beam readily accept greasy ink in an offset machine and produce long printing runs .
Example 2 An aluminum plate with an anodic oxide layer weighing 3 grams per square meter, which had been pretreated with polyvinyl Hoe 77/K 03~ (K 2455b) ~L~3~
phosphonic acid, is coated, by roller application, with a solution containing 9 . 3 parts by weight of a condensation product of diphenylamine-4-diazonium sulfate and formaldehyde, prepared in concentrated sulfuric acid and separated in the form of the chloro-zincate, and 0 . 3 3 part by weight of Rhodamine 6 GDN (C . I .
45 ,160) dissolved in 85 parts by volume oE water and 10 parts by volume of ethanol. The coated plate is irradiated with an argon laser emitting in the UV range, mainly at wave lengths of 363.8 and 351 . 1 nm, the radiation output of the laser being 0 . 8 watt and the recording speed being 50 m/sec., and the plate is then ` developed with water.
Good results are also obtained if the dyestuff Rhodamine - 6 GDN is replaced by Astrazon Orange (C.I. No. 48,040) or by Crystal Violet.
Example 3 An aluminum plate with an anodic oxide layer weighing 8 grams per square meter is coated with a solution whlch contains 5 . 5 per cent of the diazo condensation product described in Exam-ple 2 and 0.56 per cent of cobaltous chlorlde, dissolved in a mixture of 90 parts by volume of water and 10 parts by volume of methanol.
The plate is irradiated at a speed of 1 0û m/sec . with an argon laser of 5 watts output emitting in the visible range of the spectrum and is then decoated with an aqueous solution contain lng 1 per cent by weight of phosphoric acid and 0 . 5 per cent by weight of gum arabic.
Hoe 77/K 038 (K 2455b) 3~
Good results are also obtained when replacing the cobalt-ous chLoride by the same quantity of one of the following metal salts:
Cadmium nitrate, nickel chloride, manganous chloride, ammonium-iron-(II)-sulfate, or cadmium acetate.
~ .
An anodically oxidized aluminum plate with an oxide layer welghLng 3 . 5 grams per square meter is coated with a solution containing 9 . 4 parts by weight of a crude conden sation product (obtained from 3-methoxy-diphenylamine-4-diazonium chloride and formaldehyde in phosphoric acid), 0.56 part by weight of uranyl nitrate, and 0.33 part by weight of Rhodamine 6 GDN ~ dissolveà
in 80 parts by volume of water and 10 parts by volume of - ethanol. After irradiation with an argon laser emitting in the visible ra~nge, which has an output of 5 watts and a speed of 80 meters per second, the plate ls decoated with a 1 per cent solution of phosphoric acid.
Example 5 .~
An anodically oxidized aluminum plate with an oxide layer weighing 4 grams per square meter is immersed for 60 seconds, at a temperature of 80 C, in a 2 per cen~ solution of sodium silicate, rinsed, dried, and then coated with an aqueous solution containing 6 per cent of the diazo condensate described in Example 2.
The plate is irradiated with an argon laser emitting in the UV range with a radiation output of 2 . 5 and is then decoated with water. In order to increase the length of the printing run, the Hoe 77/K 038 (K 2455b) ~3~
image areas are lacquered by wiping them over with a lacquer emulsion of the following composition:
Non-aqueous phase:
30 p.b.w. of ethyleneglycol methylether acetate, 40 p.b.w. of cyclohexanone, 25 p.b.w. of xylene, 25 p.b.w. of tetrahydronaphthalene, 50 p,b.w, of a cresol-formaldehyde novolak with a melting range between ].08 and 118 C, and 5 p . b .-w . of Llthol Rubin B .
Aqueous phase: ~
3 6 p . b O w . of gum arabic, : 340 p.b.w, of water, and : 2 p .b .w . ~ of a wetting ~ agent (fatty acid/hydroxy :. ~ : : .
ethyl sulfonlc acid condensation product).
: It will be obvlous to those skilled in the art that many .....
: modifications may be made -within the scope of the present inven-tion without d.epartlng from the splrit thereof, and the invention includes ~all such modlfications. ~.
~- :
' ~ ` '
' - .
Hoe 77/K 038 (K 2455b) The invention will be further illustrated by reference to the following specific examples:
Example A roll of bright rolled alumlnum is electrolytically roughen-ed in a continuous process and then anodically oxidized for 75 seconds, at 40 C, with a 9 A/dm2 direct current in an aqueous bath containing 150 grams of H2SO4 per liter. The layer is then treated for 30 seconds, at 70 C, with a 0 . 25 per cent by weight aqueous solution of polyvinyl phosphonic acid and then dried.
The plate is then sensitized with an aqueous solution containing 5, 6 per cent by weight of a diazo polycondensate (obtained by condensing 1 mole of 3-methoxy-diphenylamine-4 diazonium sul-fate with 1 mole of 4,4' dimethoxymethyl-diphenyl ether in 85 per cent by weight phosphoric acid at 40 C and separating the reac-tion product in the form of the methane sulfonate) and 0 . 5 6 per cent by weight of cadmium chloride CdC12 2 1/2 H O which is applied by roller appllcation.
The sensitized plate is then irradiated wi~h an ar~on laser emitting within the visible range of the spectrum, mainly at wave lengths of 488 and 514 nm, the radiation output being 5 watts and the recording speed 40 meters per secondO The areas of the layer not struck by the laser beam are removed by washlng with water. The areas which were lrradiated by the laser beam readily accept greasy ink in an offset machine and produce long printing runs .
Example 2 An aluminum plate with an anodic oxide layer weighing 3 grams per square meter, which had been pretreated with polyvinyl Hoe 77/K 03~ (K 2455b) ~L~3~
phosphonic acid, is coated, by roller application, with a solution containing 9 . 3 parts by weight of a condensation product of diphenylamine-4-diazonium sulfate and formaldehyde, prepared in concentrated sulfuric acid and separated in the form of the chloro-zincate, and 0 . 3 3 part by weight of Rhodamine 6 GDN (C . I .
45 ,160) dissolved in 85 parts by volume oE water and 10 parts by volume of ethanol. The coated plate is irradiated with an argon laser emitting in the UV range, mainly at wave lengths of 363.8 and 351 . 1 nm, the radiation output of the laser being 0 . 8 watt and the recording speed being 50 m/sec., and the plate is then ` developed with water.
Good results are also obtained if the dyestuff Rhodamine - 6 GDN is replaced by Astrazon Orange (C.I. No. 48,040) or by Crystal Violet.
Example 3 An aluminum plate with an anodic oxide layer weighing 8 grams per square meter is coated with a solution whlch contains 5 . 5 per cent of the diazo condensation product described in Exam-ple 2 and 0.56 per cent of cobaltous chlorlde, dissolved in a mixture of 90 parts by volume of water and 10 parts by volume of methanol.
The plate is irradiated at a speed of 1 0û m/sec . with an argon laser of 5 watts output emitting in the visible range of the spectrum and is then decoated with an aqueous solution contain lng 1 per cent by weight of phosphoric acid and 0 . 5 per cent by weight of gum arabic.
Hoe 77/K 038 (K 2455b) 3~
Good results are also obtained when replacing the cobalt-ous chLoride by the same quantity of one of the following metal salts:
Cadmium nitrate, nickel chloride, manganous chloride, ammonium-iron-(II)-sulfate, or cadmium acetate.
~ .
An anodically oxidized aluminum plate with an oxide layer welghLng 3 . 5 grams per square meter is coated with a solution containing 9 . 4 parts by weight of a crude conden sation product (obtained from 3-methoxy-diphenylamine-4-diazonium chloride and formaldehyde in phosphoric acid), 0.56 part by weight of uranyl nitrate, and 0.33 part by weight of Rhodamine 6 GDN ~ dissolveà
in 80 parts by volume of water and 10 parts by volume of - ethanol. After irradiation with an argon laser emitting in the visible ra~nge, which has an output of 5 watts and a speed of 80 meters per second, the plate ls decoated with a 1 per cent solution of phosphoric acid.
Example 5 .~
An anodically oxidized aluminum plate with an oxide layer weighing 4 grams per square meter is immersed for 60 seconds, at a temperature of 80 C, in a 2 per cen~ solution of sodium silicate, rinsed, dried, and then coated with an aqueous solution containing 6 per cent of the diazo condensate described in Example 2.
The plate is irradiated with an argon laser emitting in the UV range with a radiation output of 2 . 5 and is then decoated with water. In order to increase the length of the printing run, the Hoe 77/K 038 (K 2455b) ~3~
image areas are lacquered by wiping them over with a lacquer emulsion of the following composition:
Non-aqueous phase:
30 p.b.w. of ethyleneglycol methylether acetate, 40 p.b.w. of cyclohexanone, 25 p.b.w. of xylene, 25 p.b.w. of tetrahydronaphthalene, 50 p,b.w, of a cresol-formaldehyde novolak with a melting range between ].08 and 118 C, and 5 p . b .-w . of Llthol Rubin B .
Aqueous phase: ~
3 6 p . b O w . of gum arabic, : 340 p.b.w, of water, and : 2 p .b .w . ~ of a wetting ~ agent (fatty acid/hydroxy :. ~ : : .
ethyl sulfonlc acid condensation product).
: It will be obvlous to those skilled in the art that many .....
: modifications may be made -within the scope of the present inven-tion without d.epartlng from the splrit thereof, and the invention includes ~all such modlfications. ~.
~- :
' ~ ` '
Claims (4)
1. In the process for the preparation of a planographic print-ing form wherein a recording material comprising a support of anodically oxidized aluminum with an oxide layer weighing at least 3 grams per square meter and a light-sensitive recording layer on the oxide layer is imagewise irradiated with a laser beam, thus rendering the irradiated portions of the recording layer oleo-philic and/or insoluble, and the non-irradiated areas of the re-cording layer are then removed with a developer liquid, the improvement comprising employing a recording layer which comprises a negative-working, light-hardenable, water-soluble diazo compound.
.
.
2. A process according to claim 1 including employing a sup-port whose oxide layer weighs between 5 and 12 grams per square meter.
3. A process according to claim 1 in which the negative-working, water-soluble diazo compound is a diazonium salt con-densation product.
4. A process according to claim 1 including employing a recording layer which additionally contains a dyestuff or a metal salt as a sensitizer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2728858A DE2728858C2 (en) | 1977-06-27 | 1977-06-27 | Process for the production of planographic printing forms with laser beams |
| DEP2728858.0 | 1977-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1103507A true CA1103507A (en) | 1981-06-23 |
Family
ID=6012436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA306,161A Expired CA1103507A (en) | 1977-06-27 | 1978-06-23 | Process for the preparation of planographic printing forms by means of laser beams |
Country Status (16)
| Country | Link |
|---|---|
| JP (1) | JPS5412907A (en) |
| AU (1) | AU521791B2 (en) |
| BE (1) | BE868456A (en) |
| BR (1) | BR7804021A (en) |
| CA (1) | CA1103507A (en) |
| DE (1) | DE2728858C2 (en) |
| DK (1) | DK285578A (en) |
| ES (1) | ES471135A2 (en) |
| FI (1) | FI782028A (en) |
| FR (1) | FR2396337A2 (en) |
| GB (1) | GB1583330A (en) |
| IT (1) | IT7850029A0 (en) |
| NL (1) | NL7806816A (en) |
| NO (1) | NO782198L (en) |
| SE (1) | SE7807170L (en) |
| ZA (1) | ZA783642B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1249944A (en) * | 1984-06-08 | 1989-02-14 | Howard A. Fromson | Lithographic light trap and process |
| DE3714157A1 (en) * | 1987-04-28 | 1988-11-17 | Hans Grabensee | Method for offset printing and offset printing plate |
| DE3716848A1 (en) * | 1987-05-20 | 1988-12-01 | Hoechst Ag | METHOD FOR IMAGING LIGHT-SENSITIVE MATERIALS |
| US5814431A (en) | 1996-01-10 | 1998-09-29 | Mitsubishi Chemical Corporation | Photosensitive composition and lithographic printing plate |
| JP3814961B2 (en) | 1996-08-06 | 2006-08-30 | 三菱化学株式会社 | Positive photosensitive printing plate |
| ES2258416B1 (en) * | 2006-05-08 | 2008-03-01 | Luminosos Regui, S.A. | SYSTEM OF MANUFACTURE OF RELIEF LABELS. |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3396020A (en) * | 1965-11-16 | 1968-08-06 | Azoplate Corp | Planographic printing plate |
| ZA6807938B (en) * | 1967-12-04 | |||
| US3867147A (en) * | 1969-05-20 | 1975-02-18 | Hoechst Co American | Light-sensitive diazo compounds and reproduction material employing the same |
| US3664737A (en) * | 1971-03-23 | 1972-05-23 | Ibm | Printing plate recording by direct exposure |
| JPS5120922B2 (en) * | 1971-10-07 | 1976-06-29 | ||
| JPS5015603A (en) * | 1973-06-15 | 1975-02-19 | ||
| DE2537724C3 (en) * | 1975-08-25 | 1981-02-26 | Hoechst Ag, 6000 Frankfurt | Use of a process for the electrochemical roughening of aluminum in the production of planographic printing plate carriers |
| DE2547221A1 (en) * | 1975-10-22 | 1977-05-05 | Johannes Ruediger | Printing pressure plate exposure and burning in system - uses laser or electron beam heat radiation source for designs and words before or after picture composition for rapid working |
-
1977
- 1977-06-27 DE DE2728858A patent/DE2728858C2/en not_active Expired
-
1978
- 1978-05-31 GB GB24957/78A patent/GB1583330A/en not_active Expired
- 1978-06-06 AU AU36874/78A patent/AU521791B2/en not_active Expired
- 1978-06-21 JP JP7530678A patent/JPS5412907A/en active Granted
- 1978-06-22 SE SE7807170A patent/SE7807170L/en unknown
- 1978-06-23 NL NL7806816A patent/NL7806816A/en not_active Application Discontinuation
- 1978-06-23 CA CA306,161A patent/CA1103507A/en not_active Expired
- 1978-06-23 NO NO782198A patent/NO782198L/en unknown
- 1978-06-26 ES ES471135A patent/ES471135A2/en not_active Expired
- 1978-06-26 ZA ZA00783642A patent/ZA783642B/en unknown
- 1978-06-26 BR BR7804021A patent/BR7804021A/en unknown
- 1978-06-26 DK DK285578A patent/DK285578A/en unknown
- 1978-06-26 FR FR7818953A patent/FR2396337A2/en active Granted
- 1978-06-26 FI FI782028A patent/FI782028A/en not_active Application Discontinuation
- 1978-06-26 BE BE188841A patent/BE868456A/en not_active IP Right Cessation
- 1978-06-26 IT IT7850029A patent/IT7850029A0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FI782028A (en) | 1978-12-28 |
| BE868456A (en) | 1978-12-27 |
| FR2396337A2 (en) | 1979-01-26 |
| DK285578A (en) | 1978-12-28 |
| FR2396337B2 (en) | 1983-07-29 |
| ES471135A2 (en) | 1979-01-16 |
| NL7806816A (en) | 1978-12-29 |
| AU3687478A (en) | 1979-12-13 |
| BR7804021A (en) | 1979-04-03 |
| JPH0251732B2 (en) | 1990-11-08 |
| DE2728858A1 (en) | 1979-01-18 |
| NO782198L (en) | 1978-12-28 |
| ZA783642B (en) | 1979-06-27 |
| GB1583330A (en) | 1981-01-28 |
| SE7807170L (en) | 1978-12-28 |
| JPS5412907A (en) | 1979-01-31 |
| DE2728858C2 (en) | 1986-03-13 |
| AU521791B2 (en) | 1982-04-29 |
| IT7850029A0 (en) | 1978-06-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |