CA1145190A - Process for the development of exposed light-sensitive printing plates based on o-naphthoquinone-diazides - Google Patents
Process for the development of exposed light-sensitive printing plates based on o-naphthoquinone-diazidesInfo
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- CA1145190A CA1145190A CA000333265A CA333265A CA1145190A CA 1145190 A CA1145190 A CA 1145190A CA 000333265 A CA000333265 A CA 000333265A CA 333265 A CA333265 A CA 333265A CA 1145190 A CA1145190 A CA 1145190A
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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Printing Plates And Materials Therefor (AREA)
- Materials For Photolithography (AREA)
- Eye Examination Apparatus (AREA)
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
Abstract
Hoe 78/K 051 PROCESS FOR THE DEVELOPMENT OF EXPOSED
LIGHT-SENSITIVE PRINTING PLATES BASED ON
O-NAPHTHOQUINONE-DIAZIDES
Abstract of the Disclosure An improvement in the process for the development of ex-posed light-sensitive printing plates having a support of anodi-cally oxidized aluminum and a light-sensitive coating which con-tains an o-naphthoquinone-diazide and an alkali-soluble; resin, wherein the exposed areas of the coating are washed off with an aqueous-alkaline developer solution, the improvement comprising that the development is effected in the presence of an ionizable compound of an clement of the groups IIa, IIIa or IIIb of the Periodic Table. The ionizable compound can be contained in the developer solution or in the printing plate, and it has the effect of reducing the attack on the oxide layer.
LIGHT-SENSITIVE PRINTING PLATES BASED ON
O-NAPHTHOQUINONE-DIAZIDES
Abstract of the Disclosure An improvement in the process for the development of ex-posed light-sensitive printing plates having a support of anodi-cally oxidized aluminum and a light-sensitive coating which con-tains an o-naphthoquinone-diazide and an alkali-soluble; resin, wherein the exposed areas of the coating are washed off with an aqueous-alkaline developer solution, the improvement comprising that the development is effected in the presence of an ionizable compound of an clement of the groups IIa, IIIa or IIIb of the Periodic Table. The ionizable compound can be contained in the developer solution or in the printing plate, and it has the effect of reducing the attack on the oxide layer.
Description
1~45190 Hoe 78/~ 051 This invention relates to a process for the development of exposed 11ght-sensltive printing plates havlng a support composed of anodically oxidized aluminum and a light-sensitive coating which contains an o-naphthoquinone diazide and an alkali-soluble resin .
Printing plates of the generic type indicated are in general developed with aqueous-alkaline solutions, preferably solutions of buffer salts, the exposed areas of the coating being dissolved in the developer .
German Offenlegungsschrlft No. 2,507,503 describes a solu-tion of borates and monovalent metal cations for the development of coatings of this type, whlch are used as photoresist coatings.
Copper is indicated as the support materlal.
For the development of planographic printing plates having supports of aluminum, solutions of alkall metal phosphates or of alkall metal sillcates are used predominantly, as can be seen from German Patent No. 1,200,133.
For the development of light-curable, that is to say negative-working, printing plates, ln partlcular those based on lmlnoquinone dlazldes, German Patent No. 1,193,366 descrlbes an approprlate aqueous-alkaline solution which additlonally contalns certain polyvalent metal cations and, lf desired, a complex-forming agent. The advantage of these developers ls a reduced attack on the light-cured image stencil. Metallic aluminum or zinc and paper sheets are lndlcated as the support materlal for the coatlngs whlch are to be developed.
.r' Hoe 78/1~ 051 ll~Sl90 Finally, German Patent No. 2, 027, 467 describes the use of developer solutions of the last-mentioned type for the development of exposed photopolymerlzable coatings which have been applied to different supports, lnter alla to aluminum which, if appropriate, can be anodlcally oxidized. The patent gives no information about a special effect of the solution in the case of certain supports.
The initially mentioned developers, known for the develop-ment of posltive coatings, also have been recently used frequently for the planographic printing plates on anodically oxidized alumi-num as the support, whlch are preferred because of their high print-ing capaclty. In this case, fluctuations occurred in the quallty and the achieved runs of the printing forms, and initially it was not possible to explain these fluctuations.
Investigating this problem, it now has been found that these fluctuations are at least in part to be ascrlbed to the fact that the developers used attack the anodically produced oxide layer and partially erode it. This phenomenon of course depends upon the concentration or the pH of the developer solution, on the tem-perature of the developer and on the duration of actlon. It also has been found, however, that the attack on the oxlde ls particu-larly pronounced when the oxide layer has been subjected to a pretreatment, for example wlth vinylphosphonic acid or polyvinyl phosphonic acid, before applying the light-sensitive coating.
It is the object of the present invention to provide a pro-cess for the development of light-sensitive printing plates havlng a support composed of anodized aluminum and a light-sensitlve coating which contains an o-naphthoquinone diazide and an alkali-~1~51~
so:Luble resin, wherein the anodically produced oxide layer is attacked to a lesser extent and a higher printing run is thus ensured.
According to the present invention there is provided a process for the development of exposed light-sensitive printing plates having a support of anodically oxidized aluminum and a light-sensitive coating which contains an o-naphthoquinone-diazide and an alkali-soluble resin, the exposed areas of the coating being washed off with an aqueous-alkaline developer solution, which developer comprises 0.001 to 0.5% by weight of an ionizable compound of an element of the groups IIa, IIIa or IIIb of the Periodic Table in the form of water-soluble salts, oxides or hydroxides, wherein the salts are halides, sulfates, nitrates, formates, acetates, propionates, maleates, lactates, levulinates, malonates, adipates or fumarates.
The invention starts from a process for the development of exposed light-sensitive printing plates having a support of anodically oxidized aluminum and a light-sensitive coating which contains an o-naphthoquinone~diazide and an alkali-soluble resin, wherein the exposed areas of the coating are washcd off with an aqueous-alkaline developer solution.
The process according to the invention comprises effecting the development in the presence of an ioni~able compound of ~n element of the groups IIa, IIIa or IIIb of the Periodic Table.
The process can be carried out particularly simply and advantageously when the ionizable compound is added to the developer solution, It is also possible, however, that the ionizable compound is a priori a constituent of the light-sensitive printing plate and is arranged in the latter in such a way that, during the development, it is at least partially dissolved in the developer. The compound here can be contained either in the light-sensitive coating or in a ; - 3 -. , .
~145190 coating which is separate from the latter and which can lie above or below the light-sensitive coating. In an advantageous embodiment, fo:r example, this compound is applied conjointly with the above-mentioned pretreatment of the oxide layer with a vinylphosphonic acid.
' - 3a -Hoe 78/EC 051 11~51~0 If the compound ls a constituent of the prlntlng plate, lt generally can be contained therein ln quantities from 0 . 01 to 6, preferably 0.1 to 3, g/m . As a rule, the amounts used ln an undercoating are here smaller than in the llght~sensitive coating or in a top coatlng.
If the compound is added to the developer solution, the latter should contain about 0 . 001 to 0 . 5% by weight, preferably 0 . 01 to 0 . 3% by weight, of the ionizable compound .
The solubility of the compounds should be at least suf-ficient for reaching the desired concentration in the corresponding solutions. As an additive to the developer solution, water-soluble salts, oxides or hydroxides are preferably used. Suitable ioniz-able salts are in particular the halides, sulfates, nitrates, form-ates, acetates, propionates, maleates, lactates, levulinates, malonates, adipates or fumarates. The ionizable compounds of calcium, strontium or barium are particularly preferred.
To increase the solubill'y of the lonizable compounds, it is possible to add to the solution a small amount of a complex-forming agent, for example of an organic compound, which is capable of formlng a chelate compound, having a 5-membered or 6-membered rlng, with the corresponding cations.
Suitable complex-formlng agents are hydroxycarboxylic acids, amlnocarboxylic acids, enolizable polycarbonyl compounds, nitro-gen compound3 containing hydroxyl or carboxyl groups, and phenols. Examples of complex-forming agents of thls type are indicated in German Patent No. 1,193 ,366.
.
Hoe 78/K 051 The main constltuents of the aqueous developer solutlon are, in known manner, substances havlng an alkaline reaction, such as weak or strong lnorganic or organic alkalles, for exam-ple alkali metal salts of weak or moderately strong acids, such as water glass, sodium metasilicate, secondary or tertiary sodium or potassium phosphate, bases, such as sodium hydroxide or potassium hydroxide, diethylamine, ethanolamine or triethanol-amine. These alkaline compounds are, if desired, used in a mixture in which they have a buffer action. Their quantity is such that the pH of the solution i5 ln the range from about 10 . 5 to 14, preferably from 12 to 13.5. The water-soluble alkali metal silicates are particularly advantageous.
Moreover, the developer solutions can contain ionic or non-ionic surface-active compounds, anti-foaming agents and water-soluble high-molecular weight compounds for increasing the viscosity, for example polyglycols, polyvinyl alcohol, or cellu-lose ethers.
Preferably, the developer solution contains water as the only solvent. It is possible, however, to add small amounts, that is to say up to about 5% by weight, of organlc solvents which are miscible with water.
The copying materials, which are to be developed by the process accordlng to the inventlon, contain o-naphthoqulnone diazides, in particular esters or amldes of naphthoquinone-(1, 2~-diazide-(2)-sulfonic acid, as the light-sens$tive substances. The light-sensitlve coatings also contain alkali-soluble resins, for example phenolic resins, copolymers of acrylic acid or methacrylic - _ 5 _ .: . .
1145190 Hoe 78/K 051 acid, copolymers of malelc acld and other polymers contalning carboxyl groups. Phenollc resins, ln particular novolaks, are preferred .
Other posslble constltuents of the coatlng are minor amounts of alkali-insoluble resins, dyes, plasticizers, adhesion promoters and other customary additives.
The support used is aluminum which carries an anodically produced porous oxide layer. Advantageously, the aluminum ls mechanically, chemically or electrolytically roughened before anodizing. Anodizing is carried out in known manner, for exam-ple ln sulfuric acid or phosphoric acid, preferably under condi-tions such that an oxlde layer having a layer weight of about 0.5 to 10 g/m2 ls obtained. In an individual case, the thickness of the oxide layer depends upon the desired application. The mild developing process according to the inventlon makes it possible to manage wlth lower oxide layer thicknesses and hence to save time and costs.
Advantageously, the oxide layer is sub~ected, before apply-ing the l1ght-sensltive coating, to a pretreatment to lmprove the hydrophllic character thereof, for example a pretreatment with a vinylphosphonlc acid, in part~cular polyvlnyl phosphonic acid, such as is described, for example, in German Patent No, 1, 621, 478 .
The result of the inventlon is that, during the development of the copying material descrlbed, the oxide layer is attacked to a substantially lesser extent than in the case of using otherwlse identlcal developer solutions or copying materlals, whlch do not 1~5i~0 Hoe 73/K 051 contaln the lonizable compounds descrlbed above. Thls advantage manifests itself in particular ln the case of supports, the oxide layer of which has been pretreated in the manner indicated. With particular advantage, the process can be used for development in automatic developing devices, where it is not possible to treat relatively large non-image areas and areas with a relatively large image cover to different extents. A further advantage which par-ticularly manifests ltself here, ls the fact that the developer re-mains usable for a longer period because it is contaminated to a lesser extent by eroded alumina.
The invention is explained with the aid of the examples which follow, wherein parts by weight and parts by volume have the same relationship as g and ml. Unless otherwise stated, percentages are percent by weight.
ExamPle 1 0. 76 part by weight of the esterification product obtained from 1 mule of 2, 3, 4-trihydroxy-benzophenone and 3 moles of naphthoquinone-(1 ,2)-diazide-(2)-5-sulfonic acid chloride, 0.58 part by weight of the esterificatlon product from 1 mole of 2, 2 '-dihydroxy-dinaphthyl-(1 ,1 ' )-methane and 2 moles of naphthoquinone-(1 ,2)-diazide-(2)-5-sulfonic acid chloride, 0 .19 part by weight of naphthoquinone-(l, 2)-diazide-
Printing plates of the generic type indicated are in general developed with aqueous-alkaline solutions, preferably solutions of buffer salts, the exposed areas of the coating being dissolved in the developer .
German Offenlegungsschrlft No. 2,507,503 describes a solu-tion of borates and monovalent metal cations for the development of coatings of this type, whlch are used as photoresist coatings.
Copper is indicated as the support materlal.
For the development of planographic printing plates having supports of aluminum, solutions of alkall metal phosphates or of alkall metal sillcates are used predominantly, as can be seen from German Patent No. 1,200,133.
For the development of light-curable, that is to say negative-working, printing plates, ln partlcular those based on lmlnoquinone dlazldes, German Patent No. 1,193,366 descrlbes an approprlate aqueous-alkaline solution which additlonally contalns certain polyvalent metal cations and, lf desired, a complex-forming agent. The advantage of these developers ls a reduced attack on the light-cured image stencil. Metallic aluminum or zinc and paper sheets are lndlcated as the support materlal for the coatlngs whlch are to be developed.
.r' Hoe 78/1~ 051 ll~Sl90 Finally, German Patent No. 2, 027, 467 describes the use of developer solutions of the last-mentioned type for the development of exposed photopolymerlzable coatings which have been applied to different supports, lnter alla to aluminum which, if appropriate, can be anodlcally oxidized. The patent gives no information about a special effect of the solution in the case of certain supports.
The initially mentioned developers, known for the develop-ment of posltive coatings, also have been recently used frequently for the planographic printing plates on anodically oxidized alumi-num as the support, whlch are preferred because of their high print-ing capaclty. In this case, fluctuations occurred in the quallty and the achieved runs of the printing forms, and initially it was not possible to explain these fluctuations.
Investigating this problem, it now has been found that these fluctuations are at least in part to be ascrlbed to the fact that the developers used attack the anodically produced oxide layer and partially erode it. This phenomenon of course depends upon the concentration or the pH of the developer solution, on the tem-perature of the developer and on the duration of actlon. It also has been found, however, that the attack on the oxlde ls particu-larly pronounced when the oxide layer has been subjected to a pretreatment, for example wlth vinylphosphonic acid or polyvinyl phosphonic acid, before applying the light-sensitive coating.
It is the object of the present invention to provide a pro-cess for the development of light-sensitive printing plates havlng a support composed of anodized aluminum and a light-sensitlve coating which contains an o-naphthoquinone diazide and an alkali-~1~51~
so:Luble resin, wherein the anodically produced oxide layer is attacked to a lesser extent and a higher printing run is thus ensured.
According to the present invention there is provided a process for the development of exposed light-sensitive printing plates having a support of anodically oxidized aluminum and a light-sensitive coating which contains an o-naphthoquinone-diazide and an alkali-soluble resin, the exposed areas of the coating being washed off with an aqueous-alkaline developer solution, which developer comprises 0.001 to 0.5% by weight of an ionizable compound of an element of the groups IIa, IIIa or IIIb of the Periodic Table in the form of water-soluble salts, oxides or hydroxides, wherein the salts are halides, sulfates, nitrates, formates, acetates, propionates, maleates, lactates, levulinates, malonates, adipates or fumarates.
The invention starts from a process for the development of exposed light-sensitive printing plates having a support of anodically oxidized aluminum and a light-sensitive coating which contains an o-naphthoquinone~diazide and an alkali-soluble resin, wherein the exposed areas of the coating are washcd off with an aqueous-alkaline developer solution.
The process according to the invention comprises effecting the development in the presence of an ioni~able compound of ~n element of the groups IIa, IIIa or IIIb of the Periodic Table.
The process can be carried out particularly simply and advantageously when the ionizable compound is added to the developer solution, It is also possible, however, that the ionizable compound is a priori a constituent of the light-sensitive printing plate and is arranged in the latter in such a way that, during the development, it is at least partially dissolved in the developer. The compound here can be contained either in the light-sensitive coating or in a ; - 3 -. , .
~145190 coating which is separate from the latter and which can lie above or below the light-sensitive coating. In an advantageous embodiment, fo:r example, this compound is applied conjointly with the above-mentioned pretreatment of the oxide layer with a vinylphosphonic acid.
' - 3a -Hoe 78/EC 051 11~51~0 If the compound ls a constituent of the prlntlng plate, lt generally can be contained therein ln quantities from 0 . 01 to 6, preferably 0.1 to 3, g/m . As a rule, the amounts used ln an undercoating are here smaller than in the llght~sensitive coating or in a top coatlng.
If the compound is added to the developer solution, the latter should contain about 0 . 001 to 0 . 5% by weight, preferably 0 . 01 to 0 . 3% by weight, of the ionizable compound .
The solubility of the compounds should be at least suf-ficient for reaching the desired concentration in the corresponding solutions. As an additive to the developer solution, water-soluble salts, oxides or hydroxides are preferably used. Suitable ioniz-able salts are in particular the halides, sulfates, nitrates, form-ates, acetates, propionates, maleates, lactates, levulinates, malonates, adipates or fumarates. The ionizable compounds of calcium, strontium or barium are particularly preferred.
To increase the solubill'y of the lonizable compounds, it is possible to add to the solution a small amount of a complex-forming agent, for example of an organic compound, which is capable of formlng a chelate compound, having a 5-membered or 6-membered rlng, with the corresponding cations.
Suitable complex-formlng agents are hydroxycarboxylic acids, amlnocarboxylic acids, enolizable polycarbonyl compounds, nitro-gen compound3 containing hydroxyl or carboxyl groups, and phenols. Examples of complex-forming agents of thls type are indicated in German Patent No. 1,193 ,366.
.
Hoe 78/K 051 The main constltuents of the aqueous developer solutlon are, in known manner, substances havlng an alkaline reaction, such as weak or strong lnorganic or organic alkalles, for exam-ple alkali metal salts of weak or moderately strong acids, such as water glass, sodium metasilicate, secondary or tertiary sodium or potassium phosphate, bases, such as sodium hydroxide or potassium hydroxide, diethylamine, ethanolamine or triethanol-amine. These alkaline compounds are, if desired, used in a mixture in which they have a buffer action. Their quantity is such that the pH of the solution i5 ln the range from about 10 . 5 to 14, preferably from 12 to 13.5. The water-soluble alkali metal silicates are particularly advantageous.
Moreover, the developer solutions can contain ionic or non-ionic surface-active compounds, anti-foaming agents and water-soluble high-molecular weight compounds for increasing the viscosity, for example polyglycols, polyvinyl alcohol, or cellu-lose ethers.
Preferably, the developer solution contains water as the only solvent. It is possible, however, to add small amounts, that is to say up to about 5% by weight, of organlc solvents which are miscible with water.
The copying materials, which are to be developed by the process accordlng to the inventlon, contain o-naphthoqulnone diazides, in particular esters or amldes of naphthoquinone-(1, 2~-diazide-(2)-sulfonic acid, as the light-sens$tive substances. The light-sensitlve coatings also contain alkali-soluble resins, for example phenolic resins, copolymers of acrylic acid or methacrylic - _ 5 _ .: . .
1145190 Hoe 78/K 051 acid, copolymers of malelc acld and other polymers contalning carboxyl groups. Phenollc resins, ln particular novolaks, are preferred .
Other posslble constltuents of the coatlng are minor amounts of alkali-insoluble resins, dyes, plasticizers, adhesion promoters and other customary additives.
The support used is aluminum which carries an anodically produced porous oxide layer. Advantageously, the aluminum ls mechanically, chemically or electrolytically roughened before anodizing. Anodizing is carried out in known manner, for exam-ple ln sulfuric acid or phosphoric acid, preferably under condi-tions such that an oxlde layer having a layer weight of about 0.5 to 10 g/m2 ls obtained. In an individual case, the thickness of the oxide layer depends upon the desired application. The mild developing process according to the inventlon makes it possible to manage wlth lower oxide layer thicknesses and hence to save time and costs.
Advantageously, the oxide layer is sub~ected, before apply-ing the l1ght-sensltive coating, to a pretreatment to lmprove the hydrophllic character thereof, for example a pretreatment with a vinylphosphonlc acid, in part~cular polyvlnyl phosphonic acid, such as is described, for example, in German Patent No, 1, 621, 478 .
The result of the inventlon is that, during the development of the copying material descrlbed, the oxide layer is attacked to a substantially lesser extent than in the case of using otherwlse identlcal developer solutions or copying materlals, whlch do not 1~5i~0 Hoe 73/K 051 contaln the lonizable compounds descrlbed above. Thls advantage manifests itself in particular ln the case of supports, the oxide layer of which has been pretreated in the manner indicated. With particular advantage, the process can be used for development in automatic developing devices, where it is not possible to treat relatively large non-image areas and areas with a relatively large image cover to different extents. A further advantage which par-ticularly manifests ltself here, ls the fact that the developer re-mains usable for a longer period because it is contaminated to a lesser extent by eroded alumina.
The invention is explained with the aid of the examples which follow, wherein parts by weight and parts by volume have the same relationship as g and ml. Unless otherwise stated, percentages are percent by weight.
ExamPle 1 0. 76 part by weight of the esterification product obtained from 1 mule of 2, 3, 4-trihydroxy-benzophenone and 3 moles of naphthoquinone-(1 ,2)-diazide-(2)-5-sulfonic acid chloride, 0.58 part by weight of the esterificatlon product from 1 mole of 2, 2 '-dihydroxy-dinaphthyl-(1 ,1 ' )-methane and 2 moles of naphthoquinone-(1 ,2)-diazide-(2)-5-sulfonic acid chloride, 0 .19 part by weight of naphthoquinone-(l, 2)-diazide-
(2)-4-sulfonic acid chloride, 5.85 parts by weight of a cresol-formaldehyde novo-lak having a softening point of 105 - 120C
and 11~5~9~) Hoe 78/K 051 0.07 part by weight of Crystal Violet, are dissolved in a solvent mixture composed of 40 parts by weight of ethylene glycol monomethyl ether, 50 parts by weight of tetrahydrofuran, and 10 parts by weight of butyl acetate.
An electrolytically roughened and anodized aluminum plate with an oxide weight of 3 . 20 g/m2 is coated with this solution.
Before applying the light-sensitive copying coating, the anodized alumlnum support was treated with an aqueous solution of poly-vinyl phosphonic acid, a coating weight of 0 . 02 g/m2 being obtained .
The presensitized material prepared in this way -was expos-ed imagewise under a transparent positive original and then de-veloped with the following solution:
0 . 5 8 part by weight of sodium hydroxide, 4 . 86 parts by weight of sodlum metasilicate 9 H2O, 1 . 00 part by welght of polyglycol 200, 0.20 part by weight of aluminum sulfate, and 100 . 00 parts by weight of fully desalinated water.
The parts of the copying coating, which had been decom-posed by the light, are removed by the development, and the un-exposed image areas remain on the support, the (positive) print-ing stencil corresponding to the original being obtained. About 200, 000 perfect prints can be produced in an offset machine from the printing form thus prepared.
The different behavior of thls developer, as compared with an otherwise identical developer but without the additlon of 1145190 Hoe 78/~ 051 aluminum sulfate, is made particularly clear when the llght-sensitive printlng plate prepared accordlng to Example 1 is sub-jected to the action of the two developer solutlons for different lengths of time after the imagewise exposure. If the imagewise exposed printing form is treated in a rocking apparatus at about 23 C with the developer solution without the addition of the aluminum compound, an attack on the oxide already can be dls-cerned after 5 minutes in discrete areas of the sùpport surface where no image ls present. Finally, after 10 minutes, an attack on a large area of the oxide is clearly visible, and the oxide surface of the anodized support, which originally appears gray, has become lighter in the non-image areas and has been covered by a white coating.
By contrast, if the imagewise exposed printing form is treated under the same experimental conditions with the developer solution indicated above, that is to say in the presence of alumi-num ions, only a very slight attack on the oxide can be dis-cerned in the non-image areas even after an action lasting for 20 minutes .
Example 2 A printing plate prepared as ln Example 1, aiter imagewise exposure under a diapositive, is developed in known manner, us-ing a solution of the following composition:
7 . 20 parts by weight of sodium metasilicate 9 H2O, 0.02 part by weight of the sodium salt of the sulfuric acid ester of a fatty alcohol polyglycol ether, O. 01 part by weight of a commercially available anti-foaming agent (antifoam 60), 1145190 Hoe 78/~C 051 0 . 03 part by weight of strontium hydroxide, 0.06 part by welght of levulinic acid, and 92 . 68 parts by weight of fully desalinated water.
About 250, 000 perfect prints can be produced in an offset machine from the printing form thus obtained.
After thls developer has acted for 15 minutes at 23 C on the exposed printing plate, no erosion of oxide can be discerned.
By contrast, if the developer solution indicated above does not contaln any strontiu m ions, an extensive erosion tabout 44% by weight) of oxide in the non-image areas results under comparable experimental condltions. The attack on the printing stencil is also remarkable; this is very conspicuously vislble at the steps of a continuous tone step wedge which has been exposed at the same time. By contrast, this attack no longer can be seen on the step wedge, when the strontlum ions added to the developer In accordance wlth the lnventlon are present.
Example 3 :
A prlnting plate prepared as in Example 1, after imagewise ; ~ exposure under a diaposltive, is developed with a solution which contains 36.00 parts by welght of sodlum metasllicate . 9 H2O, 0.1 part by welght of the anlonic wetting agent Indicated ln Example 2, 0.05 part by weight of an antl-foamlng agent, ~; 464.00 parts by welght of fully desallnated water, and 1 . 5 parts by weight of a solution of 1 . 0 9 of levulinlc acld and 0.3 ~ of calclum hydroxide ln 15 ml of water.
11~5190 Hoe 78/~C 051 This corresponds to a content of about 3 . S mg of Ca+~ ln 100 ml. of developer solution.
In the printing press, the hydrophilic character of the background of the printing form thus obtained is excellent.
If the printing plate or the unsensitized support materlal is bathed for 15 minutes in the developer solution indicated above, there is no visible change of the aluminum surface.
By contrast, a corresponding developer solution without the addition of Ca++ ions results, in the same period, in a chalky, white coatlng on the surface of the aluminum due to chemical attack.
In the Examples 4 - 7 which follow, the procedure used corresponds to Examples 1 and 2, and similar results are obtained after the exposure and development of the light-sensitive printing plates obtained. Only the formulations of the coating solutions, the nature of the anodlzed support used and the composition of the corresponding developer solution are therefore indicated for the followlng examples, as far as necessary.
ExamPle 4 A printlng form prepared as in Example 1, after imagewlse exposure under a dlapositive, is developed in known manner, using a solution of the following composition:
4.5 parts by weight of sodium metasilicate 9 H2O, 0.5 part by weight of sodium hydroxide, 0.5 part by weight of boron-III oxide, and 95.0 parts by welght of fully desalinated water.
1145190 Hoe 78/k 051 Example 5 To prepare the coating solution, l . 20 parts by weight of the esterif~cation product obtained from l mole of the ethoxyethyl ester of 4,4-bis-(4-hydroxyphenyl)-n-valeric acld and 2 moles of naphthoquinone-(l ,2)-diazide-(2)-5-sulfonic acid chloride, 6 . 00 parts by weight of the novolak indicated in Example l, 0.19 part by weight of naphthoquinone-(1,2)-diazide-(2)~4-sulfonic acid chloride, and 0. 07 part by weight of Crystal Violet are dissolved in a solvent mixture composed of 40 parts by weight of ethylene glycol monomethyl ether, and 50 parts by weight of tetrahydrofuran.
Corresponding to Example l, an electrolytically roughened and anodized aluminum plate is coated with this solution. After imagewise exposure under a diaposltlve, the print1ng form ls de-Z0 veloped, uslng a developer of the followlng composltion:
2 . 5 0 parts by welght of sodium hydroxide, 22,5 parts by weight of sodlum metasilicate . 9 H2O, 1.0 part by weight of levulinlc acld, 0 . 25 part by welght of barlum chloride, and 475.00 parts by weight of fully desalinated water.
Exam~le 6 To prepare the coating solution, 11~5190 Hoe 78/~ 051 1. 00 part by welght of the 4-(a-a-dlmethylbenzyl)-phenyl ester of naphthoquinone-(l ,2)-dlazide-(2)-4-sulfonic acid, O . 49 part by weight of the esterificatlon product ob-tained from 1 mole of 2, 2 ' -dihydroxy-dinaphthyl-(1 ,l')-methane and 1 mole of naphthoquinone-(1 ,2)-diazide-(2)-5-sulfonic acld chloride, 0.21 part by weight of naphthoquinone-(1,2)-diazlde-(2)-4-sulfonic acid chloride, 0 . 07 part by weight of Crystal Violet base, and 5 . 80 parts by weight of the novolak indicated in Example 1 are dlssolved in a solvent mixture composed of 35 parts by weight of ethylene glycol monomethyl ether, 45 parts by weight of tetrahydrofuran, and 10 parts by weight of butyl acetate.
An electrolytically roughened and anodized aluminum plate havlng an oxide weight of 3,30 g/m2 is coated with this solutlon~
After imagewise exposure under a diapositive, the printing form is fully developed, using a developer of the foll~ring composition:
2 . 90 parts by weight of sodium hydroxide, 24 . 25 parts by welght of sodium metasilicate 9 H2O, S . 00 parts by weight of polyglycol 200, 0.50 part by weight of strontium chloride 6 H2O, 1. 00 part by weight of levulinic acid, and 475 . 00 parts by welght of fully desalinated water.
~1~5191) Hoe 78~K 051 ~xample 7 A printing plate prepared as ln Example 1, after imagewise exposure under a diapositive, is developed, using a solution of the following composition:
7. 20 parts by weight of sodlum metasilicate 9 H O, 0. 02 part by weight of the anionic wetting agent indicated ln Example 2, 0 . 01 part by welght of an anti-foam agent, 0 . 20 part by weight of lanthanum chloride, and 92.60 parts by weight of fully desalinated water.
Example 8 An electrochemlcally roughened and anodlzed aluminum printing plate, which is provLded with the same light-sensitive layer as in Example 6, is, after exposure under a positive film, developed in a commercially available developing machine. There are 15 llters of the solution indicated below in one of the two developer troughs, and 5 liters in the other. The last troush contains a 1% solution of phosphoric acid in fully desalinated water, The solutlons are sprayed by means of jets onto the prlnt-ing plate to be developed and are contlnuously clrculated.
DeveloPer solution:
0.58 part by weight of sodium hydroxide, 4 . ~6 parts by weight of sodium metasilicate 9 H2O, 1.00 part by weight of polyglycol 200, 0 . 007 part by weight of strontium chloride 6 H2O, and 100.00 parts by welght of fully desalinated water.
1~451~0 Hoe 78/~C 051 As the result of developlng, a printing form corresponding to the original is obtained. The oxlde weight of the original -not yet developed - aluminum printing plate is 2, 74 g/m2 After one pass through the machine, the oxide weight in the non-image areas is 2.52 g/m2 = 92% of the original value and, after 3 passes, is still 2.16 g/m = 79%. Wlthout strontium chloride in the developer solution, the erosion of oxide is substantially great-er. After 3 machine passes, printing plates are obtained which now have no more than 60 - 55% of the original oxide weight.
Exampl e 9 0 . 75 part by weight of the esterification product ob-tained from 1 mole of 2, 3, 4-trihydroxybenzo-phenone and 3 moles of naphthoquinone-(l ,2)-diazide-(2)-5-sulfonic acid chloride, 0.58 part by weight of the esterification product obtained from 1 mole of 2, 2 ' -dihydroxy-di-naphthyl-(l ,1 ')-methane and 2 moles of naph-thoquinone-(l ,2)-diazide~(2)-5-sulfonic acid chl orlde, 0.18 part by welght of naphthoquinone-(l ,2)-diazide-(2)-4-sulfonic acid chloride, 5 . 80 parts by weight of the cresol-formaldehyde novolak indicated in Example 1, 5.00 parts by weight of strontium chloride (w1th 6 mole s of water) and 0.07 part by weight of Crystal Violet are dlssolved ln a solvent mixture composed of Hoe 78/K 051 114~5190 40 parts by welght of ethylene glycol monomethyl ether, 5 0 parts by welght of tetrahydrofuran, and 10 parts by weight of butyl acetate.
An aluminum plate prepared and pretreated as in Example 1 is coated wlth this solution.
The presensitized material prepared in thls way ls exposed imagewlse under a transparent positive original and then develop-ed, uslng the following solution:
0.58 part by weight of sodium hydroxide, 4 . 85 parts by weight of sodium metasllicate 9 H2O, 1. 00 part by weight of polyglycol 200, and 100 . 00 parts by welght of fully desalinated water.
The different behavior of this developer towards the prlnt-ing plate prepared in this way, as compared with an otherwise identical printing plate, but without the addition of strontium chloride 6 H2O, is made clea. when the correspondlng printing plates are subjected for a period of 5 to 10 minutes to the action of the developer solution after the lmagewise exposure. Whlle a severe attack on the oxlde and the coating is discernible after 10 minutes in the copying coating of the printing plate without a strontium salt, the printing plate with the copying coating con-tainlng strontium chloride shows no attack on the oxide in the non-image areas.
ExamPle 10 A copying coating of the following compositlon, in percent by weight:
Hoe 78/K 051 119~5190 10.16 parts by welght of the esterlflcation product obtalned from 1 mole of 2, 3, 4-trihydroxy-benzophenone and 3 moles of naphthoquinone-(1, 2)-diazide-(2)-S-sulfonlc acid chloride, 7 . 86 parts by weight of the esterification product obtained from 1 mole of 2, 2'-dihydroxy-dl-naphthyl-(l ,l')-methane and 2 moles of naphthoquinone-(l, 2)-diazlde-(2)-5-sulfonic acid chloride, 2 .43 parts by weight of naphthoqulnone-(l ,2)-diazide-4-suifonic acld chloride, 78 . 60 parts by weight of the cresol/formaldehyde novolak indicated in Example 1, and 0.95 part by weight of Crystal Violet is applied to an electrochemically roughened and anodized alumi-num support which had been treated beforehand with a 0.3% aque-ous solution of polyvinyl phosphonic acid. A solution of S.53 parts by weight of polyvinyl alcohol (K value 8; 12% of residual acetyl groups), 1.40 parts by weight of polyvinyl pyrrolidone, ; ~ 0.07 part by weight of a fatty alcohol polyglycol ether, and 5.00 parts by weight of strontium chlor~de 6 H2O
ln88 . 00 parts by weight of fully desalinated water ls then applied to the copying coating and the whole is dried.
The presensltlzed material prepared in this way is exposed imagewise under a transparent positive origlnal and subsequently developed, uslng the same developer as in Example 9.
11a~5190 Hoe 78/K 051 The different behavior of these printlng plates havlng a top coating containlng a strontium salt, as compared w1th a corre-sponding printing plate wlthout a content of a strontium salt, ls made particularly clear when the two prlnting plates are bathed in the developer for about 10 - 15 minutes. Already after 10 min-utes ' treatment, the skontium-free printing plate shows a marked attack on the oxide, while the printing plate having the top coat-ing contalning strontium is still perfect even after 15 minutes' treatment with the developer.
Example 11 An electrochemically roughened and anodized aluminum plate 1s treated at 60 C for one minute with an aqueous solution of 5 . 0% by welght of strontium chloride 6 H2O and 0 . 3% by weight of polyvinyl phosphonic acid .
The excess is wiped off and, after drying, the Al plate pretreated in this way Is coated with a sGlution of 0 . 75 part by weight of the esterification product obtained from 1 mole of 2, 3, 4-trihydroxy-benzophenone and 3 moles of naphthoqul-none-(l ,2)-diazide-(2)-5-sulfonlc acid chloride, 0.58 part by weight of the esterification product obtained from 1 mole of 2, 2 ' -dihydroxy-dinaphthyl-(l ,1 ') methane and 2 moies of naphthoquinone-(l, 2)~diazide-(2)-5-sulfonlc acld chloride, Hoe 78/h 051 11~5190 0.18 part by weight of naphthoquinone-(1,2)-diazide-(2)-4-sulfonlc acid chloride, 5 . 80 parts by weight of the cresol/formaldehyde novolak indicated in Example 1, and 0.07 part by weight of Crystal Violet in a solvent mixture composed of 40 parts by weight of ethylene glycol mono-methyl ether, 50 parts by weight of tetrahydrofuran, and 10 parts by weight of butyl acetate and is then dried.
The light-sensitive printing plate prepared in this way is exposed imagewise under a transparent positive original and de-veloped with the developer lndicated in Example 9.
Even after 15 minutes ' action of the developer, no attack ` ~ ~ on the oxide in the non-image areas is discernible. However, if a corresponding printing plate is prepared in which the precoating does not contain any strontlum salt, a marked attack on the oxlde is already discernlble after 10 minutes' action of the same de-2 0 veloper .
It will be obvious to those skilled in the art that many modifications may be made within the scope of the present lnven-tion without departing from the spirit thereof, and the lnvention lncludes all such modifications.
" . . . ~ ~. - ~ .
and 11~5~9~) Hoe 78/K 051 0.07 part by weight of Crystal Violet, are dissolved in a solvent mixture composed of 40 parts by weight of ethylene glycol monomethyl ether, 50 parts by weight of tetrahydrofuran, and 10 parts by weight of butyl acetate.
An electrolytically roughened and anodized aluminum plate with an oxide weight of 3 . 20 g/m2 is coated with this solution.
Before applying the light-sensitive copying coating, the anodized alumlnum support was treated with an aqueous solution of poly-vinyl phosphonic acid, a coating weight of 0 . 02 g/m2 being obtained .
The presensitized material prepared in this way -was expos-ed imagewise under a transparent positive original and then de-veloped with the following solution:
0 . 5 8 part by weight of sodium hydroxide, 4 . 86 parts by weight of sodlum metasilicate 9 H2O, 1 . 00 part by welght of polyglycol 200, 0.20 part by weight of aluminum sulfate, and 100 . 00 parts by weight of fully desalinated water.
The parts of the copying coating, which had been decom-posed by the light, are removed by the development, and the un-exposed image areas remain on the support, the (positive) print-ing stencil corresponding to the original being obtained. About 200, 000 perfect prints can be produced in an offset machine from the printing form thus prepared.
The different behavior of thls developer, as compared with an otherwise identical developer but without the additlon of 1145190 Hoe 78/~ 051 aluminum sulfate, is made particularly clear when the llght-sensitive printlng plate prepared accordlng to Example 1 is sub-jected to the action of the two developer solutlons for different lengths of time after the imagewise exposure. If the imagewise exposed printing form is treated in a rocking apparatus at about 23 C with the developer solution without the addition of the aluminum compound, an attack on the oxide already can be dls-cerned after 5 minutes in discrete areas of the sùpport surface where no image ls present. Finally, after 10 minutes, an attack on a large area of the oxide is clearly visible, and the oxide surface of the anodized support, which originally appears gray, has become lighter in the non-image areas and has been covered by a white coating.
By contrast, if the imagewise exposed printing form is treated under the same experimental conditions with the developer solution indicated above, that is to say in the presence of alumi-num ions, only a very slight attack on the oxide can be dis-cerned in the non-image areas even after an action lasting for 20 minutes .
Example 2 A printing plate prepared as ln Example 1, aiter imagewise exposure under a diapositive, is developed in known manner, us-ing a solution of the following composition:
7 . 20 parts by weight of sodium metasilicate 9 H2O, 0.02 part by weight of the sodium salt of the sulfuric acid ester of a fatty alcohol polyglycol ether, O. 01 part by weight of a commercially available anti-foaming agent (antifoam 60), 1145190 Hoe 78/~C 051 0 . 03 part by weight of strontium hydroxide, 0.06 part by welght of levulinic acid, and 92 . 68 parts by weight of fully desalinated water.
About 250, 000 perfect prints can be produced in an offset machine from the printing form thus obtained.
After thls developer has acted for 15 minutes at 23 C on the exposed printing plate, no erosion of oxide can be discerned.
By contrast, if the developer solution indicated above does not contaln any strontiu m ions, an extensive erosion tabout 44% by weight) of oxide in the non-image areas results under comparable experimental condltions. The attack on the printing stencil is also remarkable; this is very conspicuously vislble at the steps of a continuous tone step wedge which has been exposed at the same time. By contrast, this attack no longer can be seen on the step wedge, when the strontlum ions added to the developer In accordance wlth the lnventlon are present.
Example 3 :
A prlnting plate prepared as in Example 1, after imagewise ; ~ exposure under a diaposltive, is developed with a solution which contains 36.00 parts by welght of sodlum metasllicate . 9 H2O, 0.1 part by welght of the anlonic wetting agent Indicated ln Example 2, 0.05 part by weight of an antl-foamlng agent, ~; 464.00 parts by welght of fully desallnated water, and 1 . 5 parts by weight of a solution of 1 . 0 9 of levulinlc acld and 0.3 ~ of calclum hydroxide ln 15 ml of water.
11~5190 Hoe 78/~C 051 This corresponds to a content of about 3 . S mg of Ca+~ ln 100 ml. of developer solution.
In the printing press, the hydrophilic character of the background of the printing form thus obtained is excellent.
If the printing plate or the unsensitized support materlal is bathed for 15 minutes in the developer solution indicated above, there is no visible change of the aluminum surface.
By contrast, a corresponding developer solution without the addition of Ca++ ions results, in the same period, in a chalky, white coatlng on the surface of the aluminum due to chemical attack.
In the Examples 4 - 7 which follow, the procedure used corresponds to Examples 1 and 2, and similar results are obtained after the exposure and development of the light-sensitive printing plates obtained. Only the formulations of the coating solutions, the nature of the anodlzed support used and the composition of the corresponding developer solution are therefore indicated for the followlng examples, as far as necessary.
ExamPle 4 A printlng form prepared as in Example 1, after imagewlse exposure under a dlapositive, is developed in known manner, using a solution of the following composition:
4.5 parts by weight of sodium metasilicate 9 H2O, 0.5 part by weight of sodium hydroxide, 0.5 part by weight of boron-III oxide, and 95.0 parts by welght of fully desalinated water.
1145190 Hoe 78/k 051 Example 5 To prepare the coating solution, l . 20 parts by weight of the esterif~cation product obtained from l mole of the ethoxyethyl ester of 4,4-bis-(4-hydroxyphenyl)-n-valeric acld and 2 moles of naphthoquinone-(l ,2)-diazide-(2)-5-sulfonic acid chloride, 6 . 00 parts by weight of the novolak indicated in Example l, 0.19 part by weight of naphthoquinone-(1,2)-diazide-(2)~4-sulfonic acid chloride, and 0. 07 part by weight of Crystal Violet are dissolved in a solvent mixture composed of 40 parts by weight of ethylene glycol monomethyl ether, and 50 parts by weight of tetrahydrofuran.
Corresponding to Example l, an electrolytically roughened and anodized aluminum plate is coated with this solution. After imagewise exposure under a diaposltlve, the print1ng form ls de-Z0 veloped, uslng a developer of the followlng composltion:
2 . 5 0 parts by welght of sodium hydroxide, 22,5 parts by weight of sodlum metasilicate . 9 H2O, 1.0 part by weight of levulinlc acld, 0 . 25 part by welght of barlum chloride, and 475.00 parts by weight of fully desalinated water.
Exam~le 6 To prepare the coating solution, 11~5190 Hoe 78/~ 051 1. 00 part by welght of the 4-(a-a-dlmethylbenzyl)-phenyl ester of naphthoquinone-(l ,2)-dlazide-(2)-4-sulfonic acid, O . 49 part by weight of the esterificatlon product ob-tained from 1 mole of 2, 2 ' -dihydroxy-dinaphthyl-(1 ,l')-methane and 1 mole of naphthoquinone-(1 ,2)-diazide-(2)-5-sulfonic acld chloride, 0.21 part by weight of naphthoquinone-(1,2)-diazlde-(2)-4-sulfonic acid chloride, 0 . 07 part by weight of Crystal Violet base, and 5 . 80 parts by weight of the novolak indicated in Example 1 are dlssolved in a solvent mixture composed of 35 parts by weight of ethylene glycol monomethyl ether, 45 parts by weight of tetrahydrofuran, and 10 parts by weight of butyl acetate.
An electrolytically roughened and anodized aluminum plate havlng an oxide weight of 3,30 g/m2 is coated with this solutlon~
After imagewise exposure under a diapositive, the printing form is fully developed, using a developer of the foll~ring composition:
2 . 90 parts by weight of sodium hydroxide, 24 . 25 parts by welght of sodium metasilicate 9 H2O, S . 00 parts by weight of polyglycol 200, 0.50 part by weight of strontium chloride 6 H2O, 1. 00 part by weight of levulinic acid, and 475 . 00 parts by welght of fully desalinated water.
~1~5191) Hoe 78~K 051 ~xample 7 A printing plate prepared as ln Example 1, after imagewise exposure under a diapositive, is developed, using a solution of the following composition:
7. 20 parts by weight of sodlum metasilicate 9 H O, 0. 02 part by weight of the anionic wetting agent indicated ln Example 2, 0 . 01 part by welght of an anti-foam agent, 0 . 20 part by weight of lanthanum chloride, and 92.60 parts by weight of fully desalinated water.
Example 8 An electrochemlcally roughened and anodlzed aluminum printing plate, which is provLded with the same light-sensitive layer as in Example 6, is, after exposure under a positive film, developed in a commercially available developing machine. There are 15 llters of the solution indicated below in one of the two developer troughs, and 5 liters in the other. The last troush contains a 1% solution of phosphoric acid in fully desalinated water, The solutlons are sprayed by means of jets onto the prlnt-ing plate to be developed and are contlnuously clrculated.
DeveloPer solution:
0.58 part by weight of sodium hydroxide, 4 . ~6 parts by weight of sodium metasilicate 9 H2O, 1.00 part by weight of polyglycol 200, 0 . 007 part by weight of strontium chloride 6 H2O, and 100.00 parts by welght of fully desalinated water.
1~451~0 Hoe 78/~C 051 As the result of developlng, a printing form corresponding to the original is obtained. The oxlde weight of the original -not yet developed - aluminum printing plate is 2, 74 g/m2 After one pass through the machine, the oxide weight in the non-image areas is 2.52 g/m2 = 92% of the original value and, after 3 passes, is still 2.16 g/m = 79%. Wlthout strontium chloride in the developer solution, the erosion of oxide is substantially great-er. After 3 machine passes, printing plates are obtained which now have no more than 60 - 55% of the original oxide weight.
Exampl e 9 0 . 75 part by weight of the esterification product ob-tained from 1 mole of 2, 3, 4-trihydroxybenzo-phenone and 3 moles of naphthoquinone-(l ,2)-diazide-(2)-5-sulfonic acid chloride, 0.58 part by weight of the esterification product obtained from 1 mole of 2, 2 ' -dihydroxy-di-naphthyl-(l ,1 ')-methane and 2 moles of naph-thoquinone-(l ,2)-diazide~(2)-5-sulfonic acid chl orlde, 0.18 part by welght of naphthoquinone-(l ,2)-diazide-(2)-4-sulfonic acid chloride, 5 . 80 parts by weight of the cresol-formaldehyde novolak indicated in Example 1, 5.00 parts by weight of strontium chloride (w1th 6 mole s of water) and 0.07 part by weight of Crystal Violet are dlssolved ln a solvent mixture composed of Hoe 78/K 051 114~5190 40 parts by welght of ethylene glycol monomethyl ether, 5 0 parts by welght of tetrahydrofuran, and 10 parts by weight of butyl acetate.
An aluminum plate prepared and pretreated as in Example 1 is coated wlth this solution.
The presensitized material prepared in thls way ls exposed imagewlse under a transparent positive original and then develop-ed, uslng the following solution:
0.58 part by weight of sodium hydroxide, 4 . 85 parts by weight of sodium metasllicate 9 H2O, 1. 00 part by weight of polyglycol 200, and 100 . 00 parts by welght of fully desalinated water.
The different behavior of this developer towards the prlnt-ing plate prepared in this way, as compared with an otherwise identical printing plate, but without the addition of strontium chloride 6 H2O, is made clea. when the correspondlng printing plates are subjected for a period of 5 to 10 minutes to the action of the developer solution after the lmagewise exposure. Whlle a severe attack on the oxlde and the coating is discernible after 10 minutes in the copying coating of the printing plate without a strontium salt, the printing plate with the copying coating con-tainlng strontium chloride shows no attack on the oxide in the non-image areas.
ExamPle 10 A copying coating of the following compositlon, in percent by weight:
Hoe 78/K 051 119~5190 10.16 parts by welght of the esterlflcation product obtalned from 1 mole of 2, 3, 4-trihydroxy-benzophenone and 3 moles of naphthoquinone-(1, 2)-diazide-(2)-S-sulfonlc acid chloride, 7 . 86 parts by weight of the esterification product obtained from 1 mole of 2, 2'-dihydroxy-dl-naphthyl-(l ,l')-methane and 2 moles of naphthoquinone-(l, 2)-diazlde-(2)-5-sulfonic acid chloride, 2 .43 parts by weight of naphthoqulnone-(l ,2)-diazide-4-suifonic acld chloride, 78 . 60 parts by weight of the cresol/formaldehyde novolak indicated in Example 1, and 0.95 part by weight of Crystal Violet is applied to an electrochemically roughened and anodized alumi-num support which had been treated beforehand with a 0.3% aque-ous solution of polyvinyl phosphonic acid. A solution of S.53 parts by weight of polyvinyl alcohol (K value 8; 12% of residual acetyl groups), 1.40 parts by weight of polyvinyl pyrrolidone, ; ~ 0.07 part by weight of a fatty alcohol polyglycol ether, and 5.00 parts by weight of strontium chlor~de 6 H2O
ln88 . 00 parts by weight of fully desalinated water ls then applied to the copying coating and the whole is dried.
The presensltlzed material prepared in this way is exposed imagewise under a transparent positive origlnal and subsequently developed, uslng the same developer as in Example 9.
11a~5190 Hoe 78/K 051 The different behavior of these printlng plates havlng a top coating containlng a strontium salt, as compared w1th a corre-sponding printing plate wlthout a content of a strontium salt, ls made particularly clear when the two prlnting plates are bathed in the developer for about 10 - 15 minutes. Already after 10 min-utes ' treatment, the skontium-free printing plate shows a marked attack on the oxide, while the printing plate having the top coat-ing contalning strontium is still perfect even after 15 minutes' treatment with the developer.
Example 11 An electrochemically roughened and anodized aluminum plate 1s treated at 60 C for one minute with an aqueous solution of 5 . 0% by welght of strontium chloride 6 H2O and 0 . 3% by weight of polyvinyl phosphonic acid .
The excess is wiped off and, after drying, the Al plate pretreated in this way Is coated with a sGlution of 0 . 75 part by weight of the esterification product obtained from 1 mole of 2, 3, 4-trihydroxy-benzophenone and 3 moles of naphthoqul-none-(l ,2)-diazide-(2)-5-sulfonlc acid chloride, 0.58 part by weight of the esterification product obtained from 1 mole of 2, 2 ' -dihydroxy-dinaphthyl-(l ,1 ') methane and 2 moies of naphthoquinone-(l, 2)~diazide-(2)-5-sulfonlc acld chloride, Hoe 78/h 051 11~5190 0.18 part by weight of naphthoquinone-(1,2)-diazide-(2)-4-sulfonlc acid chloride, 5 . 80 parts by weight of the cresol/formaldehyde novolak indicated in Example 1, and 0.07 part by weight of Crystal Violet in a solvent mixture composed of 40 parts by weight of ethylene glycol mono-methyl ether, 50 parts by weight of tetrahydrofuran, and 10 parts by weight of butyl acetate and is then dried.
The light-sensitive printing plate prepared in this way is exposed imagewise under a transparent positive original and de-veloped with the developer lndicated in Example 9.
Even after 15 minutes ' action of the developer, no attack ` ~ ~ on the oxide in the non-image areas is discernible. However, if a corresponding printing plate is prepared in which the precoating does not contain any strontlum salt, a marked attack on the oxlde is already discernlble after 10 minutes' action of the same de-2 0 veloper .
It will be obvious to those skilled in the art that many modifications may be made within the scope of the present lnven-tion without departing from the spirit thereof, and the lnvention lncludes all such modifications.
" . . . ~ ~. - ~ .
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Process for the development of exposed light-sensitive printing plates having a support of anodically oxidized aluminum and a light-sensitive coating which contains an o-naphthoquinone-diazide and an alkali-soluble resin, the exposed areas of the coating being washed off with an aqueous-alkaline developer solution, which developer comprises 0.001 to 0.5% by weight of an ionizable compound of an element of the groups IIa, IIIa or IIIb of the Periodic Table in the form of water-soluble salts, oxides or hydroxides, wherein the salts are halides, sulfates, nitrates, formates, acetates, propionates, maleates, lactates, levulinates, malonates, adipates or fumarates.
2. A process as claimed in claim 1 wherein the ionizable compound is a compound of calcium, strontium or barium.
3. A process as claimed in claim 1 wherein additionally a compound is used which is capable of forming complexes with the cations of the ionizable compound.
4, A process as claimed in claim 1 wherein the developer solution has a pH from 10.5 to 14.
5. A process as claimed in claim 1 wherein the anodically produced oxide layer of the support is pretreated with a solution of vinylphosphonic acid or polyvinyl phosphonic acid before applying the light-sensitive coating.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782834958 DE2834958A1 (en) | 1978-08-10 | 1978-08-10 | METHOD FOR DEVELOPING EXPOSED LIGHT-SENSITIVE PRINTING PLATES |
| DEP2834958.8 | 1978-08-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1145190A true CA1145190A (en) | 1983-04-26 |
Family
ID=6046629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000333265A Expired CA1145190A (en) | 1978-08-10 | 1979-08-07 | Process for the development of exposed light-sensitive printing plates based on o-naphthoquinone-diazides |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0008394B1 (en) |
| JP (1) | JPS5525100A (en) |
| AT (1) | ATE2637T1 (en) |
| AU (1) | AU531673B2 (en) |
| BR (2) | BR7905131A (en) |
| CA (1) | CA1145190A (en) |
| DE (2) | DE2834958A1 (en) |
| ES (1) | ES483328A1 (en) |
| FI (1) | FI69716C (en) |
| ZA (1) | ZA794131B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4500625A (en) * | 1982-11-05 | 1985-02-19 | Fuji Photo Film Co., Ltd. | Developer for light-sensitive lithographic printing plate precursor |
| US4931103A (en) * | 1988-08-11 | 1990-06-05 | E. I. Du Pont De Nemours And Company | Tricholine phosphate surface treating agent |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5752053A (en) * | 1980-09-12 | 1982-03-27 | Asahi Chem Ind Co Ltd | Manufacture of photosensitive resin plate |
| US4330614A (en) * | 1980-10-14 | 1982-05-18 | International Business Machines Corporation | Process for forming a patterned resist mask |
| DE3126636A1 (en) | 1981-07-06 | 1983-01-27 | Hoechst Ag, 6000 Frankfurt | HYDROPHILIZED CARRIER MATERIALS FOR OFFSET PRINTING PLATES, A METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DE3126626A1 (en) | 1981-07-06 | 1983-01-20 | Hoechst Ag, 6000 Frankfurt | HYDROPHILIZED CARRIER MATERIALS FOR OFFSET PRINTING PLATES, A METHOD FOR THEIR PRODUCTION AND THEIR USE |
| JPS5854341A (en) * | 1981-09-28 | 1983-03-31 | Fuji Photo Film Co Ltd | Developing method and developing solution |
| JPS58190952A (en) * | 1982-04-30 | 1983-11-08 | Fuji Photo Film Co Ltd | Developing solution of photosensitive printing plate |
| DE3230171A1 (en) * | 1982-08-13 | 1984-02-16 | Hoechst Ag, 6230 Frankfurt | AQUEOUS ALKALINE SOLUTION AND METHOD FOR DEVELOPING POSITIVE WORKING REPRODUCTION LAYERS |
| JPS5955438A (en) * | 1982-09-24 | 1984-03-30 | Konishiroku Photo Ind Co Ltd | Photoengraving method |
| JPS59121336A (en) * | 1982-12-28 | 1984-07-13 | Fuji Photo Film Co Ltd | Developing solution for photosensitive lithographic printing plate |
| JPS6088945A (en) * | 1983-10-20 | 1985-05-18 | Toyobo Co Ltd | Aqueous processing solution for image copying material |
| JPS61203456A (en) * | 1985-03-06 | 1986-09-09 | Fuotopori Ouka Kk | Formation of pattern |
| EP0732628A1 (en) | 1995-03-07 | 1996-09-18 | Minnesota Mining And Manufacturing Company | Aqueous alkaline solution for developing offset printing plate |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB772112A (en) * | 1955-07-04 | 1957-04-10 | Warren S D Co | Coated paper product for planographic printing masters |
| BE581434A (en) * | 1958-08-08 | |||
| BE606642A (en) * | 1960-07-29 | |||
| ZA6807938B (en) * | 1967-12-04 | |||
| CA1001473A (en) * | 1972-12-22 | 1976-12-14 | Eastman Kodak Company | Lithographic printing plate |
| JPS50108005A (en) * | 1974-01-31 | 1975-08-26 | ||
| CA1035189A (en) * | 1974-02-26 | 1978-07-25 | Richard R. Wells | Developer for photosensitive coatings |
-
1978
- 1978-08-10 DE DE19782834958 patent/DE2834958A1/en not_active Withdrawn
-
1979
- 1979-08-02 DE DE7979102769T patent/DE2964899D1/en not_active Expired
- 1979-08-02 AT AT79102769T patent/ATE2637T1/en not_active IP Right Cessation
- 1979-08-02 EP EP79102769A patent/EP0008394B1/en not_active Expired
- 1979-08-07 CA CA000333265A patent/CA1145190A/en not_active Expired
- 1979-08-08 FI FI792465A patent/FI69716C/en not_active IP Right Cessation
- 1979-08-08 ZA ZA00794131A patent/ZA794131B/en unknown
- 1979-08-09 JP JP10081379A patent/JPS5525100A/en active Granted
- 1979-08-09 AU AU49757/79A patent/AU531673B2/en not_active Ceased
- 1979-08-09 BR BR7905131A patent/BR7905131A/en not_active IP Right Cessation
- 1979-08-10 ES ES483328A patent/ES483328A1/en not_active Expired
- 1979-08-10 BR BR7905153A patent/BR7905153A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4500625A (en) * | 1982-11-05 | 1985-02-19 | Fuji Photo Film Co., Ltd. | Developer for light-sensitive lithographic printing plate precursor |
| US4931103A (en) * | 1988-08-11 | 1990-06-05 | E. I. Du Pont De Nemours And Company | Tricholine phosphate surface treating agent |
Also Published As
| Publication number | Publication date |
|---|---|
| AU531673B2 (en) | 1983-09-01 |
| ATE2637T1 (en) | 1983-03-15 |
| BR7905131A (en) | 1980-05-06 |
| FI69716C (en) | 1986-03-10 |
| ES483328A1 (en) | 1980-04-16 |
| DE2964899D1 (en) | 1983-03-31 |
| BR7905153A (en) | 1980-05-06 |
| FI69716B (en) | 1985-11-29 |
| JPH0258618B2 (en) | 1990-12-10 |
| FI792465A (en) | 1980-02-11 |
| AU4975779A (en) | 1980-02-14 |
| EP0008394A1 (en) | 1980-03-05 |
| EP0008394B1 (en) | 1983-02-23 |
| JPS5525100A (en) | 1980-02-22 |
| ZA794131B (en) | 1980-08-27 |
| DE2834958A1 (en) | 1980-02-21 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |