Activator solution containing copper (II) ions, halide and a mild oxidizing agent
United States Patent 1191 Blake 1 [451 Apr. 15, 1975 1 1 ACTIVATOR SOLUTION CONTAINING [56] References Cited COPPER (II) IONS, HALIDE AND A MILD UNITED STATES PATENTS OXIDIZING AGENT 3,083,097 3/1963 Lassig et 81.. 96 33 75 Inventor: Ralph Kingsley Blake, westfield 3,257,941 6/1966 Wolfson et a1. 96/29 L NJ 3,561,961 2/1971 Blake 96/33 3,625,687 12/1971 Dunkle 96/33 [73] Assignee: E. I. du Pont de Nemours and 3,676,125 7/1972 de Hanes et a1. 96/29 L Company, Wilmington, Del. Filed Nov 15 l97&#39;2 Primary ExaminerDavid Klein [21] App]. No.: 306,620 [57] ABSTRACT Related Application Data A lithographic printing plate having an ink-receptive Division of Ser No 60 619 Au 3 1970 Pat No image comprising a hydrophilic colloid binder, an in- 3 736 871 which isaco ntinuatbiin art of Ser No Soluble Salt or complex of copper (I) wlth an 0160- b 8 1969 abandoned p philogenic compound, and metallic silver is made by treating a hydrophilic colloid-silver image with an acti- [52] U S C] 252/186, 96/29 96/33 vator containing cupric ions and said oleophilogenic [51] i 13/00 compound. Activators are aqueous solutions contain- [58] Field of Search 96/33, 29 L; 252/186 mg (11) and a 7 Claims, No Drawings ACTIVATOR SOLUTION CONTAINING COPPER (II) IONS, HALIDE AND A MILD OXIDIZING AGENT CROSS REFERENCE TO RELATED APPLICATIONS This application is a division of application Ser. No. 60,619 filed Aug. 3, 1970. now U.S. Pat. No. 3,736,871 which is a continuation-in-part of application Ser. No. 864,867, filed Oct. 8, 1969, now abandoned.  
  An element useful in making images of the type disclosed in this application is described in Assignees copending application by Blake, filed Aug. 4, 1969, Ser. No. 847,399, now U.S. Pat. No. 3,635,399, which also discloses activator solutions.  
 BACKGROUND OF THE INVENTION This invention relates to lithographic printing plates and more particularly to improved colloid lithographic plates. Still more particularly it relates to lithographic images on colloid plates having improved quality and press life.  
  Methods of preparing lithographic images from gelatino-silver images are well known.  
  An exposed gelatino-silver halide emulsion layer may be treated with a tanning developer which hardens the gelatin in the imaged areas and makes it ink-receptive. In the bromoil process oleophilic hardened gelatin images are produced by treating a gelatino-silver image (produced by conventional photographic methods) with a tanning bleach which hardens the gelatin in the silver image areas of the layer but does not affect those portions of the gelatin layer having no silver. The silver in a gelatino-silver image may also be used to catalyze the oxidative degradation of the gelatin in the imaged areas so that it can be washed away to reveal an oleophilic underlayer.  
  Lassig, et al., U.S. Pat. No. 3,083,097 disclose a process for making a lithographic image from a gelatinosilver image by converting the silver image into an image of heavy metal and/r silver compounds and reacting these with sparingly soluble organic compounds containing SH. SeH, OH, or NH groups to form organic salt-like or complex compounds which are less soluble than the original products of oxidation. The presence of the organic salt-like or complex compounds makes the imaged areas oleophilic and there- SUMMARY OF THE INVENTION It is an object of this invention to prepare from colloido-silver halide emulsion layers more durable lithographic plates having improved image quality and longer press life. A further object is to prepare such plates by improved and simpler processes.  
  The improved lithographic images of this invention comprise a hydrophilic colloid binder capable of forming a complex with copper (1) ion, an insoluble complex or salt of copper (I) ion with an oleophilogenic compound and metallic silver.  
  The process for making lithographic images comprises exposing imagewise a photographic element comprising a support bearing a layer of a dispersion of light-sensitive silver halide in a macromolecular organic protein colloid binder; developing the exposed layer with a silver halide developing agent to form a silver image; treating the developed silver image with an aqueous solution containing a. a water-soluble, inorganic copper salt yielding copper (II) ions in a concentration of 0.01 molar to about 2.0 molar,  
 b. a water-soluble, inorganic halide yielding a halogen ion forming a silver salt no more soluble in water than silver chloride in a concentration of 0.01 to 0.5 molar,  
 to reduce copper (ll) ions, the reduction being terminated before all superficial silver image is oxidized, characterized in that an oleophilogenic compound is present l at least when the element is treated with the aqueous solution or (2) after formation of copper (I) ions.  
  These lithographic images are simply and conveniently formed by treating a colloido-silver image with a solution comprising copper (II) ions and the sulfuror nitrogen-containing organic compound until the metallic silver has reduced enough copper (II) ions to copper (I) ions, which form an insoluble complex with said oleophilogenic organic compound to make an inkreceptive image. This treatment should be discontinued before all of the superficial silver image has reacted with copper (11) so that the remaining silver can provide the metallic silver component of the lithographic image. This oleophilogenic compound can also be added after formation of copper (1) ions.  
  To obtain the lithographic images. activator solutions are used in the process. The activator solution comprises an aqueous solution having a pH of 0.5 to 6.0, preferably between 1 and 3. and contain a. copper (II) ions in a concentration of 0.01 molar to about 2.0 molar;  
 b. a water-soluble, inorganic halide yielding a halogen ion forming a silver salt no more soluble in water than silver chloride in a concentration of 0.01 to 0.5 molar;  
 and are characterized in that the activator contains at least one of the following 1. an oleophilogenic compound in a concentration of 0.1 to 10 grams or more per liter of the solution;  
 2. a mild oxidizing agent in a concentration such that the ratio of copper (II) to oxidizing agent is between 1 to 5 and to 1.  
  Useful oleophilogenic compounds are described below. Suitable mild oxidizing agents which can be present in the activator, either in combination with the oleophilogenic compound or not, include, e.g., iron (lll) ion, benzoquinone, mercury (II) chloride, in a concentration ratio of copper (ll) ion of from about 5/1 to H100, preferably from 3/1 to l/30. Such oxidizing agents have been found to reduce or prevent background scum on the plates.  
  Citric acid and other complexing agents may be used to control available copper (II) ion concentration. Other adjuvants such as 1,2,3-triphenyl guanidine and cyanoguanidine may be added to the activator solution to give the plate a more rapid start-up capability.  
  3 The resulting lithographic plates start to print rapidly on the press, have a long press life (up to 30,000 copies or more).  
 DESCRlPTlON OF THE PREFERRED EMBODIMENTS The hydrophilic binder for the lithographic images is a stratum of a film-forming colloid-containing chemical groups capable of forming complexes or salts with copper (l) ions, thus binding them to said stratum. A preferred such binder is gelatin, although any hydrophilic binder capable of forming a strong complex or salt with copper (I) ions may be used, e.g., other macromolecular proteins, including casein and zein.  
  The binder preferably should form stronger complexes with copper (1) ions than with copper (ll) ions. The binder should be hardened sufficiently so that none of the colloid is transferred to the printed surface.  
  The copper (l) ions which are distributed imagewise in the ink-receptive portions of the lithographic image may be produced by any appropriate means for generating an image of copper (l) ions. A copper (1) solution may be applied mechanically as with a pen or a gravure printing press. A particularly preferred method of producing a copper (1) ion image is to generate copper (1) ions by imagewise reduction of copper (ll) ions using a metallic silver image as the reducing agent. This may be done by treating the col&#39;loido-silver image with an aqueous solution of copper (Il) ions in a concentration of 0.0l to 2.0 moles per liter, and a suitable anion. e.g., a halide forming a silver salt no more soluble in water than silver chloride, in a concentration of from about 0.01 to about 0.5 molar, preferably between 0.0l and 0.l molar.  
  The metallic silver component of the image is required for a long-lived lithographic image. In the absence of metallic silver the lithographic image deteriorates fairly rapidly. A preferred method of producing the metallic silver in intimate association with the copper (l) ion image is to produce said image by using a metallic silver image to reduce copper (ll) ions, stopping the process before all of the superficial silver image is oxidized. This may be achieved by stopping the reduction while at least some silver image is still visible.  
  The olephiliogenic compound used in this invention is a compound which forms an insoluble salt or complex with copper (1) ions and an appreciably more soluble complex or salt with copper (ll) ions and at the same time imparts an oleophilic character to the hydrophilic colloid binder. Usually the molecules of such compounds will have an oleophilic moiety and a copper-complexing or salt-forming moiety. The coppercomplexing or salt-forming moiety frequently is comprised of one or more nitrogen, sulfur or oxygen atoms. The oleophilic moiety may be a hydrocarbon residue. Generally speaking, the more soluble the compound is in water, the more effective it will be, for larger concentrations of the molecules will be available to react with the copper (I) ions. The organic compounds preferably contain at least two hetero atoms to be effective in making an oleophilic, ink-receptive image. Nitrogencontaining compounds are usually the most effective but compounds containing sulfur and oxygen may also be used. Particularly preferred compounds are substituted organic indoles, diazoles, triazoles, and tetrazoles. Representative operative compounds are potassium thiocyanate, benzotriazole, 2-mercaptothiazoline, 6-nitrobenzimidazole, 3-aminol ,2,4-triazole, tannic acid, potassium hexacyanoferrate (II), and potassium hexacyanoferrate (III).  
  In practicing a preferred embodiment of this invention a conventional photographic gelatino-silver halide emulsion is exposed to actinic radiation through a process transparency, then developed in a conventional silver halide latent image developer to produce a metallic silver image. The developed image is then bathed for 5 to 90 seconds in a bath comprising copper (ll) chloride or bromide at a concentration of between 0.05 and 0.5 mole per liter, citric acid at a concentration of 0.01 to 0.25 mole per liter, and benzotriazole at a concentration of 0.1 to 10 grams per liter. The treatment should be stopped before all the superficial silver image is oxidized. After this treatment, the lithographic plate is placed on a press, inked with lithographic ink and used to print offset or direct negative lithographic copies of the original.  
  The following examples will illustrate the practice of this invention but are not intended to limit its scope.  
 EXAMPLE I An ortho-sensitized gelatino-silver chlorobromide emulsion having a /30 mole per cent bromide/chloride ratio and containing 111 g of gelatin per mole of silver halide was coated at a coating weight of 88 mg/dm of silver halide on a polyethylene terephthalate film base prepared as described in Example IV of Alles, US. Pat. No. 2,779,684. The dried emulsion was then overcoated with a gelatin antiabrasion layer at a coating weight of 2.5 mg/dm of gelatin. A sample of this element was exposed for 10 seconds through a negative halftone and line original with a No. 2 RFL photoflood operated at 22 volts at a distance of2 feet. The exposed sample was developed in a conventional high pH pmethylaminophenol/hydroquinone developer for 30 seconds at 70F, bathed in 2 per cent acetic acid for l5 seconds, then bathed for 30 seconds in a bleach at a pH of 2 to 6 prepared according to the folowing procedure.  
 Solutions A and B were prepared:  
 Solution A 3 molar potassium bromide (aqueous) 100 ml 3 molar copper (ll) nitrate (aqueous) 100 ml 1 molar potassium citrate (aqueous) 50 ml Water to make I000 ml Solution B Benzotriazole solution 10 ml (1 g/ZO ml of ethanol) Water 990 ml Solution B was added to Solution A. The plate was then rubbed with a conventional gum-asphaltumemulsion used commercially for treating lithographic plates, inked with black offset litho ink using a swab moistened with 2 per cent acetic acid, mounted or an offset office duplicator (A.B.Dick) and used to print several hundred offset copies on bond paper using 2 per cent acetic acid as the fountain solution.  
 EXAMPLE ll Samples of the element of Example I were developed 15 seconds at F in a conventional high pH l-phenyl- 3-pyrazolidone/hydroquinone developer in white light, bathed 15 seconds in 2 percent acetic acid, and bleached 30 seconds in a bleach having the following composition:  
 3 molar potassium bromide (aqueous) I ml 3 molar copper (ll) nitrate (aqueous) 50 ml Water 850 ml The bleached strips were bathed 30 seconds in test EXAMPLE &#34;I A sample of the element of Example l was exposed through the base in contact with a halftone negative transparency for 10 seconds to a No. 2 RFL photoflood solutions of the various compounds listed in Table l 5 operating at volts at a distance of 2 f The rubbed with black lltho ink using a swab moistened posed Sample was developed 1 minute in a c0nven with a working fountain solution prepared as follows. tionul high pH p methylaminophenollhydroquinone developer. water-washed 5 minutes then bathed 2 minlo utes in the following solution to make a lithographic printing plate. Stock Fountain Solution:  
  3 molar orthophosphoric acid l0 ml 0.5 molar trisodium phosphate ml water 1&#34; i 1000 ml 3 molar copper (ll) nitrate (aqueous) 5 ml Workmg Fountain Solution: &#39;5 Gklciu] acetic acid 1 m| swck l wlumm 3 ml 3 molar sodium chloride (aqueous) 5 ml GP&#34;! Arab&#34;: l g/mo will&#34;) ml 1 molar potassium acetate (aqueous) 10 ml Dlethylcnc glycol monobutyl ether ml pmussium thiocvanmc 4 m] m make 1000 ml (0.! g/ml aqueous solution) Water ml 0.37: aqueous colloidal silica sol 10 ml 1-&#34; b r3073!&#34; Other samples were tested using a swab moistened 20 mm 100 m| with 2 percent acetic acid. The test solutions were prepared by diluting 5 ml of a concentrated solution of the chosen compound with ml of water. Results of the Offset lithographic copies on bond paper were ink acceptance test are tabulated in Table l following printed on an office duplicator (A.B.D|ck) using I per- Example ll]. 25 cent acetic acid as the fountain solution.  
 TABLE I INK ACCEPTANCE FOUN TAlN CONCENTRATED SOLUTION 2% SOLUTION ACETlC OF COMPOUND SOLVENT AMOUNT ACID EXv ll Benzotriazolc Ethanol l g/ ml Yes Yes 3,5-dimethyl-l .2,4  
  triazole Yes No 6-nitroquinoline Yes No Z-mercaptobenzimidazole Yes No S-nitrobenzotriazole YE YES 2-mercaptobenzoxazole YES NO thioglycolic acid Yes No thiobarhituric acid Yes Yes 1 .Z-naphthotriazole Yes No 2-mercaptobenzothiazole Yes No G-nitrobenzimidazolc nitrate Yes Yes phenolphthalcin Yes No Z-mercaptoethanol Yes No 2-mercaptothiazoline Yes Yes 2-mercapto-4- phenylthiazole Yes No l-phenyl-S- mercaptotetrazole Yes No 3-ethylrhodanine Yes No tolutriazole Yes Yes 4-phenylcatechol Yes No Z-chlorobenzothiazolc Yes No thiosalicylic acid Yes No tetrachlorohydroquinone 2-amino-6- Yes No methylbenzothiazole 3amino-l,2,4-triazole Ethanol l g/lOO ml Yes Yes potassium hexacyanoferrate (ll) Water Yes Yes potassium hexacyanoferrate (lIl) Yes Yes guanidine thiocyanate Yes Yes Congo red Yes No sodium thiosulfate Yes No potassium thiocyanate Yes Yes S-aminotetrazole monohydrate Yes Yes methyl-7-hydroxy&#39;l 2.3-triazoleindolizine 0.26N NaOH 5.2 g/l()() ml Yes No 6-nitroindazole 20% ethanol/ Yes No 0.2N NaOH 1 g/lOO ml TABLE 1 Continued INK ACCEPTANCE FOUN- TAIN W SOLUTION ACETlC OF COMPOUND SOLVENT AMOUNT ACID EX. ll  
 5-nitroindazole Yes No guanine 0.2N NaOH 1 g/2(l() ml Yes Yes ethylenethiourea ethanol/ Yes Yes water 1 g/l()() ml hypoxanthine 0.007N NaOH 1 g/l()() ml Yes No 3-ehloro-6-nitroindazole Ethanol Yes No hexamethylene tetramine Water Yes No phenylisothiocyanate Ethanol Yes No 2.4,5-triphenylimidnzole Yes No 2guanidinohenzimidazole Yes No 2-aminohenzimidazole Yes No w.m-hispiperidine methyl urea Water 1 g/l()() ml Yes No pentamethylenetetrazole Ethanol Yes No DLfi-phenylalanine W1 acetic acid Yes No histamine dihydrochloride Water Yes No L-histidine Yes No LIU-phenanthroline Ethanol Yes No dihydroxynonanophenone Yes No l.2.3-triphenylguanidine Yes No l-phenyl-Z-methyl henzimidazole l g/l000 ml Yes No 2-methyl-l.3-diethyl henzimidazole iodide Yes No l-phenyl-3-ethyl-2- Ifl-ethylhenzothiazolepropylidinolhenzimidazolium iodide Yes No 3. l &#39;-disulfopropyl- S-methyl-Z-benzothiazole-Z- quinoline cyanine l g/500 ml Yes No Remazol Brilliant Blue (C.l. Reactive blue l9) Water I g/lOO ml Yes No Stilbene Yellow (C.l. Direct Yellow ll) Yes No Condensation product of sodium hisulfite and a polyacrolein resin of molecular weight 400,000. (Carbon to sulfur atomic ratio 6) Water I g/lOO ml Yes No tannic acid Yes Yes EXAMPLE W The sample was rubbed with lithographic ink using a 3 molar copper (ll) nitrate (aqueous) l0 ml 3 molar potassium bromide (aqueous) 10 ml 1 molar orthophosphoric acid 5 ml Potassium thiocyanate (0.l g/ml aqueous solution) 4 ml Sodium nitrite (50 g/litcr aqueous solution) 5 ml Water 7] ml moistened swab. The imaged portion of the sample accepted ink.  
 EXAMPLE V A sample of the element of Example I was partially immersed in a conventional high pH p-methylaminophenol/hydroquinone developer for 30 seconds at 68F. with white room lights turned on. Excess developer was removed by squeegeeing and the sample was bathed l5 seconds in an activator prepared according to the following procedure. Solutions A and B were prepared.  
  The treated sample was then squeegeed lightly against the emulsion side of another sample of the element of Example I and held in contact for 45 seconds. The strips were separated and the undevloped strip was rubbed with lithographic ink using a cotton swab moistened with 2 percent acetic acid. The part of the receptor layer which had been in contact with the developed portion of the first strip accepted ink.  
 EXAMPLE VI A geIatino-silver image on a polyethylene terephthalate support prepared by conventional photographic methods from the element of Example I was treated in an aqueous copper (II) bromide solution for IO seconds. then placed in contact with a sample of the element of Example I, also wet with the bleach solution. for seconds, and then separated. The receptor layer was bathed in an aqueous benzotriazole solution for 10 seconds and rubbed with lithographic ink using a cotton swab moistened with 2 percent acetic acid. The receptor layer was found to have an ink receptive image.  
 EXAMPLE VII A hardened gelatin receptor layer on a polyethylene terephthalate support was prepared by fixing, washing, and drying an undeveloped sample of the element of Example I. Example VI was repeated using this receptor layer in place of the gelatino-silver chlorobromide receptor of that example. An ink-receptive image was obtained on the receptor layer.  
 EXAMPLE VIII A photographic high speed x-ray type geIatino-silver iodobromide emulsion having a 3/97 mole percent iodide to bromide ratio and containing 120 g of gelatin per mole of silver halide was coated at a coating weight of I 10 mg/dm of silver halide on the subbed polyethylene terephthalate support of Example I. The dried emulsion was overcoated with a gelatin antiabrasion layer having 10 mg/dm of gelatin. Example V was repeated using this element as the photosensitive layer. An ink-receptive image was obtained on the receptor layer.  
 EXAMPLE IX A sample of the element of Example I was imagewise exposed, developed, and fixed by conventional photographic techniques. The resulting gelatino-silver image and a sample of the element of Example I were bathed for 10 seconds in a solution of the following composition.  
 3 molar copper (II) nitrate (aqueous) 5 ml 3 molar potassium bromide (aqueous) I0 ml 3 molar citric acid (aqueous) 10 ml Water ml The bathed strips were placed in contact for 20 seconds and separated. The receptor was bathed for IS seconds in a solution of the following composition.  
 Benzotriazole I g/l00 ml of alcohol) 10 ml 3 molar citric acid (aqueous) I0 ml Water ml The receptor was then rubbed with lithographic ink using a cotton swab moistened with 2% acetic acid containing a small amount of gum arabic. A black ink image appeared on the receptor layer.  
 EXAMPLE X A hardened gelatin receptor layer on a polyethylene terephthalate support was prepared as in Example VII. Example IX was repeated using this receptor layer in place of the gelatino-silver chlorobromide receptor of that example. A black ink image was obtained on the receptor.  
 EXAMPLE XI A sample of hardened gelatin on a polyethylene terephthalate support prepared as in Example VII was soaked for about 30 seconds in a cupric bromide solution. then soaked for about 30 seconds in a benzotriazole solution to which a small amount of sodium nitrite has been added. The treated sample was then rubbed with lithographic ink using a swab moistened with 2 percent acetic acid. The gelatin was found to be inkreceptive.  
 EXAMPLE XII A sample of the element of Example I was exposed and processed as in Example I using instead of the bleach of Example I a bleach of the following composition.  
 Glacial acetic acid I00 ml Benzotriazole (I g/IOO ml of alcohol) I00 ml I molar potassium citrate (aqueous) I00 ml 3 molar potassium bromide (aqueous) 50 ml 3 molar copper (II) nitrate trihydrate (aqueous) 25 ml I molar iron (III) nitrate nonahydrate (aqueous) 25 ml 1.2.3-triphenyl guanidine I g/I00 ml of alcohol) 50 ml Water to make I000 ml The plate when used as in Example I gave good offset copies free of background scum.  
 EXAMPLE XIII A high speed ortho-sensitized geIatino-silver iodobromide emulsion having about l.2% silver iodide and containing about g of gelatin per mole of silver halide was coated on an 0.008 inch waterproof, polyethylene coated, photographic base at a coating weight of 27 mg/dm of silver bromide and overcoated with mg/dm of gelatin hardened with 4 g of formaldehyde per 100 g of gelatin.  
  A sample of this element was exposed on a phototypesetting machine in which each character was separately exposed using a xenon flash tube source having a flash duration of 2 to 3 microseconds and an energy output of 100 millijoules. The exposed sample was tray developed for 30 seconds in a conventional high pH 1- phenyl-3-pyrazolidone/hydroquinone developer containing 0.25 g of benzotriazole per liter, water washed for 30 seconds, and treated for 30 seconds in an activator of the following composition:  
 Glacial acetic acid 100 ml Benzotriazole solution 1 g/l()() ml of ethanol) 100 ml 1 molar potassium citrate (aqueous) 100 ml 0.6 molar potassium bromide (aqueous) 250 ml 0.3 molar copper (ll) nitrate (aqueous) 250 ml Water to make 1000 ml The treated sample was then washed with water for 30 seconds and rubbed with a conventional commercial plate treating asphaltum-gum emulsion. The plate was then placed on an offset office duplicating machine (A.B.Dick) and used to print 30,000 copies using a fountain solution prepared as follows.  
 Stock Fountain Solution 3 molar phosphoric acid 10 ml All copies showed good quality offset images.  
 EXAMPLE XIV A high-speed ortho-sensitized aqueous gelatino-silver iodobromide emulsion was coated at 25 mg equivalent AgBr/dm on polyethylene coated, gelatin subbed, waterproof paper base under low intensity red safelights. A gelatin antiabrasion layer containing formaldehyde hardener was coated over the wet emulsion layer at mg/dm and the two layers dried. A 25.4 X 38.1 cm sample of the paper coating was soaked for 1 minute at 22C. in 1000 ml of water containing 10 g benzotriazole and 1.5 g of the sodium salt of p-tert-octylphenoxydiethyleneglycol sulfonic acid. After air drying, the sample was exposed through a test pattern in a vacuum frame to a k&amp;m, 100-watt, -volt tungsten filament point source incandescent lamp at 1 14.3 cm for 9 seconds at tap setting 2 (16 volts) and through a glass Wratten (Registered Trademark) 18A UV filter plus a 0.6 neutral density filter. The exposed sample was processed at 22C. for 40 seconds in a 4-tray processor, e.g., on Agfa-Gevaert Fotorite (Registered Trademark) model DDl437 stabilization paper processor using a conventional high pH l-phenyl-3- pyrazolidone/hydroquinone developer in the first three trays and Solution A in tray 4. Solution A is as follows:  
 Solution A 3M KBr 50 ml 3M Cu(NO .3H O 5 ml 3M Citric Acid 50 ml 1M Fe(NO;,);,.9H. .O 50 ml l-Cyanoguanidine l g/100 ml H 0) 50 ml Triphenyl Guanidine l g/lOO ml ethanol) 50 ml Water up to 1000 ml pH 1.10  
 The processed sample was then placed on a duplicating machine, e.g., an A. B. Dick 320 Office Duplicator, and using Fountain Solution B 25 good offset copies were made using a black lithographic ink. Fountain Solution B is:  
 Stock Fountain Solution Described in Example ll pH 3.9 20 ml Gum Arabic (1 g/l00 ml H 0) 20 ml Diethylene glycol mono-n-butyl ether 50 ml Water to make 1000 ml pH 3.90  
 A similarly exposed and processed sample of the same paper emulsion coating which had not been bathed in the benzotriazole solution would not accept ink or give printed offset copies.  
 EXAMPLE XV An ortho-sensitized gelatino-silver chlorobromide emulsion having a /30 mole percent bromide/chloride ratio and containing 111 g of gelatin per mole of silver halide was coated at a coating weight of 88 mg/dm of silver halide on a polyethylene terephthalate support described in Example I. The dried emulsion was overcoated with a gelatin antiabrasion layer at a coating weight of 2.5 mg/dm of gelatin hardened with 4.25 g of dimethylolurea per 100 g of gelatin. The prepared photographic film was exposed through a halftone and line test negative for 6 seconds with a 500- watt RSP-2 reflector photospot lamp having a tungsten filament operated at 15 volts at a distance of 127 cm. The exposed photographic film was developed for 30 seconds in the developer solution of Example XIV, except that the developer contained 2 g/liter of benzotriazole, and then activated for 30 seconds at 20C. in an aqueous bath of the folowing composition.  
 3 molar cupric nitrate solution 5 ml 3 molar citric acid solution 10 ml 3 molar potassium bromide solution 10 ml Water ml The activated film was rinsed in water for 5 seconds, mounted, e.g., on an offset office duplicating machine, and using 2% by weight acetic acid as the fountain solution and a lithographic ink good quality negative oleophilic lithographic images were obtained. When a developer was used without any benzotriazole present no oleophilic lithographic image was formed.  
 EXAMPLE XVI A high-speed, ortho-sensitized gelatino silver iodobromide emulsion having 1.2 mole percent silver iodide and a gelatin to silver halide ratio of 0.36 was coated at a coating weight of 7.2 milligrams of silver bromide per square decimeter on a polyethylene terephthalate Solution A Water 800 ml Nickel (ll) nitrate hcxahydrate 0.75 g Potassium citrate monohydrate 0.6l g Solution B Water 190 ml Potassium hexacyanoferrate (ll) trihydrate 1.06 g  
 Sodium octyl phenoxy ethoxysulfonate l ml (4.2% aqueous solution) Solution A was added to Solution B with vigorous stirring. The sol overcoat was then dried with a current of hot air.  
  The element was exposed through a step wedge and line image transparency for-.10 seconds with the K&amp;M light source described in Example XlV at a distance of 127 cm using an ultra violet filter and a neutral density filter of 0.6 optical density. The exposed element was developed for seconds at 22C. in a conventional high pH hydroquinone/l-phenyl-3-pyrazolidone developer containing 0.25 g of benzotriazole per liter. rinsed in water for 5 seconds. and then activated for 30 seconds at 22C. in an aqueous bath of the following composition:  
 3 molar copper (ll) nitrate 25 ml 3 molar potassium bromide 25 ml 3 molar citric acid I00 ml Benzotriazole 0.25 g Water to make I000 ml pH adjusted to 2.0  
 3 molar aqueous orthophosphoric acid solution I0 ml 0.5 molar aqueous trisodium phosphate solution 25 ml Water to make I000 ml The fountain solution was then prepared from the concentrate according to the following formula:  
 Fountain solution concentrate Gum arabic solution (I g/l00 ml water) 20 ml Diethylene glycol monobutyl ether 50 ml Water to make I000 ml Satisfactory lithographic images were obtained.  
 EXAMPLE XVII A nickel (ll) hexacyanoferrate (ll) sol was prepared as follows:  
 Solution A 0.1 molar potassium citrate (aqueous) 20 ml 0.1 molar nickel (ll) nitrate (aqueous) 10 ml Water I70 ml -Continued Solution B 0.l molar potassium hexacyanoferrate (ll) 30 ml Partial sodium salt of N-lauryl beta imirlodipropionate l g/l00 ml of alcohol) 4 ml Water I66 ml Solution A was added to Solution B in 15 seconds with rapid stirring. 1  
  A high-speed, ortho-sensitized gelatino-silver iodobromide emulsion having about 1.2% silver iodide and containing about &#39;120 g of gelatin per mole of silver halide, coated at a coating weight of about 25 mg/dm on a smooth. polyethylene coated, photographic paper base was overcoated with the sol by skim coating at a speed of 2.44 m per minute and hot air drying.  
  Two samples were exposed through a step wedge and line image transparency for 10 seconds with a K&amp;M, I00-watt, 20-volt tungsten point source incandescent lamp at tap setting 2- 16 volts) at a distance of 127 cm using an ultra-violet filter and a neutral density filter of 0.6 optical&#39;density. &#39;The exposed samples were developed for 30 seconds at 22C. in-a conventional high pH hydroquinone/ l -phenyl-3-pyrazolidone developer containing 0.25 g of benzotriazole per liter. One sample was activated for 8 seconds in the following activator solution:-  
 3 molar copper (ll) nitrate l6.3 ml 3 molar potassium bromide 15.5 ml 3 molar citric acid 1000 ml Benzoquinone 0.79 g Water to make 1000 ml The second sample was activated for 8 seconds in the following activator solution:  
 3 molar copper (ll) nitrate 25 ml 3 molar potassium bromide 25 ml 3 molar citric acid I00 ml 0.2 molar mercury (ll) chloride 50 ml Water to make I000 ml Each activated sample was dried by hot air and used on an office duplicator to print good offset copies using a lithographic ink and fountain solution described in Example XVI.  
 EXAMPLE XVlll Element A is a high-speed ortho sensitized aqueous gelatino-silver iodobromide emulsion which was coated at 25 mg equivalent AgBr/dm on polyethylene-coated, gelatin-subbed. waterproof paper base under low intensity red safelights. A gelatin antiabrasion layer containing formaldehyde hardener was coated over the wet emulsion layer at 15 mg/dm and the two layers dried. Element B consists of Element A overcoated by skim coating at 38C. and 2.74 m per minute using a nickel (ll) hexacyanoferrate (ll) sol prepared as follows:  
  Water 800 ml Nickel (ll) nitrate hexahydrate 0.75 g Potassium citrate monohydrate 0.6l g Solution B Water ml Potassium hexacyanoferrate (ll) trihydrate L06 g Sodium octyl phenoxy ethoxysulfonate (4.2% aqueous solution) 10 ml Solution A was added to Solution B with vigorous stirring. The sol overcoat was then dried with a current of hot air.  
  Element A was exposed and processed as described in Example XIV. Processed Element A was rewet with Solution A described in Example XlV and squeeged in contact with Element B for 30 seconds at 22C. The elements were separated and Element B was then placed on an offset office duplicating machine and, usng Fountain Solution B in Example XlV and a lithographic ink. copies were prepared.  
  This example was repeated except that prior to the exposure and processing of Element A in the above procedure. both Elements A and B were soaked in a 0.01 molar solution of potassium ferrocyanide for two minutes. Excess solution was drained from the elements and the elements were air dried. Up to 500 offset images were obtained during the printing operation.  
  The lithographic images of this invention are more easily and rapidly prepared than those used hitherto. Lithographic plates using these images start to print more rapidly. have longer life, and greater resistance to aging than other plates prepared from gelatino-silver halide emulsion layers.  
  The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:  
  1. An activator solution comprising an aqueous solution having a pH of 0.5 6.0 containing a. copper (ll) ions in a concentration of 0.0] molar to about 2.0 molar;  
 b. a water-soluble, inorganic halide yielding a halogen ion forming a silver salt no more soluble in water than silver chloride in a concentration of 0.01 to 0.5 molar;  
 characterized in that the activator contains an oleophilogenic compound in a concentration of 0.1 to 10 grams or more per liter of solution.  
  2. An activator solution according to claim 1, characterized in that the oleophiligenic compound is benzotriazole.  
  3. An activator solution according to claim 1, containing ferric nitrate.  
  4. An activator solution according to claim 1, containing benzoquinone.  
  5. An activator solution according to claim 1, containing mercury (Il) chloride.  
  6. An activator solution according to preceding claim 1, characterized in that the inorganic halide is potassium bromide.  
  7. An activator solution according to preceding claim 1, characterized in that citric acid is present at a concentration of 0.01 to 0.25 mole per liter of solution.