DE2038312B2 - PROCESS FOR THE PRODUCTION OF FLAT PRINT FORMS - Google Patents

Description

The invention enables the production of planographic printing forms from photographic recording materials possible in a very simple and fast way. A particular advantage of the new planographic printing plates is that they can be used in a very short time can be made ready for printing, enable perfect flat printing of 1000 and more prints and have a long service life.

A photographic developer substance is expediently worked into the emulsion layer.

The gelatin-silver halide emulsion layer can contain silver chloride, silver chlorobromide, and silver bromide or silver iodobromide crystals dispersed in a gelatin binder. According to one embodiment of the invention, the emulsion layer is applied to a layer ^{substrate with a layer weight of at least mg silver halide / dm 2.} The amount of silver halide used will depend somewhat on the results desired, but it must be at least 1 mg / dm ² to provide a lithographic image. There is no upper limit for usable layer weights per se, but there is no advantage in using more than 100 mg / dm ^{2 of} silver halide. Flawless results are obtained according to a further embodiment of the invention when layer weights of about 5 to 50 mg / dm ^{2 of} silver halide are set. The emulsion can be sensitized in a panchromatic manner.

According to a further embodiment of the invention, the emulsion layer is covered with a thin abrasion protection layer made of gelatine or similar, water-permeable, protein-containing colloids, which contain imidazole groups. The anti-abrasion layer can then according to one embodiment of the Invention containing the Hexacyanoferra'.sol, but it has proven particularly useful, the Hexacyanoferrat finally to be applied either over the emulsion or the abrasion protection layer, if any. Suitable protein-containing colloids that can be processed instead of or in addition to gelatin are Casein and zein.

The hexacyanoferrate sol comprises an aqueous dispersion of hexacyanoferrate ion (II), (ferrocyanide), or hexacyanoferrate ion (III), (ferricyanide), with a suitable heavy metal cation. Cations are copper (II), nickel (II), cobalt (II), palladium (II) and rhodium (II). That for coating the GcIatine silver halide emulsion The hexacyanoferrate sol used advantageously contains 0.005 to 0.1 mol of the hexacyanoferrate per 1. Coating aids can be added to the sol as well as complex-forming substances, for example citrate ions, can be added. Latter serve to regulate the concentration of free cation for the purpose of delivering optimal results.

A sufficient amount of hardening agents should preferably be present in the photosensitive layer which are added to either the emulsion and / or the abrasion protection layer and / or the hexacyanoferrate sol so that no substantial amounts of colloid are transferred during printing.

In the context of carrying out the invention, the material is exposed imagewise to actinic radiation, with the aid of a conventional developer for latent silver halide images to form a silver image developed, watered if necessary and then in a copper (II) ion containing at least 0.01 mol per 1 Solution, which also contains halide ions, activated. The silver image can be completely converted into silver ion be transferred, however, the activation is preferably only continued until a part, however not all of the superficially developed silver, with simultaneous formation of copper - (!) - ion in Silver ion is transferred. Preferably the activator contains a copper (II) halide which developed it Silver converted back into silver halide.

After this treatment, the exposed areas of the gelatin layers are receptive to oily Printing inks and the plate can be placed directly in a printing press.

In another use of the recording material of the invention one uses the light-sensitive, material coated with hexacyanoferrate or any light-sensitive material free of silver halide Coating of the hexacyanoferrate sol on or in a suitably hardened form lying on a layer support, hydrophilic, water-permeable, gelatin

^ao or protein-containing layer which contains imidazole groups as a receiving material for a transfer process. In such a procedure, a conventional silver image is activated in contact with a receiving material. On the silver-free reception

^A 5 material is an image that accepts printing inks and, after the receiving material has been separated, it can be used as a planographic printing plate.

The activator solutions required to practice the invention consist of the following Substances:

1. Copper (II) ion in a concentration of appropriate at least 0.01 molar, preferably at least 0.03 molar,

2. a halide ion which is capable of forming a silver salt which is at most as soluble as Silver chloride, and which is added to have a concentration of 0.01 molar to about 0.5 molar, preferably 0.01 to 0.1 molar, and

3. expediently iron (III) ion in such a concentration, that the ratio of the concentration of copper (U) ion to iron (HI) ion between 1: 5 and about 100: 1, preferably between 1: 3 and 30: 1. The pH of the activator solution should between 0.5 and 6, preferably between 1 and 3, are.

The activator solution can contain other auxiliaries that improve the quality of the lithographic plate. Cyanoguanidine, 1,2,3-triphenylguanidine, benzotriazole and 1,10-phenanthroline are useful adjuvants to be added to the activator solution can. Activator solutions containing cyanoguanidine and 1,2,3-triphenylguanidine provide forms that start printing much faster in the press than solutions that do not contain these substances contain. Benzotriazole-containing activator solutions provide improved printing forms that are characterized by a longer service life. The activation rate of the solution can be adjusted by adding 1,10-phenanthroline, which slows down the activation reaction.

The invention is suitable for the production of Planographic printing forms which are directly suitable for automatic collotype printing devices. One can Also perform Koniakt or reflex exposures to plates for quick, easy document duplication to manufacture.

The following examples illustrate the invention.

Example I.

A nickel UO hexacyanoferrate UD sol was like is made as follows:

Solution a

0.1 molar potassium citrate solution 10 ml

0.1 molar nickel (II) nitrate solution 5 ml

Solution b
0, lmolaie potassium hexacyanoferrate

(H) solution 15 ml

Saponin (10% aqueous solution) 1 ml

Thymol (5 g / 100 ml ethanol) 2 ml

Water 82 ml

Solution A became solution b within 15 seconds added with vigorous stirring at 24 ° C.

An ortho-sensitized gelatin-silver chlorobromide emulsion was applied to a carrier film made of polyethylene terephthalate, which had been prepared according to Example 4 of US Pat Contained 111 g of gelatin per mole of silver halide; the layer was applied while setting a layer weight of 88 mg / dm ^{2 of} silver halide. The dried emulsion layer was coated with an abrasion protection layer made of gelatin, setting a layer weight of 2.5 mg / dm ^{2 of} gelatin, which had been hardened with 4.25 g of dimethylolurea per 100 g of gelatin. The material was then covered with nickel (II) hexacyanoferrate (II) sol in a red safety light, a speed of 2.44 m / min and a temperature of 24 ° C. and then dried with hot air.

A sample of the material was screened through a halftone and line test negative for 6 with a 500 watt RSP-2 reflector light spot filament lamp exposed, which was echoed at a distance of 127 cm and at a voltage of 15 volts worked. The exposed sample was 20 seconds at 22 ° C in a standard hydroquinone / l-pheriyl-3-pyrazolidone developer Developed from high pH, containing 0.25 g of benzotriazole per 1; it was then rinsed with water for 5 seconds and then activated without further fixing for 30 seconds at 22 ° C. in an aqueous bath with the following composition:

3 molar copper (II) nitrate solution 50 ml

3 molar citric acid solution 50 ml

3 molar potassium bromide solution 5 ml

! molar iron (III) nitrate solution 15 ml

Remainder: water to 1000 ml

The activated sample was rinsed for 5 seconds, placed in an office machine for offset copies and with a rubbed in the moisturizing solution prepared as indicated below.

First, a concentrate of the moistening solution was prepared with the following composition:

3 molar aqueous orthophosphoric acid solution 10 ml

0.5 molar aqueous solution of

Trisodium phosphite 25 ml

Remainder: water / ii 1000 ml

The moisturizing solution of the following composition was then made on the basis of this concentrate prepared:

Concentrate of the humidifying solution .. .20 ml
Gum arabic solution (I part by weight

to! 00 parts by volume of water) 20 ml

Diethyl glycol monobu'yl ether 50 ml

Remainder: 10 ml of water

ίο The plate was then covered with lithographic printing ink colored and used to print 10,000 offset copies on white hard paper. The record started very quick to print, all prints were of good quality.

Example 2

According to Example 1, a sample was produced using a cobalt (II) hexacyanoferrate (II) sol instead of nickef- (if) -hexacyanoferrate - ('f! - sols. The sol was prepared as indicated in Example I, but cobalt (II) nitrate instead of Nickel (II) nitrate applied. The sample was as in Example 1 indicated exposed, activated, colored with printing ink and used for printing, with good Copies were obtained on hard paper.

Example 3

A sample was produced according to Example 1, with copper (II) hexacyanofrate (II) sol correspondingly the information of Example 1 was prepared by using copper (II) nitrate instead of Converted nickel (II) nitrate. The produced hexacyanoferrate sol was used as a coating for the gelatin-silver halide layer. Became the rehearsal exposed, activated, colored and used for printing as described in Example I, negative results were obtained Receive offset copies.

Example 4

A sample was prepared according to Example 1 using the following hexacyanoferrate sol instead of the one described in example 1:

Solution a

Water 75 ml

Gum arabic (1 g / 100 ml water). 10 ml
0.1 molar aqueous nickel (II) -

nitrate hexahydrate solution 5 ml

Polyacrylic acid (5 ml / 100 ml water) ... 10 ml

Solution b

Water 70 ml

Gum arabic (1 g / 100 ml water). 10 ml
0.1 molar potassium hexacyanoferrate (II) -

solution., 10 ml

Polyacrylic acid (5 ml / 100 ml water) ... 10 ml

Solution A was added to solution B within 5 seconds with vigorous stirring.

After exposure, activation, inking and printing as in Example 1, negative offset copies were made obtain.

Example 5

Example 4 was repeated with the exception that the activating solution deteriorated would have:

3molaiv copper-) I Π-nii rait ri hydra t-

solution (aqueous)? ■ ml

3 molar aqueous potassium bromide solution. 50 ml 1 molar aqueous potassium calcium solution M) O mi

I molar aqueous iron (III) nitrate ion hydrate solution 100 ml

Rest: water / u. . ' 1000 ml

After coloring and printing as indicated in Example I. good negative oil copies were obtained. which were free of foam in the unexposed areas.

Example 6

It was a nickcl- (II) -hcxaeyanoferrat- (lH) -sol produced in compliance with the procedure of Example 4, except that potassium hexacyanoferrate-dll) Potassium Hoxacyanofeirate (ll) Place Applied became. Analogously to the information for Example 1, a photographic material was produced and replaced by a 2-step keii exposed using one! otoflutlichtlampc, which worked at 35 volts and a distance of 0.61 m. The exposed material was in a l-Phcnyl ^ -pyrazolidon · 'hydroquinone developer of a high ρ Η value, the 0.25 g benzotriazole each contained I, after which 30 seconds in 2 "igei acetic acid treated, washed and dried. The sample was then placed in an activating solution for 20 seconds bathed with the following composition:

3 molarc potassium bromide solution 100 ml

3 molar copper i ll) nitrate solution 50 ml

Water 850 ml

The sample was then rubbed with the dampening solution from Example 1, colored and used for printing. Good planographic prints were obtained.

Example 7

According to Example 6, a sample was prepared using nickel (II) hexacyanoferrate

Solution a

Water 95 ml

0. lmolarc aqueous nickcl- (U) -

nitral hexahydrate solution 5 ml

Solution b

Water 85 ml

0.1 molar aqueous potassium hexacyanoferrate (II) solution 15 ml

Solution A was added to solution B with vigorous stirring. The sample was exposed, developed and activated as indicated in Example 1. After treatment with ink, printing became good Get copies.

Example 8

According to Example 7, a sample was prepared using a coating which had been prepared from the following solution:

Solution a 0.1 molar aqueous solution of

Chewing citrate 10 ml

ö, imoiare wäBfige Nn, kel- {11) -

nitrate solution 5 ml

Water 85 ml

Solution B

0.1 molar potassium hexacyanoferrate (II) -

dissolving 15 ml

Saponin (10 "solution in one

Mki'inil-water mixture) 1 ml

rhwnol (5 g / 100 ml alcohol) 2 ml

Water 82 ml

The sample was exposed for 3 seconds through a line and halftone test negative with a photo floodlight lamp that worked at 15 full and was held at a distance of 101.6 cm. The exposed sample was 30 lake in a l-phenyl-3-pyrazolidone / hydroquinone Entwicklcr from high pH developed, see with Wasscr 10 washed and a ¹ J ₂ minutes in an activator solution of the activated nachsiehenden composition:

Molar aqueous copper (II) nitrate solution 50 ml

3 molar aqueous citric acid solution. 50 ml. Molar aqueous potassium bromide solution. 5 ml 1 molar aqueous ice cream (III) nitrate

solution 5 ml

Remainder: water to 1000 ml

The sample was then washed and used to make 1400 copies in an office offset copier using the wetting solution of Example 1. Good offset copies were made obtain.

Example 9

It was a nickel-ulhiexacyanoferrat-OlJ-sol manufactured as follows:

Solution a

0.1 molar aqueous potassium citrate solution .20 ml 0.1 molar aqueous nickel (II) nitrate

solution 10 ml

Water Γ 170 ml

Solution b

0.1 molar potassium hexacyanoferrate (II) solution 30 ml

Calcium salt of N-lauryl - /? - iminodipropionate (1 g / 100 ml alcohol) ... 4 ml

Water 166 ml

Solution A was added to solution B within 15 minutes with vigorous stirring.

A highly sensitive, ortho-sensitized gelatin silver iodobromide emulsion with a content of about 1.2 percent by weight silver iodide, containing about 120 μg of gelatin per mole of silver halide and setting a coating weight of about 25 mg / dm ² on a smooth, with polyethylene coated photographic carrier paper was applied, was coated with the sol by smear coating while maintaining a speed of 2.44 m min and dried with hot air.

The samples were tested through a bar and half gate test negative with the help of a 500 watt photo floodlight lamp exposed at 15 volts at a distance

from 127 cm worked. The exposed samples were rinsed in water for 20 seconds in the development of Example 1, then activated for 20 seconds in an activator solution with the following composition:

609 527/21

3niolarc aqueous potassium chromide solution. 15 nil 3 molar aqueous copper (11) nitrate

solution 25 ml

3 molar aqueous citric acid solution. 25 ml molar aqueous iron (III) nitrate

non-anhydride solution 25 ml

Triphynylguanidine (1 g / 100 ml alcohol) 50 ml water: remainder to 1000 ml

The activated plate was rinsed with water for 5 seconds, inserted into an offset office copier, with the fertilization of Example 1 and used to print more than 500 offset copies.

Example 10

As indicated below, a nickel (II) hexacyanoferrate (II) sol prepared: solution A

Water 800 ml

Nickcl-OD-nitrate hydroxahydrate 0.75 g ^:

Potassium cilrate monohydrate 0.61 g

Solution b

Water 190 ml

Potassium hydroxacyanofcrrate RO trihydrate. 1.06g Sodium octylphynoxyethoxysulfonate (4.2% aqueous solution) 10 ml

Solution A was quickly added to solution B with vigorous stirring.

Example 9 was repeated using the sol described above as a coating. It was received an excellent planographic printing plate which could be used to make several thousand offset copies to print.

Example i 1

Example 9 was repeated using an activating solution of the following composition:

Glacial acetic acid! 0OmI

Benzolriazole (1 g / 100 ml alcohol) ... 100 ml 1 molar aqueous potassium citrail solution. 100 ml 3 molar aqueous potassium bromide solution. 50 ml 3mol; iro Ki! Pfer- (II) -nitrate trihydrate-

solution: 25 ml

1 molar ice (IU) niirate mono-

hydronic solution 25 ml

Triphenylguanidine (1 g / 100 ml alcohol) 50 ml Remainder: water to 1000 ml

A good flattened print was obtained, which can be distinguished by a quick reference to the Press excelled without any sub-surface foam occurring.

Example 12

Example 7 was repeated with the exception that the activator solution had the following composition exhibited:

3 molar aqueous copper (II) nitrate

trihydrate solution 12.5 ml

3 molar aqueous potassium bromide solution 25 ml 1 molar aqueous potassium acetate solution. 100 ml 1 molar aqueous potassium citrate solution. 100 ml! Molar aqueous ice (III) nitrate

monohydrate solution 100 ml

Remainder: water to 1000 ml

Good color planographic printing copies were obtained.

Example 13

Example 7 was repeated with the exception that
the asset solution

.lic the following composition

the

/ unu had:

3 molar aqueous copper-dl-nitrate

solution 50 ml

3 molar aqueous citric acid solution. 50 ml
3 molar aqueous potassium bromide solution. ? ml
1 molar aqueous iron (II) -nitiral solution 5 ml
Remainder: water to 1000 ml

Good color planographic printing copies were obtained.

Example 14

A nickel (II) hexacyanofcrratsol was manufactured as follows:
Solution a

Water 665 ml

O. molar aqueous nickel (II) nitrate

Hydroxahydrate solution 20 ml

0.1 molar aqueous potassium citral mono-

hydrate solution 15 ml

Solution b

Water 72 ml

0.1 molar potassium hexacyanofcrraH 11) -

trihydrate solution 20 ml

Condensation product of coconut fatty acid and diethanolamine
(1 g / 100 ml alcohol) S ml

Solution A was added to solution B over the course of 15 seconds with vigorous stirring at 24 ° C.

A commercially available stabilizer was incorporated into this sol. "- Enlargement paper dipped in the photosensitive emulsion of which developer was incorporated. the sol was drained and dried.

A sample was screened through a negative line and halftone image transparency using a 100 watt tungsten filament lamp that worked at 8 full. exposed, with a setting 1 and a distance of 139.7 cm has been complied with. The exposed sample was treated with a basic activator solution for 30 seconds and then 10 seconds with the lithographic activator solution of Example 9. The treated sample was buffed with the moistening solution of Example 1, colored with printing ink and zui Used to make good planographic copies.

Example 15

The emulsion of Example 9 was applied to a smooth, polyethylene-coated photographic paper, ^{setting a layer weight of about 25 mg / dm 2, and dried.} The emulsion layer was covered with the nickel-UD-hexacyanoferrate sol of Example II according to the instructions in Example 14, to which 40 g / l hydroquinone and 5 gy sodium sulfate had been added. The sample was exposed according to Example 14 with the exception that an exposure time of 3 seconds was observed. The exposed sample was treated analogously to Example 1 and good planographic copies were obtained

Example 16

According to the information from the I! SA. -Patenisthrift 34 45 23 became a direct positive veiled silver chloride

35

40

45

Prepared emulsion and applying a layer weight of 57 mg silver halide / dm ² to a polyethylene terephthalate carrier film, the preparation of which is given in Example 4 of US Pat. No. 2,779,684, followed by drying. The emulsion was then covered with a nickel (II) hexacyanoferrate (I!) Sol of Example 5 at 2.74 m / min and 38 ° C. under a red safety light and then dried with hot air.

A sample was seen through a positive streak and halftone image transparency with a 500 watt RFL photo flood lamp exposed, which worked at 110 volts at a distance of 0.61 m. The exposed sample was developed for 30 seconds in the developer of Example 1, rinsed for 5 seconds with water and 20 seconds with the activator solution of example 9 activated. After treatment with the humidifying solution of Example 1, the Plate for printing good positive proof color copies related ;.

Example 17

A sample of the material of Example 16 became transparent through positive line and halftone image transparency exposed with a 500 watt RFL photo floodlight lamp, which acted for about 20 seconds at 110 volts and a distance of 0.61 m. The sample was then 30 seconds at 23 C in a 1-phenyl-3-pyrazolidone / hydroquinone developer of high pH, containing 0.25 g / L benzotriazole and 0.5 g / L 1-caynoguanidine. The developed sample was incubated for 8 seconds at 23 ° C. in an activator solution of the type described below Manufacturing activated.

First, solutions A and B were prepared.

Solution a
3mo! Are aqueous copper (II) nitrate

trihydrate solution 25 ml

3 molar aqueous potassium bromide solution. 15 ml
3 molar aqueous citric acid solution. 25 ml
Imolar aqueous iron (II) nitrate solution 10 ml

Remainder: water to 900 ml

Solution b
1,10-phenanthroline

(1 g / 100 ml alcohol) 50 ml

1,2-bis (2-chloroethoxy) ethanol 10 ml

The activator solution corresponded to the following preparation:

Solution A 900 ml

Solution B 60 ml

Remainder: water to 1000 ml

The activated plate was sucked dry, placed on an office copier, with the dampening solution of Example 1 and used to print several hundred ink copies. There were good positive planographic images received.

10 mg, dm gelatin were present, which with 2.96 g formaldehyde and 11.25 g of dimethylolurea per 100 g of gelatin had been hardened. The material was then with the nickel (II) hexacyanoferrate (II) sol of Example 10 with smear coating at 38 ° C and 2.74 m / min covered and dried with hot air.

A sample of the material was passed through a step wedge and image transparency for 10 seconds with a

ίο lamp that comes with a setting 2 at a distance of 127 cm worked (same light source as in Example 14, voltage: 16 volts) exposed. It was an ultraviolet filter and a neutral density filter of 0.6 optical density were applied. The exposed sample was developed for 30 seconds in the developer of Example 1 and S see in an activator solution of the following composition activated:

3 molar copper (II) nitrate trihydrate solution 25 ml

3 molar potassium bromide solution 15 ml

3 molar citric acid solution 25 ml

Imolar iron (III) nitrate mono-

hydrate solution 10 ml

Remainder: water to 1000 ml

The plate was then rubbed with a 1% aqueous dispersion of colloidal SiO ₂ and used on an office copier to print offset copies using the ink and dampening solution of Example 1.

Example 19

A sample of the coated emulsion of the example 15 was bathed in a palladium (II) Hexacyanoferrat- (l I) -sol layered, which had been prepared as indicated below, wonac! was dried:

40

45

Example 18

A highly sensitive, orthosensitized gelatin-silver iodobromide emulsion containing 1.2 mol percent silver iodide and ^{having a gelatin to silver halide ratio of "5} " of 0.36 was coated on a photographic carrier film made of polyethylene terephthalate, with an excess weight of 7.2 mg Silver bromide per dm ^2. The emulsion was coated with an abrasion protection layer, in solution A

Water 665 ml

0.1 molar aqueous palladium (II) -

chloride solution 20 ml

0.1 molar aqueous potassium citrate solution. 15 ml

Solution b

Water 72 ml

0.1 molar potassium hexacyanoferrate (II) -

solution 20 ml

Condensation product of coconut fatty acid and diethanolamine

(1 g / 100 ml alcohol) 8 ml

Solution A was quickly added to solution B at 24 ° with vigorous stirring.

The sample was through a step wedge at one; Exposing a 0.0001 sec flash with an exposure device The exposed sample was developed for 30 seconds in developer d Example 1, washed for 5 seconds and activated for 15 seconds with an activator solution of the following composition:

3 molar aqueous copper (II) nitrate

solution 25 ml

3 molar aqueous potassium bromide solution. 15 ml 3 molar aqueous citric acid solution. 25 ml Rest. Water to 1000 ml

The activated sample was buffed with the moistening solution from Example 1 and then n

lithographic ink treated; good planographic prints were obtained.

Example 20

Example 19 was repeated with the exception that rhodium (H) chloride was used in place of palladium chloride was applied. Good planographic prints were obtained.

Example 21

A material prepared according to Example 10 was exposed on a photo printing device which had a cathode ray tube reading and below

operated under the conditions normally used for the exposure of folographic printing films. The exposed sample was 30 seconds in a suitable Developed developing device which was filled with the developer of Example 1, after which 8 sec in activate a suitable further treatment machine which was filled with the activator from example 9! became. Now the test was on the office copier of Example 1, buffed with the dampening solution of Example 1, with lithographic Cin-dyed printing ink and used to print hundreds of good quality offset copies on white Hard paper used.

Claims (7)

Claims: A layer of a gelatin-silver halide emulsion treated with a tanning developer which converts the gelatin in the image-bearing areas into an oleophilic colloid. The developed gelatin silver image can also be used to produce a bottle printing form. The silver image can be used to catalyze the oxidative degradation of the gelatin in the image areas and in this way to expose an oleophilic underlayer. In the known bromine oil printing process, the gelatin silver image is treated with a bleaching bath which tans the gelatin in the image-bearing areas so that it becomes receptive to printing inks. According to a known method, one of associated 1. Process for the production of planographic printing plates with imagewise exposure of a one
Photographic films containing a silver halide layer
Actinic radiation recording material
and development of the in this emulsion layer
present, latent image, characterized in that one of a resolution io
Drawing material goes out that has a layer support with an overlying, water-permeable
Gelatin-silver halide emulsion layer
and a hexacyanoferrate-containing layer acting on the surface thereof, which contains a silver halide-free silver image including a heavy metal hexacyanoferrate (II) or a heavy gelatin silver image converted into a planographic printing image metafl-hexacyanoferrate (JlI), which can be done by Carries out the following process heavy metal copper (H), nickel (II), cobalt (II), and metal stages in succession: Palladium (II) or rhodium (II) is, and that one first treats the picture with a bleach the exposed and, if necessary, watered finish, which converts the silver image into an image made of heavy duty material transferred with a copper (11) ion and / or silver compound, and sets Aqueous solution containing halide ions then mixes these compounds with an alkaline one treated. Solution of only slightly soluble organic compounds 2. The method according to claim 1, characterized in bonds around the — SH, —SeH, —OH or —NH groups draws that one contains a recording material in order to form compounds 7u which are less in which the hexacyanoferrate are content-soluble as the starting products of the odation tende layer on the surface of the emulsion and the image-bearing areas of the plate oleophilic layer lies. do. 3. The method according to claim 1, characterized in that the records corresponding to the state of the art that you can proceed from a normal silver image or a recording material in which the hexacyanoferrate contains a gelatin silver image that is tending layer on a thin, water-permeable, against the emulsion layer Abrasion-protective, colloidal intermediate layer made of protein is located. 4. The method according to claim I to ί, characterized in that a nickel-IIO-hexacyanoferraHll) or a nickel (II) -hexacyanoferrate (III) is used as the hexacyanoferrate. graphic methods from a gelatin silver halide containing photosensitive layer was obtained. These methods have several disadvantages. They are limited in their uses as these require a lot of experience, are of a complex nature, run slowly and involve fixing and washing stages require. Also own the won plates 5. The method according to claim 1 to 4, characterized in that 40 printing forms only have a short service life, characterized in that the layer support is a The invention is based on the object of providing a photographic FiIm from a hydrophobic, macromolecular, organic polymer applies. indicate graphic process with which lithographic printing forms can be quickly produced that are within very short) printable time characterized in that the layer weight of the 45 can be set and a long service life is set to at least 1 mg / dm ² as printing plates silver halide. The invention is based on a method for the production of planographic printing forms with imagewise Exposure of a layer containing a silver halide Gelatin-silver halide emulsion as emulsion 5 ° tend photographic recording material with layer used. actinic radiation and development of it 8. The method according to claim 1 to 7, characterized in that emulsion layer present latent image. Characteristic is that one starts out from a recording material which has a layer support with an on-55 lying water-permeable layer of a gelatin-silver halide emulsion and one on theirs Surface acting hexacyancefrrat containing Has layer which has a Sehwcrmetallhexacyanoferrat- (II) or a heavy metal hydroxacyanoferrate (III) The invention relates to a method for producing ^6o holds, the heavy metal copper- (II), nickel- (II). »On planographic printing forms with imagewise exposure is cobalt (II), palladium (U) or rhodium (H), and a photographic recording material containing a silver halide layer with actinic 6. The method according to claim I to 6, characterized preferably to 5 to 50 mg / dm ² . 7. The method according to claim 1 to 6, characterized in that one is an orthochromatic to 7, characterized in that one uses a photographic developer incorporated into the suspension. Radiation and development of the emulsion that the exposed and optionally watered starting material with a Kupfcr-OU-ion and Aqueous solution containing halide ions bc- • latent silver halide images present. ⁶ 5 is to transform the developed silver image into silver ions. It is known to transform lithographic plates from gelatin, whereby the exposed areas of the Emulsion layer for oily printing ink to be receptive. Silver halide emulsion layer preparation. To an associated process is an exposed