DE2305978A1 - PHOTOPLATE MANUFACTURING METHOD AND DEVICE FOR IT - Google Patents

Description

DR. E. WIEGAND DIPL-ING. W. NIEMANN DR. M. KÖHLER DIPL-ING. C GERNHARDT

MÖNCHEN HAMBURG TELEPHONE: 55547 «8000 MÖNCHEN 15, TELEGRAMS: KARPATENT NUSSBAUMSTRASSE 10

V. 41 467/73 - Ko / Ne February 7, 1973

Fuji Photo Film Co., Ltd. Minami Ashigara-shi, Kanagawa (Japan)

Photo plate making method and apparatus therefor

The invention relates to and relates to a photoplate manufacturing method and apparatus therefor in particular to a method for producing photographic plates as a sheet or web material, which consists of a hydrophilic Surface part or a hydrophilic layer, which is on an oleophilic support, and a photosensitive Halide emulsion layer superposed on the surface part or the layer, as well as an apparatus for carrying out the photoplate manufacturing process s.

The subject of the invention is a photoplate manufacturing method for manufacturing a printing plate and an apparatus to carry out the procedure.

The photographic plate manufacturing method according to the invention comprises the steps (1) of imagewise exposure

309833/0912

a plate substance for making a photo plate, r which consist of a hydrophilic surface part or a There is a hydrophilic layer present on an oleophilic carrier and therein silver deposition cores for diffusion transfer and a silver halide emulsion layer applied over it, (2) the development to form a positive silver image on the hydrophilic surface part or on the hydrophilic layer, (3) washing with water to remove the silver halide emulsion layer, (4-) Treating the hydrophilic surface part or the hydrophilic layer with a final bleaching treatment Release of the oleophilic surface portion that corresponds to the silver image, and (5) treatment of the arrangement with a specialist treatment, whereby any residues damaged by the JLtz bleaching treatment can be removed be made fragile.

The device according to the invention for producing photographic plates consists of (a) a plurality of pinch rollers to promote the plate substance to produce a planographic printing plate, (b) a development tray, a wash trough, a caustic bleach trough and a post-treatment trough to carry out the appropriate treatments of the plate substance, (c) facilities for removal the silver halide emulsion layer in the wash tub; and (d) means for removing the etched damage Residue in the cargo handling trough.

The present apparatus can be combined with photographic equipment which (1) a Manuscript support bed, (2) a magnification control device to determine the position of the photographic Lens according to the desired photographic magnification, (3) a camera for photographing the manu-

309833/091 2

scripts on the disk substance, which is in a magazine is contained as a housing, by means of a lens and (4) means for conveying the photographed plate substance in the form of a roll on a photogravure device and devices for cutting off the conveyed Part for automatic and continuous execution the photographing operation and the photographic plate making process contains.

There have been various methods of making photographic plates using a photosensitive layer to a photosensitive silver halide emulsion layer suggested, but showing various errors. For example, in the US patent 2,448,861, a dichromate is used as the photosensitive substance. With this procedure lies the photosensitive range of the photosensitive substance is mainly in the ultraviolet range and it is not only the sensitivity of the substance is low; it is also the preservation or storability of it produced light-sensitive web substance extremely poor.

According to the Japanese patent publication 27242/69 or U.S. Patent 3,385,701 In the process, the printing plate consists of an oleophilic support and one applied to the surface of the support hydrophilic layer. However, these methods show various defects in that the adhesion of the surface of the oleophilic support and the hydrophilic layer is low, so that the hydrophilic layer in the unexposed Parts can be easily separated from the surface of the support during printing and are hydrophilic Surface due to the deposition of oily

309833/0912

Printing inks from this can show staining. The hydrophilic layer used in this process is made of gelatin, colloidal silica and the like, and the hydrophilic properties of the layer are not always sufficient. Therefore, oil-like inks gradually separate on the non-image parts with increased amounts of pressure until the hydrophilic surface begins to stain shows. Therefore, a sufficient number of high quality printed reproductions cannot thereby be made can be obtained. .

In addition to the usual procedures outlined above, British Patent Nos. 913,591 and 998 447 A method of making lithographic Printing plates in which a metal plate such as an aluminum plate having a hydrophilic surface is used wherein the metal plate has an activity of reducing the silver salt by the diffusion transfer method and an oleophilic silver image is formed on the metal plate so that the silver image is the forms oleophilic part. However, aluminum is easily oxidized by air to form aluminum oxide, so that the activity of the same as diffusion transfer nuclei bad is. Furthermore, the density of the deposited silver image is low and consequently it is in the process required according to British patent specification 913 591, to use a specific treatment solution including a chemical agent which has an activity for the deposited silver image has to improve the oleophilic properties of the deposited silver image. In British patent specification 998 447 there is one treatment with a strongly alkaline solution, e.g. lithium hydroxide solution, is necessary to dissolve the aluminum oxide layer. ·.

309833/0912

The Sirber salt diffusion transfer processes are well known in the art and in these processes the imagewise unexposed silver halides become of the photosensitive silver halide emulsion is converted imagewise into distributions of a soluble silver complex and the complex then diffuses into silver deposition nuclei, which convert the soluble silver complex transported by diffusion: into silver.

The German Offenlegungsschrift 2 048 594 describes an improved photolithographic process free from the foregoing defects. The procedure includes the steps of forming a reverse silver image, after which a photosensitive sheet material composed of a organic, acidic cellulose ester sheet with a hydrophilic Surface part consists of the core substances for the diffusion transfer process contains, and one light-sensitive silver halide emulsion layer coated on the hydrophilic surface, has received an original image exposure, corresponding to the original in the hydrophilic surface means a diffusion transfer process and then with an aqueous solution containing hydrogen peroxide is treated to remove the hydrophilic surface in the areas where the silver image is present, so that the oleophilic surface of the organic, acidic cellulose ester sheet is released.

For this method, however, it is necessary to greatly increase the hydrophilic surface during Itz bleaching rub in order to release the oleophilic surface and due to the friction, hydrophilic parts or frequently remain scratches form. As a result, it is difficult to fully expose the oleophilic surface. if

309833/0912

Furthermore, the hydrophilic superficiality-enteil is diluted so that the oleophilic surface by slightly rubbing the same is released, the ETicht-image areas show a tendency to J ¹ Ieckenbildung during printing and thin lines are hardly or not be played.

The invention provides an improved photographic plate making process which is free from the defects of the usual methods, as well as an apparatus for carrying out the improved method.

The objects of the invention are summarized below:

1) A method of making a printing plate, which produce a large number of high quality print reproductions can deliver,

2) a photo plate making process which can only be carried out by a single worker,

3) an apparatus for the photographic plate making process for making printing plates having a large Number of high quality prints.,

4-) a device for the printing plate making process, which is automatic by only one worker can be carried out in a bright room,

5) an automatic handling system for a photo plate making process, by which a printing plate can be made automatically, a number of which of high quality print reproductions can be made with this system by only a single worker Can be run in a bright room.

The above tasks are according to the invention Process achieved, which after the imagewise exposure of a plate, which consists of a hydrophilic surface part or a hydrophilic layer that is on top

309833/091 2

an oleophilic carrier, and one applied to the hydrophilic surface part or this layer Silver halide emulsion consists, through the stages of development, of washing with water, of undergoing a Etching-bleaching treatment and the subsequent exposure a follow-up treatment is marked.

The device for carrying out the present purposes comprises in combination devices for promoting the plate substance to be treated successively through a developing trough, a washing trough, an etching-bleaching trough and a post-treatment trough, the respective treatment solution to achieve the stated purposes contain means for removing the silver halide emulsion layer in the washing trough and facilities for removing the damaged residues in the after-treatment trough.

In a further embodiment, the apparatus described above is provided with a photographing device for the exposure of the plate substance combined, which a manuscript carrier bed (original carrier bed), facilities for controlling the desired magnification of the original for exposure of the plate substance, devices in which the plate substance is exposed; and means for conveying the exposed plate substance to that in the foregoing Paragraph covered device consists. If the plate substance is in the form of a roll, are Cutters are provided for cutting the plate substance to the desired length prior to development and the like.

In the drawings is

1 shows a cross section of a treatment device according to of the invention, in section along the direction of the photosensitive material for a printing plate being conveyed will,

309833/0912

Hg. 2 shows a Seitansicht a Ausführungsfοnn dei ¹ the present device, and

Fig. 3 is a side view showing the inside of a magazine box shows.

The hydrophilic surface part that is on an oleophilic Carrier is present forms a structure wherein at least one surface of a plastic sheet hydrolyzes is to make them hydrophilic. The hydrophilic surface part and the oleophilic layer are thus integral . and the hydrophilic surface part has excellent * mechanical strength, which is different from the hydrophilic layer differs, as explained below. Therefore, the hydrophilic surface part does not easily peel off from it oleophilic carrier. The thickness of the entire arch is usually about 80 to 300 η taking into account the Strength of the wearer, the cost and the ease of use, even if greater or lesser strengths are used can. The strength of the hydrophilic surface part is thinner than that of the arch and is from about 0.1 to about 30 µ, preferably from about 0.3 to about 10 µ and thickest preferably 0.3 to 3 tu

Suitable plastic sheets are those whose contact angle to water more than 45 ° before the hydrophilic treatment, but less than 45 ° after the hydrophilic treatment at normal temperature is. Illustrative examples for plastic sheets that can be treated in the above manner are, for example, organic, acidic cellulose ester sheets, such as cellulose diacetate sheets, cellulose triacetate sheets or sheets consisting of a mixture of these two acetates, cellulose acetate sheets, cellulose propionate sheets, cellulose butyrate sheets, Cellulose acetate butyrate sheet or similar material or organic, acidic cellulose

3 09833/0912

ester sheets, such as cellulose nitrate sheets, polyvinyl ester sheets, such as polyethyl en terephthalate sheets, polystyrene sheets, polyvinyl acetate sheets or the like, polyvinyl acetal type sheets such as polyvinyl acetal sheets and the like.

The surface parts of these sheets can be made hydrophilic by hydrolyzing them with an alkaline agent will. In some cases, other treatments can be carried out to improve the hydrophilic properties of the To achieve part of the surface. These treatments include, for example, acid hydrolysis of polyvinyl acetal or Modification of polyethylene terephthalate, polystyrene and The like. Using dichromic acid or nitric acid or oxidation of the same by means of ozonization and / or High frequency discharge. Methods typically used are in U.S. Patents 2,448,861 and 2,494,053 specified. Examples of treatment baths are 50 g NaOH, 400 cm3 of ethyl alcohol, 1 liter of water and 200 cm ^ 10% NaOH, 400 cm5 ethyl alcohol, 10 cm ^ acetone, 1000 cm ^ Water and the like

In the hydrophilic surface part obtained in this way, silver deposition nuclei such as heavy metals such as cadmium, tin, zinc, chromium, nickel, cobalt and the like, noble metals such as gold, platinum, palladium and the like, or sulfates and selenates of such heavy metals or noble metal salts , for example, SnC ^, AgNO ,, silver citrate and the like., Introduced. Such materials are known per se, for which reference is made, for example, to the report of the meeting of the Liège Conference, April 15-17, 1948 by Hautot, and US Patents 2,698,237, 2,698,238, 2,774 and 2,698,245.

309833/0912

The silver deposition nuclei can be in the hydrophilic Surface part introduced simultaneously with the treatment for hydrophilization or after the hydrophilization treatment will.

For the purpose of introducing the silver deposition cores, the above-mentioned silver deposition cores can be found in Water can be dispersed to form a colloidal dispersion and then contacted with the hydrophilic surface portion will. In this case, alcohols, ketones or chlorinated hydrocarbons can be used. These solvents in particular have the property of swelling celluloses, so that if celluloses are used, it is preferred to use these solvents singly or in the form of a mixture or together with water, so that the kernels can be easily inserted into the celluloses. The most preferred embodiment of the The invention therefore consists in the use of organic cellulose acid ester sheets of the plastic films listed above to achieve the hydrophilic properties of these ester sheets.

Examples of usable alcohols and ketones include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, Butyl alcohol, ethylene glycol, propylene glycol, polyethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone and similar materials. Solvent mixtures such as water-methyl alcohol, water-ethyl alcohol-acetone are particularly preferred and the like, since they can accelerate the hydrolysis.

As is known, the concentration of the core substance can vary widely, e.g. For example, the concentration of NiS generally of such a small amount, such as 5 x ΊΟ "* ³ mol l up to an amount as large as about 5 x 10 ^-2 mol / / l.

309833/0912

The core insertion temperature is around 15 to about 60 ° C and can be up to about 10 ° C lower than the boiling point of the solvent, with the preferred Range is 20 to 50 ° C.

The reaction time varies depending on the temperature, for example at 50 ° C 5 seconds to 60 seconds, at 35 ° C 20 seconds to 120 seconds and at 20 ° C 35 seconds to 240 seconds.

On the other hand, under the hydrophilic layer present on an oleophilic support, that on a plastic sheet becomes coated hydrophilic colloid layer as indicated above, understood. Examples of hydrophilic Colloids include gelatin derivatives such as gelatin, phthalated gelatin and the like, gasein, alginates, polyacrylic acid, Maleic anhydride-methyl methacrylate copolymers, vinyl derivatives derivatives, for example polyvinyl alcohol, polyvinylpyrrolidone, or salts thereof, for example the metal salts, like Na, K, Li ^, - salts.

The thickness of this layer is usually about 0.3 / U to about 10yu, preferably 0.3yu to 3 Ά · If the thickness is too large, it becomes difficult to carry out the etching bleaching.

For the purpose of introducing the silver deposition nuclei into the hydrophilic layer, those listed above are used Silver precipitation nuclei are dispersed in the aqueous, hydrophilic colloid solution, as described above, and applied to an oleophilic carrier.

A silver halide emulsion layer is formed on the above-mentioned hydrophilic surface part or on the hydrophilic layer applied, the preferred strength of the dried emulsion 1 generally to 15 / U and the preferred amount of silver is between 30 lags / cm to

309833/091 2

900yUg / cm.

The ratio of silver halide to binder is not essential. In general, the silver halide emulsion layer is used drawn onto the hydrophilic surface part or the hydrophilic layer and dried, and the plate covered thereby then stored. If the plate is to be used, it can be exposed imagewise. The emulsion layer is preferably not hardened or only slightly hardened, so that the development can be carried out easily.

The silver halide emulsion is one which is prepared by dispersing an emulsion of a silver halide became, as in general in the photographic art known and used, for example silver chloride, silver bromide, Silver iodide, silver bromochloride, silver bromide iodide, silver bromide jo de hl ο rid and the like., In the above. on led hydrophilic colloid! The silver halide emulsion may contain additives generally known in the photographic Specialty are used, such as dye sensitizers, Fog preventive agents, stabilizers, hardeners, surface active agents and the like.

A layer of one-in-one natural or synthetic High molecular weight material such as an intermediate layer, protective layer, or the like, may be interposed between the hydrophilic surface part or the hydrophilic layer and the silver halide emulsion layer may be present and if desired, pigments can be incorporated into the hydrophilic layer or the intermediate layer can be incorporated.

The exposed silver halide emulsion layer is then developed to form the silver halide emulsion layer is contacted with the hydrophilic surface part or hydrophilic layer. Become a developer for development

309833/091 2

for the diffusion sub-transfer process, which uses a solvent used for the dissolution of silver halide, such as sodium or potassium thiosulphate. The exposed Silver halide emulsion layer and the hydrophilic surface part or the hydrophilic layer are in the Developer, and in particular, the layers are preferably immersed in the developer together with the oleophilic carrier immersed from the point of view of easy handling. The developers that can be used are based on the photographic Known in the art and described in detail in "Processing Chemistry" by Mason (The Focal Press, 1966). According to the In the invention, the usable developers can be selected from the known diffusion transfer developers without any specific one Critical choice must be made with regard to the particular developer employed, although typically developers with hydroxyl groups and amino groups in the o- or p-position are used, for example dihydrobenzene, such as hydroquinone, Chlorohydroquinone, bromohydroquinone, toluhydroquinone, tert-butylhydroquinone, p-methylphenol sulfate, triaminophenol, Pyrogallol, alkoxy-substituted hydroquinones, where the compounds with an amino / phenol group are often used as salts, for example of HCl, ^ S (X, 3-pyrazolidone, for example 1-phenyl-3-pyrazolidone, pyrimizine, for example 4-amino-5i6-dihydroxy dimethylpyrimizine and similar materials.

The developers are used in the amounts usually used, for example 5 Ms 35 g / l for Dihydro xybenzenes.

The silver halide dissolving agents can be selected from those known in the art, for example NaSCN, KSCN and NapS20, and they are commonly used in used amounts used, for example 4 · g / l to 30 g / l.

309833/091 2

In the method of the present invention, if a non-hardened or slightly hardened emulsion is used for the purpose of carrying out the treatment quickly and stably, the development must be carried out at such a temperature that the emulsion layer does not melt. This temperature is generally lower than 30 ° ^C. On the other hand, the lower limit of the temperature is preferably higher than 0 ° C in order to prevent the developing speed or developing sensitivity from becoming too slow. The generally used practical developing temperature is 10 to 35 ° ^C. , preferably 15 to 25 ° C. The developing time can be easily determined by those skilled in the art depending on the kind of the developer, the developing temperature and other conditions, and is usually 10 seconds to 50 seconds. preferably 20 to 40 seconds.

Having a positive silver image on the silver deposition cores formed by the diffusion transfer treatment, the silver halide emulsion layer becomes unnecessary, so that this layer from the hydrophilic surface part of the hydrophilic layer by washing with water Will get removed. In this treatment, if the protective layer or intermediate layer described above is present is removed along with the emulsion layer.

The temperature for washing with water is selected so that the removal of the emulsion layer from the hydrophilic surface part or the hydrophilic layer is easy, and generally it is at least 35 ° C., with a minimum value of 40 ° C. giving better results. The preferred working range is 45 to 55 ° ^C. The hydrophilic surface part is made up of the oleophilic carrier

309833/091 2

just peeled off with difficulty compared to hydrophilic layer, so when the hydrophilic surface part is used, the emulsion layer thereof by means of a roller or the like without damaging the hydrophilic Surface part can be peeled off.

If desired, can be added to the water used for washing Accelerators, such as protein degradation enzymes, Thioeyanate, urea and the like. Incorporated, which make washing with water easier to carry out.

The hydrophilic surface part or the hydrophilic layer which has been washed with water then becomes one Etched bleach treatment. The caustic bleach treatment represents a measure for exposing the oleophilic surface in accordance with the SjILberbildteil. By this treatment the hydrophilic surface part or the hydrophilic layer corresponding to the image part is damaged. With the The term "damage" denotes the phenomenon that the hydrophilic surface part or the hydrophilic layer, containing the silver image is easily removed from the plastic sheet by means of an etching-bleaching treatment with the parts that do not contain a silver image. Even so, the sheets treated in this way have errors when used as a printing plate.

The caustic bleach solution used contains an oxidizing agent, which is used in common photobleaching solutions, for example sodium ferric hexacyanate dichromate, Hydrogen peroxide and the like. In particular, peroxodisulfate has good stability in solution, so that Peroxosulfate or peroxodisulfates are preferred oxidizing agents. These can be used individually or in the form of Mixtures are used and the most effective amount is 0.55 "to 30% by weight of the treatment solution.

309833/0912

In order to accelerate the etching effect, at least one copper (II) salt, an acid or a substance that reacts with silver halide to form a complex of low solubility is present in the etching solution be. Examples of useful copper (II) salts include water-soluble copper (II) salts, such as Eupfer (II) chloride, Copper (II) bromide, copper (II) nitrate, copper (II) sulfate, Copper (II) citrate and the like. The "copper (II) halides are preferred. Examples of suitable acids include organic acids such as acetic acid, citric acid, tartaric acid, Phthalic acid, maleic acid, benzenesulfonic acid and the like, and examples of inorganic acids include hydrochloric acid, nitric acid, Sulfuric acid and similar materials.

Examples of substances which react with silver to form a compound of low solubility include the halides, tartrates, carbonates, chromates or ormates. In particular, the halides are preferred, for example NaBr, KCl., KBr, LiBr, HH ₄ Br, Ha3, KJ, and similar materials,

Accelerators and / or such materials that react with silver are e.g. B. in U.S. Patent 3,385,701, British Patent 587,957 and German OLS 2 048 594 indicated.

These accelerators can be used singly or in combination. The amount of the accelerator is usually 0.05 to 50% by weight of the treatment solution. Some compounds have a solubility of less than 50%, although an amount thereof of more than 0.05 ° / ° is sufficient.

If a peroxodisulfate together with at least one the etching accelerators listed above (copper (II) salts, acids or substances that interact with silver

309833/091 2

forming a. Complex of low solubility react) is used, the amount of peroxodisulfate, calculated as ammonium peroxodisulfate, 0.0125 to 30% by weight of the treatment solution.

The preferred amount of the peroxodisulfate is ^ however, calculated as ammonium peroxodisulfate, 0.1 to 20% by weight when the stability of the etching solution with the lapse of time and the stability of the light-sensitive material is being considered. When using this solution, the parts of the hydrophilic layer are corresponding to the Silver image etched at 5 to 40 ° C within 30 seconds and damaged.

The etching-bleaching treatment temperature is usually 50 ° ^{C. to} 45 ° C., preferably 10 to 40 ° C. in consideration of the stability of the etching-bleaching solution with the lapse of time and the reaction rate. The etch-bleach time can vary widely, but 10 to 60 seconds is sufficient for most elements being treated.

The preferred caustic bleach solutions contain an oxidizing agent, an acid and a material which forms an insoluble compound with silver, referring to the British Patent 587 9571 US Patent 833 274-, See U.S. Patent 3,385,701 and OLS 2,048,593 will.

The surface of the sheet material treated by etching is rubbed weakly, thereby making the surface part hydrophilic according to the silver image is easily removed so that the oleophilic surface of the arch is exposed will. On the other hand, the hydrophilic surface part free from the silver image remains as such. The on this Wise-made printing plate can be used as a direct printing plate or an offset printing plate according to the usual methods

309833/0912

be used. In addition, the plate can be subjected to a post-treatment to a desired piano graphic printing plate with better properties obtain.

The term "post-treatment" denotes a treatment whereby the residues damaged by the above etching-bleaching treatment become fragile. ¹ and include, for example, a treatment of the hydrophilic surface part or the hydrophilic layer, which has been subjected to etching bleaching, with a solution of a chloro-oxygen acid, such as chlorous acid, hypochlorous acid or perchloric acid or a salt of such an acid, a water-soluble thiocyanate, a dye that is physically attached to is adsorbed on the hydrophilic surface part or the hydrophilic layer and has one or more anionic substituents, or mixtures thereof.

The "fragile" residues that result have been damaged or made fragile by the bleaching treatment and can be completely removed by this post-treatment, or in certain cases they can be easily removed by only lightly wiping the surface with a sponge, cotton wool, and the like without damaging the hydrophilic surface part or the hydrophilic layer in the non-image part, so that the operational efficiency is extremely improved. The printing plate finally obtained produces print reproductions with extremely high sharpness and resolution.

If the embodiment with the hydrophilic surface part is used, a particularly superior effect can be achieved by the post-treatment.

In the embodiments working without dye

309833/0912

After treatment, the temperature is generally between about 5 and about 80.degree. C., preferably 10 to 40.degree. C., the concentration of the active ingredient generally 0.1 to 50 %, preferably 0.2 to 5% by weight, based on 1 liter of the aftertreatment bath is, although in the case of KSCN the concentration is favorably 0.1 to 20% and in the case of NaClO the use of 2 to 30 mol% of NaClO with a content of 10 % effective Cl per liter is favorable.

Examples of the dyes listed above include direct dyes, basic dyes, Naphthol dyes (coupling components of azo dyes), acidic dyes and the like described in Japanese publication "Handbook for Dyes" (Maruzen Publishing Co., 1970), pp. 83 and 245 "through 246. Examples for anionic, useful substituents include

2-2

the sulfon group, sulfin group, CO ^ group, CS ^ group, carboxyl group and the like, in the form of an acid and / or a salt, for example an Na, K or NH ^ salt.

The direct dyes contain one or more anionic substituents such as a sulfonic group and the like. In the post-treatment according to the invention, any type of direct dye can be used and especially preferred dyes are, for example: CI. Direct Yellow 11, CI. Direct Yellow 12, CI. Direct Yellow 26, CI. Direct Yellow 39, CI. Direct Yellow 44-, CI. Direct Yellows 50, CI, Direct Orange 6, CI. Direct Orange 8, CI. Direct Orange 10, CI. Direct Orange 26, CI. Direct Orange 39, CI. Direct Orange 49, CI. Direct Orange 51, CI. Direct Red 1, CI. Direct Red 2, CI. Direct Red 4, CI. Direct Red 9, CI. Direct Red I3, CI. Direct Red 20, CI. Direct Red 23, CI. Direct Red 28, CI. Direct Red 3I,

309833/091 2

C.I. Direct Red 37, C-I-Direct Red 62, C.I. Direct Red 79, C.I. Direct Red 80, C.I. Direct red 81, C.I. Direct Red 8J, C.I. Direct red 89, C.I. Direct red 224, C.I. Direct red 225, C.I. Direct red 226, C.I. Direct Red 229, D.I. Direct Red 230, C.I. Direct violet 4-7, C.I. Direct blue 1, C.I. Direct Blue 71, C.I. Direct blue 78, C.I. Direct Blue 86, C.I. Direct Blue 98, CI. Direct Blue 106 and the like

Many basic dyes contain cationic groups such as methylene blue, malachite green crystal violet, Victoria blue and the like, and do not contain any anionic groups Substituents. Such basic dyes cannot be used according to the invention. on the other hand basic dyes which have anionic substituents, e.g. C.I. Basic Violet 10 (Rhodamine B) and similar materials can be used according to the invention, whereby, the same effect as in the case of the direct dyes listed above can be obtained.

The ITaphthol dyes which can be used are those of Naphthol series, the coupling components of Azo dyes represent, for example 2-hydroxynaphthalene-3-carbonylanilide-A -'-sodium sulfonate and similar. In other words, the ITaphthol dyes are substances that act as the basic structure have the 2-hydroxy-3-naphtho-anilide group. That's why are compounds which have one or more additional substituents and / or condensed rings in the naphthalene ring and / or benzene ring of 2-hydroxy-3-naphthoic anilide, included from the class of naphthoI dyes, which can be used according to the invention, for example alkyl-, alkoxy-, phenyl-, anthraquinone-substituted Materials or materials with similar substituents.

Acid dyes which have anionic substituents

3 09833/0912

are generally transparent to direct dyes inferior to physical adsorbability on plastics, in particular on hydrophilic cellulose materials at normal temperature. However, if the temperatures of the aqueous solutions of the dyes are increased be, for example to 50 ^ is 90 ° C, the physical Adsorptive capacity can be improved, so that these dyes according to the invention increased in them Temperatures can be used. Illustrative examples of such acidic dyes are e.g. B. C.I. acid Yellow 19, CI. Acid Yellow 99 and the like.

Most of the acidic dyes containing anionic substituents are similar to those listed above, however, some acidic dyes can give the same effect as direct dyes even at normal temperature. Although this class of dyes is very limited, such acidic dyes include those according to the Invention are effective, for example C.I. Acid Blue 158, CI. Acid Bed 186, CI. Acid Red 265 and similar materials.

The direct dyes, basic dyes, naphthol dyes and acidic dyes listed above can be used singly or as mixtures of two or more thereof.

The concentration of the solutions of these dyes can depend on the type of dyes used, the properties of the layers to be etched, such as the degree of hardness, type, thickness and the like. Of the layer, as well as the The temperature of the solution of the dyes vary. Although the concentration thus depends on a number of Depending on factors, the dye will generally be present in an amount greater than 0.01% by weight of the solution. the

309833/0912

Dyes can also be in the form of a supersaturated solution be present at certain temperatures and within a certain solution composition. Preferably contains the solution about 0.5 to 5% by weight of the dyes.

The pH of the solution of the dyes can be acidic, neutral or alkaline. However, it is especially alkaline State preferred, with a neutral to slightly alkaline state of pH 7 to 11 being most preferred will. As a result, proper adjustment of the pH of the dye solution is usually made if necessary executed. An alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate can be added to this setting and the like, or an acid such as acetic acid, sulfuric acid, hydrochloric acid, nitric acid and the like are used will.

The temperature used for the dye solution used is generally in the range from 2 to 90.degree and more preferably 10 to 50 ° C. The treatment period varies depending on the properties of the ones to be etched. Layer, the composition of the solution of dyes and the like. In general, the treatment period ranges from 5 seconds to 5 minutes.

Z.U the solution of the dyes, the at least one anionic Contain substituents and which are physically located on the hydrophilic surface part of the hydrophilic layer adsorb according to the invention, additional organic solvents, which are miscible with water, can be used as auxiliary solvents be added, e.g. B. Hydroxyl groups Solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol and the like., Solvents of the ketone series such as acetone, methyl ethyl ketone and the like., Or solvents of the Ether series, such as ethylene glycol monomethyl ether, ethylene

309833/0912

glycol diethyl ether and the like. In general, 2 to 60% organic solvent, "based on the solution weight, can be used, with organic solvents in small amounts (2 to 20%) in water being particularly preferred.

The use of such post-treatment solutions which contain dyes gives a particularly excellent result Effect for celluloses with a hydrophilic surface part or for celluloses, the hydrophilic layer.

The treatment by using these treatment solutions is generally carried out after the treatment using the caustic bleach solution. A water wash can be performed between these two treatments.

According to the above post-treatment, various advantageous effects, as discussed above, can be achieved can be achieved, so that a high quality printing plate can be obtained, of which a number of Print reproductions can be produced with a high degree of sharpness can.

Another effect is the following: If the dyes listed above except the naphthol dyes are used as dyes, they are only adsorbed on the non-image parts that are not etched so that different kinds of colored reversal images according to the kind of the dye used can be obtained. If, therefore, the post-treatment according to the invention during the treatment in the photoplate manufacturing process carried out, the question can be whether the etching process was complete or whether the reproduction of a manuscript is sufficient or not, usually answered without inking the printing plate obtained will. As a result, the operational efficiency of the present process is also markedly improved.

309833/0912

If one obtainable by the process according to the invention Printing plate is placed in a heat pro ^ ector, before it is colored with an ink, eye spots do not appear because the difference between that with the Dyes colored parts and the non-colored parts is extremely powerful. -..-- ·

It should be noted that, generally speaking, developing, water washing, etching bleaching and post treatment finishes within 15 to 4-5 seconds and that using the device described above extremely rapid and effective treatment can be carried out, for example within a period of 1 minute to 3 minutes. ·

The apparatus for producing photographic plates according to the invention will be described in detail below with reference to the enclosed Drawings explained.

In Fig. 1, 10 denotes the entire device arrangement. Each of the treatment troughs 22A to 22D is with a treatment solution used in accordance with the present photographic plate manufacture. The device 10 has practically the same construction as a common automatic treatment machine used for DP treatment (photographic development and printing) and the like are used except that the sponge rollers 28 and the pressing plates 27 are mounted in the fourth trough 22D, such as explained below.

A brief explanation of the device 10 is as follows: The treatment troughs 22A to 22D consist of troughs of a developing bath 22A, a water washing bath 22B, a caustic bleach bath 220 and an aftertreatment bath 22D. The substance to be treated is conveyed by means of nip rollers 24 and guide plates 23 and 25,

309833/0912

d. H. the conveyor system consists of a roller conveyor.

Heating facilities: 26 and cooling facilities of the water circuit 36 are if desired for the purpose the control of the liquid temperature. A Aufnahmeegli.ed 32 is for the purpose of recording the in the first trough 22A and the second trough 22B treated plate and generally the member 22 is closed, to block the light from inside the treatment troughs. The developer can according to the extent of the development of the developed plate.

A detailed explanation is given below with reference to the device 10 shown in FIG. 1 with regard to the treatment and the method of the printing plate according to the invention, which consists of a hydrophilic surface part or a hydrophilic layer, which is silver deposition nuclei for diffusion transfer and which is attached to an oleophilic support, wherein a silver halide emulsion layer is superposed on or is on the surface portion or layer.

The plate usable for printing which photographs by means of a camera for photographing or the like is brought into the interior of the device 10 by means of a guide plate 19 and then becomes sequential to the first trough, the second trough, the third trough and the fourth trough in this order and forms finally the printing plate.

The first trough 22A represents the development bath. This trough is filled with a developer which is selected from the specified Components is filled at a temperature above 0 to 30 ° C. The plate is fed into the development bath, whereby the exposed silver halide emulsion

309833/0912

si ons layer on the plate of diffusion transfer development is subjected. When the plate has reached the outlet of the first trough 22A, it is a positive Silver image, in the hydrophilic surface part or the hydrophilic one Layer of the plate formed.

The second tub 22B is a water washing bath. The plate that has passed through the first trough is placed in the water wash bath 22B conveyed along the guide plate 25 where the SiI overhalide emulsion layer Will get removed. If auxiliary layers, such as protective layers, intermediate layers or the like., are present, these layers are also removed at the same time. The water for laundry is warm Water with a temperature higher than 40 ° C. To remove the emulsion layer, it is effective to use a rotary removing device Or the like. To be installed in this trough that does not cause any damage, such as scratches or the like, to the plate substance cause. In particular, it is effective to mount pairs of rollers in the second trough for the linear speed the rotating device different from the conveying speed the plate so that a higher effect is achieved.

In Fig. 1, an embodiment of a removal device is shown, which consists of sponge rollers 27 and a Pressure plate 28 consists. The sponge rollers 27 can also Be attached face to face against one another. The removal device is not limited to sponge rollers. The rotary removal device can also, if desired be present at the outlet of the water wash bath 22B.

In the plate discharged from the second tray 22B the silver halide emulsion layer is removed and the hydrophilic surface part or the hydrophilic layer, which contains a silver image is released.

30 9 833/0912

The third trough 22C represents an etch-bleach bath. The one conveyed from the second trough 22B to the third trough Plate is subjected to the etching-bleaching treatment in the third vat. The various conditions, such as composition the. liquid supplied to the third trough, temperature of the liquid and the like is selected within a wide range as in the case of the treatments in the first tub 22A and the second tub 22B will. The etching-bleaching treatment makes the hydrophilic Surface part or the hydrophilic layer corresponding to the image part is damaged. At this stage the plate can are used as a printing plate, but usually does not give sufficient print reproductions. Therefore be the plates thus subjected to the etching-bleaching treatment continue to be conveyed to the fourth tray 22D.

The fourth tub 22D is an after-treatment bath in which the plate that has been subjected to the etching-bleaching treatment is post-treated. The post-treatment measures exist therein, as stated above, that the hydrophilic surface part or the hydrophilic layer which is formed by the The caustic bleach solution has been damaged, is made brittle. Therefore, the plate discharged from the fourth tray 22D can be used as a printing plate as such or just after rubbing the Surface of the plate by means of an elastic substance such as a sponge, cloth or the like. Can be used.

TJm the treatment for rubbing the surface of the plate with the elastic substance after the post-treatment can be omitted in the fourth trough 22D, or to make treatment easier, in the fourth trough 22D a Removal device be present, d. H. a device that has the same effect as that within the second Trough 22B existing device for the purpose of

309833/0912

removal of the silver halide emulsion layer provides. In particular, the hydrophilic surface part or the hydrophilic layer damaged in third tray 22C and any remaining silver halide emulsion layers by means of sponge rollers corresponding to the rollers 27 and a press plate corresponding to the press plate 28 removed. All substances that have a removal effect can be used for this removal measure and do not damage the surface of the plate.

The plate, with which the treatment in the treatment trough 22D has ended, is optionally placed on a receiving plate J1 as an original plate for printing over a drying device, which is attached to the end part of the device 10, given.

In Pig. 2 is an apparatus for a photographic plate making process, that the device according to Pig. 1, with a camera device combined with it shown. Specifically, this device is made from a manuscript support bed 8, a photo enlargement control device for changing the relative position of the mirror 4 and a lens 5 »a device for promoting a Plates sub s tan ζ to the photographic equipment and to the Cutting the conveyed part, whereby the plate substance was photographed inside a camera device, for example by photographing the image of the manuscript onto the disk substance in the form of a roll, which is contained in the magazine box 1, by means of the mirror 4- and the lens 5 »and the photo-engraving device 10, such as shown in Fig. 1, constructed.

The manuscript carrier bed 8 is parallel to the earth's surface to change the relative position with respect to the

3 0 9833/0912

Idnsenreiheneinrichtung "movable to any desired Photography, for example enlargement, same size or reduced size, by means of the photo enlargement control device to achieve.

For photographic purposes, the manuscript is attached to the manuscript support bed 8 by means of a glass plate in such a way that the manuscript is kept flat.

A light projector 7 is movable so that the surface of the manuscript is exposed evenly. When the intensity of the lighting on the manuscript bed through Use of a plurality of light sources is increased, the luminosity of the respective light source can often individually vary over time. In order to avoid such individual variation of the lighting, the relative The position and angle of the light source and the manuscript support bed are adjustable.

It is necessary that a positive image of the manuscript on the printing plate substance is photographed by means of the camera device 9. For this purpose, the mirror 4, a prism or the like is included in the optical system. The lens 5 and a closing iris are the same as in the lens system of a photogravure camera. The elements "2. And 3" are explained in detail in the discussion of FIG. 3.

Fig. 3 shows the interior of the magazine box 1. The leading end part of a plate substance 12, which is in the form · a roll is wound in a spool 11, is conveyed over the nip rollers 13 and the guide plates 20 and the plate substance is flat on a plate carrier plate 15 »d. H. in the position where the plate substance photographed is held by the nip rollers 13 and 13 '. The photosensitive material 12 can

309833/0912

. - 30 -

by applying suction to the material 12 im Vacuum from the back surface of the photosensitive surface hereof "be held in place or by pressing the entire surface of the material 12 onto the camera back 15 by means of a plate which is translucent.

The plate substance 12 is moved downwards by means of the Rollers 13 promoted and after a plate with the desired Large was promoted to the desired position by the action of a cam 17, which by means of a timer (not shown) is operated, the plate 12 is formed into a sheet by means of a cutter 16 cut, which for interaction with the cam 17 is set up. The sheet cut in this way becomes the photo-engraving device via a slit 18 promoted in a flexible container 3. The guide 19 conveys the cut plate substance to the operator.

A light closure curtain 14 is slidably provided, so that the front surface of the plate 15 when actuated a handle 2 on the outside of the magazine box 1 is covered so that the plate substance 12 can be exploited economically according to the size of the manuscript.

As the plate substance, an arc type substance can of course be used.

The process of photographing and promoting the Plate substance to the photogravure device is described below based on the combination device on the camera device 9 and the photo plate making device described.

A manuscript that has just been placed on the manuscript support bed 8 is enlarged with the necessary photo enlargement.

309833/0912

Appropriate control of the positions of the carrier bed 8 and lens 5 according to the desired photo magnification held. Then the manuscript is photographed onto the plate substance, which is on the plate support plate 15 by means of the lens 5 was made. After the end of the photograph, the plate substance is inserted in the necessary length through the Pinch rollers 13 and 13 'conveyed and cut by the cutter 16. The cut sheet material becomes to the photogravure device via the slot 18 in the housing 3 led. On the other hand, the remaining disk substance roll 12 is held on the disk support plate 15 and is ready for the next photograph.

Then in the respective treatment troughs Treatments to be performed on the photographic plate manufacturing apparatus have already been explained in detail above.

According to the photographic plate making apparatus of the invention, continuous processing can be performed from the photography of the manuscript to the photographic plate production of a printing plate automatically all in one bright room by operating a control box (not shown) for the device.

It follows from the above explanation that the method and the device according to the invention have the following advantages:

(1) Printing plates can do with good reproductive quality and high resistance to printing, these plates reproducing prints with excellent image quality reproduce. This effect becomes particularly noticeable when post-treatment has been carried out.

(2) Printing plates can be produced which are visually by coloring the same without printing paste

309833/0912

coloring can be checked.

(3) The silver halide emulsion layer may after Development entirely by means of a pair of nip rollers in the water wash trough to remove the silver halide emulsion layer can be removed without any formation of foam in the wash water. This effect is beneficial for the post-wash treatments.

(4) Printing plates can be made quickly and easily by a single worker.

(5) The printing plates can be inserted automatically and quickly a bright room can be created by a single worker.

The advantages listed above are particularly noteworthy when using the method according to the invention is combined with a device according to the invention and it is particularly advantageous and preferred to use a hydrophilic Use surface part to achieve the effects for practice. Sufficient effects can of course can also be obtained by means of the other embodiments.

The following examples serve to further illustrate the invention without limiting the invention.

3 0 9 8 3 3/0912

example 1 2305978 Solution; A. Glycerin 50 ml Methyl alcohol H ₂ O) 300 ml Sodium sulfate (9 (1 H ₂ O) 1.2 g Sodium 0.5 S water 10 ml Solution b H ₂ O) Cadmium acetate (2 13.3 6 water 10 ml

Solution B became solution A over 5 minutes was added with stirring to form a solution C in which the cadmium sulfate was dispersed. 100 g of solution C were mixed with a solution D of the following composition to form a solution E.

Solution; D.

Water 800 ml

Sodium hydroxide 200 ml

Ethyl alcohol 1200 ml

A sheet of cellulose triacetate with a thickness of 135 H was added to solution E for 40 seconds at 40 ° C immersed and washed with warm water and dried, so that an image receiving sheet for diffusion transfer printing was formed.

A silver bromoodide emulsion (5 mol% silver iodide) which 1.2 mol of silver contained per 1 kg of emulsion, which means a sensitizing dye was ortho-sensitized,

309833/0912

_ 34 -

was drawn up to a thickness of 5 y- ^au-on the bow.

The silver halide emulsion layer was exposed imagewise and then using a developer following composition for 30 seconds at 20 ° C developed:

Development association;

Water 750 ml

p-methylaminophenol sulfate 5 S

-sodium sulfite anhydrous 65 g

anhydrous sodium thiosulfate 10 g

Hydroquinone 15 g ■

Sodium hydroxide - 20 g

1000 ml of water

After development, the sheet was immersed in warm water of 50 ° C, leaving the silver halide emulsion layer was kept in contact with the hydrophilic surface part, so that the silver halide emulsion layer was removed from the hydrophilic surface part. At that time, a positive deposited by development was Silver image present in the hydrophilic surface layer.

The hydrophilic surface part was then immersed in an Xtz bleach solution of the following composition for 25 seconds immersed at 15 ° C:

Composition; the caustic bleach solution; Eäipfer (II) chloride (2 H ₂ O) _j 10 g. Acetic acid 10 g

Peroxoammonium disulfate 120 g

150 ml of water

300833/0912

At this stage, the hydrophilic surface part containing the silver image was damaged. To complete the To remove the damaged part, the surface had to be strong with cotton, full or another soft cloth be rubbed. The cellulose triacetate sheet with the. hydrophilic The surface part and the oleophilic part obtained at this stage can be used as a printing plate as such can be obtained.

The cellulose triacetate sheet, that of the etching-bleaching treatment was further subjected to a post-treatment solution of the following composition at 40 ° C immersed for 20 seconds.

Composition of the aftertreatment solution; CI. Direct Blue 76 32 g

Water 950 & 1

The damaged! Residue in the silver picture part was very easily removed from the aftertreated hydrophilic surface part. The printing plate thus obtained was in the non-image parts colored, d. H. the parts that did not contain a silver image, indicating that the etch was exactly executed.

This printing plate was set on an offset printing machine for printing, and 5,000 prints were obtained. During the printing, the hydrophilic properties of the non-image part of the printing plate were not damaged and there were no scratches on the surface of the printing plate, so that the image lines of the prints produced were very large were sharp. This means that the printing resistance of the printing plate obtained by the above method is superior to a printing plate, which is merely through

309833/0912

received the Itz-Blei'ch treatment or without any follow-up treatment became.

Example 2

A sheet of cellulose diacetate (thickness 155 xO) was inserted into the the following solution D xv immersed for 45 seconds at 40 ° C, whereby the surface part of the sheet was hydrolyzed and became hydrophilic and at the same time, nickel sulfate was in introduced the surface part. It became a picture-taking sheet obtained for diffusion transfer.

Solution a .

Glycerin. 100 g

Ammonium sulfate (aqueous solution,

where the sulfur content is 14.5%

is) - 40 ml

Solution b

Glycerin 180 g

Nickel nitrate (6H ₂ O) 0.5 g

Solutions A and B were mixed together at 30 ° C mixed for 5 minutes with stirring to form solution C. 250 g of solution C were made with a solution 4000 g of methyl alcohol, 2000 g of water and 500 g of sodium hydroxide were mixed to form solution D.

On the image acquisition sheet listed above, to a thickness of 3> * an emulsion layer of silver bromochloride (Silver chloride 75 mol%) applied, which contained 1 mol of silver per kg of the emulsion and the one Had been subjected to gold sensitization and ortho-sensitized by means of a sensitizing dye was. This silver halide emulsion layer was imagewise exposed and applied for 25 seconds at 25 ° C

309833/0912

developed by the following developer:

Developer assemblies;

Anhydrous sodium sulfite 100 g

Hydroquinone 20 g

1-phenylpyrazolidone 1 »0 g

Sodium thio sulfate 10 g

Potassium bromide 2.5 S

Potassium hydroxide 18 g 1000 ml of water

After development, the sheet was immersed in warm water at 55 C, the silver halide emulsion layer and the hydrophilic surface portion is kept in contact, the silver halide emulsion layer being separated from the hydrophilic Part of the surface has been removed.

Then the hydrophilic surface part was immersed in an etching bleaching solution of the following components immersed for 25 seconds at 25 ° C:

Composition of the caustic bleaching solution;

Copper (II) sulfate (5H ₂ O) 20 g

Citric acid 90 g

Potassium bromide 5 p

Peroxoammonium disulfate 65 g

1000 ml of water

At this stage the hydrophilic surface part, that contained the silver image, damaged. However, in order to completely remove the damaged part, the surface had to be be rubbed vigorously with a cloth, sponge or cotton. The cellulose diacetate sheet with the hydrophilic one Surface part and an oleophilic part which is in

309833/0912

this stage was obtained, but can be used as a printing plate, used as it is.

The cellulose diacetate sheet described above, which had been subjected to an etz bleaching treatment, Further, a post-treatment solution consisting of the following components was used at 25 G for 30 seconds immersed:

Composition of the aftertreatment solution CI. Direct Orange 39 20 g

Sodium carbonate 1 g

Water . 1000 ml

The damaged residues in the silver image part were easily removed from the hydrophilic after-treated in this way Part of the surface can only be removed by lightly rubbing the surface with a soft sponge.

The non-image portion of the printing plate thus obtained was colored and the inspection of the plate was easy. the The plate was offset printed and 6000 sharp reproductions were obtained.

Example 3

Silver was deposited on a cellulose triacetate film by vacuum evaporation drawn up and then the film dissolved in methylene chloride. A polyethylene terephthalate film (starch 100 u), which was coated with a gelatin base layer, became one with the solution obtained upon dissolution Coated thickness of about 4 u.

This sheet was made with a solution of the following ingredients to form a hydrophilic surface part

309833/0912

les about 1.2µ thick of the silver deposition nuclei contained, hydrolyzed:

Composition of the hydrolyzing solution
Lithium hydroxide 35 S

Ethylene glycol 100 g

Methyl alcohol 550 g

Water 400 ml

A silicon chloride emulsion layer was applied to the hydrophilic surface layer (Ratio of silver to gelatin 1: 2) drawn to a thickness of about 4 u and then the emulsion layer was imagewise exposed.

This plate substance was then turned into a developer of the following composition for 30 seconds at 20 ° C immersed:

Developer composition

Anhydrous sodium sulfite 75 g

Hydroquinone 18 g anhydrous sodium thiosulfate 10 g

Potassium bromide 2 g

Potassium hydroxide 19 g water to 1000 ml

After the development, the plate was washed with water of 40 ° C for 30 seconds, removing the layers were kept in contact. During the wash, the SiI overhalide emulsion layer became removed and a positive silver image was deposited in the hydrophilic surface portion.

This plate was made with an etching bleaching solution of the following Composition treated for 30 seconds at 25 ° C:

309833/0912

Composition of the caustic bleach solution copper (II) boromid ^ g

Phosphoric acid - 6 ml

Peroxopotassium disulfate 140 g

1000 ml of water, ..

At this stage, the hydrophilic surface part containing the silver image was damaged. However, to the injured To completely remove part, the surface had to be rubbed vigorously with a cloth or sponge will. -.

The hydrophilic one subjected to the etching-bleaching treatment Layer was then put into a post-treatment solution of the following Composition immersed at 45 ° C for 14 seconds, creating a printing plate with a high pressure resistance and obtained for reproducing printed images of good sharpness.

Composition of the aftertreatment; slösunp; CI. Direct Blue 71 30 g.

Water . 1000 ml

This printing plate was used for offset printing and 8,000 high quality prints were obtained.

Example 4

A cellulose acetate butyrate sheet of J8 U. thickness and a polyethylene terephthalate sheet of thickness of 100 u were layered and hydrolyzed for 6 minutes at 20 C using the following solution:

309833/0 912

2305978 500 G 500 ■ Β 70 6th

water

Methyl alcohol
Sodium hy droxi d

The sheet, the surface part of which was hydrolyzed, was dried using an aqueous 5% acetic acid solution neutralized and then washed with water and dried. This sheet was immersed in a 0.03% chloroaurate-methyl alcohol solution immersed at 35 ° C for 30 seconds and then dried. Ultraviolet drying is preferred, however, even without such drying, if the sheet as such is during normal temperature Left for 1 day, a sufficient amount of diffusion transfer nuclei in the hydrolyzed surface part of the cellulose triacetate sheet deposited.

A Silberbromchloridemulsionsschicht (silver chloride 70 mol%) containing 1 mole of silver per kg of emulsion was coated ^u on the sheet to dner thickness of 3 and then the layer was imagewise exposed and for 40 seconds at 25 ° C using a developer of the following composition:

Water 750 ml

p-methylaminophenol sulfate 5 g

anhydrous sodium sulfite 65 g

Hydroquinone 15 6

Potassium thiocyanate 25 g

Sodium hydroxide 20 g water to 1000 ml

After removing the silver halide emulsion layer in warm water of 50 ° C, a positive silver image became

309833/0912

obtain.

The. The plate was then immersed in an Itz bleach solution following composition "at 25 ° C. for 30 seconds immersed:.

Copper (II) bromide (2 H ₂ O) 12 g

Glacial acetic acid 50 ml

35% hydrogen peroxide solution 100 ml

Water 900 ml

At this stage, the residues, which by means of the caustic bleach solution were damaged only by strong Rub the surface of the plate away. After the plate with the tray treatment solution of the following composition had been treated, on the other hand, ■ the damaged residues could be removed very easily and it no scratches occurred on the non-image part. This made a printing plate, the image part of which was sharply etched, obtain. -The plate obtained was used for offset printing used and it could print more than 15,000 copies can be obtained.

Composition of the post-treatment lb'sunp;

2-hydroxy-naphthalene-3-carboxyaniline-4 -'-sodium sulfonate 30 g

1000 ml of water

Example 5

A sheet of polystyrene (thickness 120 u) was concentrated in Sulfuric acid for 10 seconds at 50 ° C for Sulfonation of the surface part of the same immersed,

309833/0912

washed with water and then in an in sodium hydroxide solution immersed to neutralize the acid. The sheet was washed again with water and dried.

Then this soil was in a dispersion of colloidal nickel sulfide, which in 80 g of ethylene glycol monobutyl ether, 15 g of methyl alcohol and 5 g of water were formed (concentration of colloidal nickel sulfide = 3 χ 10 "^ mol / l), for 60 seconds at 30 ° C for introduction The nickel sulfate is immersed in the surface part, creating a sheet with a transparent hydrophilic Surface part was obtained.

A silver chloride emulsion layer in which the ratio of silver to gelatin was 1: 2 was overlaid The surface was drawn up and then the layer was exposed and washed with water as in Example 3. A black one a positive silver image was obtained. This was with the Itz bleach solution according to Example 1 for 25 seconds treated at 30 ° C and continued with the following solution treated for 30 seconds at 25 ° C, so that the Printing plate was obtained:

CI. Direct Red 31 25 g

1000 ml of water

This printing plate was used for offset printing and sharp print reproductions were obtained.

In the foregoing, the invention has been described on the basis of preferred embodiments without being limited thereto is.

309833/0912

Claims (1)

^ 44 - · Claims fi) Photoplate manufacturing method for manufacturing of printing plates, characterized by the stages of (1) Mldwise suspension of a disk subsistence for Production of a photographic plate, wherein the plate substance consists of a hydrophilic surface part or one on a The hydrophilic layer on the oleophilic carrier consists of silver deposition cores for the diffusion transfer process and a silver halide emulsion layer is coated thereon, and 'subsequent development the exposed plate substance to form a positive silver image on the hydrophilic surface part or on the hydrophilic layer, (2) washing the developed plate substance with water to remove the silver halide emulsion layer, (5) Treatment of the hydrophilic surface part or the hydrophilic layer with an Xtz bleach treatment Exposure of the oleophilic surface part that forms the silver image corresponds to, and (4) According to the drawing of the product after stage (3) one Post-treatment, whereby the residues of the etched-bleached parts are made fragile, and subsequent removal of the residues. 2 «. Photo plate production method for producing printing plates according to claim 1 _9, characterized by the steps of a (1) Mld-wise exposure of a plate substance to produce a photographic plate, the plate substance consists of a hydrophilic surface or a hydrophilic layer on an oleophilic carrier and contains silver deposition nuclei for the diffusion transfer process and a silver halide emulsion layer superposed thereon having-, (2) Development in a development tray to form a positive silver image on the hydrophilic surface part or hydrophilic layer, (5) Wash with water in a washing tub for removal the silver halide emulsion layer, (4) treatment of the hydrophilic surface part or the hydrophilic layer in an etching-bleaching trough to release the oleophilic surface corresponding to the silver image and (5) Post-treatment in a post-treatment trough to the residues of the etch-bleached parts that were damaged by the etch-bleaching treatment, and subsequent Removal of residues. 5 · Photo plate making method of manufacture of printing plates according to claim 1, characterized by the steps of a (1) imagewise exposing a plate substance to produce a photographic plate, the plate substance consists of a hydrophilic surface part which is present on an oleophilic carrier and which contains silver separation cores for the diffusion transfer process and has a silver halide emulsion layer coated thereon, (2) Development in a development trough for education a positive silver image on the hydrophilic surface part, (3) washing with water in a washing tub to remove the silver halide emulsion layer, (4) Treatment of the hydrophilic surface part in an etching-bleaching trough to release the oleophilic surface according to the silver picture, and (5) Post-treatment in a post-treatment trough to 309833/0912 ■ - 46 ~ the residues damaged by the etching-bleaching treatment to make them brittle, and then remove the residues. - 4-. Method according to claim 1 to 3 * characterized thereby- ' indicates that the hydrophilic materials have a contact angle with water of less than 4-5 and the oleophilic carriers have a contact angle with water greater than 4-5 ° "at normal temp era door. 5- The method according to claim 4-, characterized in that that a cellulose ester is used as an oleophilic carrier. ■ - - ■ 6. The method according to claim 1 to 5 *, characterized in that that a total thickness of the oleophilic carrier and hydrophilic surface part or layer of about 80 to about 500 / rev is applied. 7. The method according to claim 6, characterized in that the hydrophilic surface part or this layer for example 0.1 to about 30 η thick. 8. The method according to claim 1 to 7, characterized in that the silver deposition cores only in the hydrophilic materials are present. 9 «Method according to claim 1 to 8, characterized in that that development with a diffusion transfer developer containing a developing agent and a solvent for dissolving the silver halide. . 10. The method according to claim 9? characterized in that the etching bleaching with an aqueous etching bleaching bath, containing an oxidizing agent takes place. 11. The method according to claim 10, characterized in that that the aftertreatment with an oxyacid of chlorine, a water-soluble thiocyanate or a dye, which 309833/0912 physically, on the hydrophilic surface part or the hydrophilic layer is adsorbed, this dye has at least one anionic substituent will. 12. Apparatus for the photographic plate manufacturing process, consisting of (1) a plurality of rollers for conveying a plate substance for making the photographic plate, the Plate substance consisting of a hydrophilic surface part located on an oleophilic carrier or a hydrophilic surface part Layer containing silver deposition nuclei for diffusion transfer and a silicon halide emulsion layer applied thereon consists, (2) a developing trough, a washing trough, an etching-bleaching trough, and a post-treatment trough, respectively Treatment of the plate substance, which are arranged in the order given, with the troughs the plate substance take up, (3) Removal means for removing the silver halide emulsion layer in the wash basin and (4) Removal devices to remove the through Etching of damaged residues in the post-treatment trough. 13. Device for continuous photographing and photoengraving consisting of photo plate devices and photographing devices, wherein the photo plate devices consist of: (1) a plurality of nip rollers for conveying a plate substance for making a photogravure plate, wherein the plate substance consists of an oleophilic Hydrophilic surface part or a hydrophilic layer located on the carrier, the silver deposition nuclei for the Contain diffusion transfer, with a 309833/0912 brought silver halide emulsion layer ", . (2) A developing trough, a washing trough, an etching-bleaching trough and a post-treatment trough, each for Treatment of the plates sub stance in the order given are arranged, with the troughs receiving the plate substance, (3) Removal means for removing the silver halide emulsion layer in the wash basin and (4) Removal devices for removing the residues damaged by the etching in the post-treatment trough, while the photographing device consists of (5) manuscript holding facilities, (6) Magnification control means for determining the position of the photographic lens in accordance with FIG desired photographic enlargement of the manuscript on the manuscript holder facility, (7) Camera equipment for photographing the manuscript on the plate socket by means of the lens and (8) Facilities to promote the photographed Plate substance still in the form of a roll to the photoplate manufacturing facility and for cutting the exposed portion of the plate substance from the roll, and means sur conveying the cut plate substance to the photo plate manufacturing facility o 309833/0912 Blank page