DE1522418A1 - Process for producing multicolor reproductions by the subtractive process - Google Patents

Description

AGFA-GEVAERTAG

PATENT PART UNQ LEVERKUSEN

17th Dec. 1233

Process for the production of multicolor reproductions according to the subtractive method

The invention relates to a method for producing color photographic Images where the image dye consists of an organic metal complex with excellent lightfastness The invention also relates to photographic light-sensitive materials for practicing the foregoing Procedure.

The term "toning process" includes such processes understood, which make it possible to convert a silver image into a color image of any color. The silver pictures can be color extracts represent, briefly called blue, QrUn and red from train, and after converting the extract into an image, of the orange extract in a purple picture and the rotau extract ""

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in a blue-green image after precisely fitting coverage Reproductions of the original. For example, the silver image of the blue extract can first be treated with potassium ferricyanide, whereby the metallic silver is converted into silver ferrocyanide. Silver ferrocyanide gives insolubles with a lead salt solution Lead ferrooyanide, which is converted to yellow, very lightfast lead chromate by further treatment with a chromate solution will. The orange extract can also be converted into silver ferrocyanide using potassium ferricyanide. Treatment with a nickel salt produces nickel ferrocyanide, which is treated with an aqueous-alcoholic solution of dimethylglyoxylm provides a very real red colored nickel complex of dimethylglyoxime. The messenger train is in the first Step also treated with potassium ferricyanide. The educated In a second step, silver ferrocyanide reacts with Eieen III salt to give Berlin blue.

Such color images can also be produced with the aid of a single metal cation, for example with the aid of a nickel salt. In each case, the silver image of the three color extracts is first converted into silver ferrocyanide with potassium ferricyanide. Treatment with a nickel salt creates images)
ο massive nickel elephant errocyanid in all extracts. The Blauausacug

^ is then treated with dicyandlamidine sulfate, whereby ^ a yellow nickel complex is formed. The extract is in

- »Treated in a known manner with dimethylglyoxime, whereby to

a red nickel complex arises and the red extract with it

1, 2-diaminoanthraquinone-j5-sulfonic acid, here ent-. ,. »

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is a blue colored nickel complex. In any case, must the nickel salt image of each individual extract with the dye former, here with a solution of the organic one Complexing agent to be implemented. Although these methods have advantages in that they provide color images in relation to the light fastness the color developer Produced photographic images are vastly superior, these processes could be complicated because of the complexity Do not enforce processing in practice. In particular, in the context of these proceedings it is not possible the coloring organic complexing agent, e.g. dirnethylglyoxime and the metal salt, e.g., the nickel salt, in a solution to act on the silver image or, what would be more decisive with regard to a three-layer dressing, the coloring complexing agent diffusion-proof in the light-sensitive Store shift.

The invention is based on the object of modifying the above method so that processing is simplified simultaneous application of the organic complexing agent and the metal ions, the organic complexing agent being more soluble Form or can be used in the light-sensitive layer in diffusion-proof form, becomes possible.

It has now been found that in a surprisingly simple manner Color images of excellent lightfastness, which are made from colored Heavy metal complex compounds can be prepared by reacting them in a photographic layer

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Evenly distributed silver halide with dissolved complex compounds of heavy metals of the subgroups of the periodic system of elements with such complexing agents, or ligands, which result in a more stable complex with silver than with the heavy metals, with this conversion is carried out in the presence of other organic complexing agents, the free ions of the heavy detail formed in the above conversion (double conversion), form a colored complex compound, the dissociation constant of these colored complex compounds should be greater or equal) but not be significantly smaller than that of the original heavy metal complex.

The method according to the invention is based on a photographic one Layer containing silver halide in an image-wise distribution. Such a layer can depend on whether a positive or negative image of the original is desired can be produced in various ways. In the first Trap, the exposed halide silver emulsion layer is developed in the usual way, with a negative silver image of the recorded object is created. The silver halide remaining in the layer then forms a positive invisible one Silver halide image of the subject.

If a negative silver halide image is to be assumed, the procedure is as above, initially in the usual way exposed and developed, then this is then done in the

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Layer of remaining silver halide removed by fixing and finally the silver image is converted back into silver halide. '

For a better understanding of the method according to the invention, the principle is illustrated below using a specific example explained; To generate the colored image, the silver halide containing the image-wise distribution is first used Layer implemented with a solution of the nickel tetracyano complex. Since the dissociation constant of this complex is larger than that of the silver cyanocomplex Places where silver halide is present, the nickel complex destroys and image-wise released nickel ions. If other complexing agents are present, which result in colored complex compounds with nickel ions, this is now formed in an image-wise manner through reaction with the free nickel ions, a dye is formed that is exactly proportional in its density to the silver image is. The latter is based on the obvious fact that when the silver cyanocomplex is formed, the stoichiometric amount of nickel ions is released.

As already stated above, is for the invention

measures the ratio of the dissociation constant cd ■
° the seriousness involved in the process

^ metal complexes essential. By appropriate coordination of the - ^. Sehwermetallionen, the ligands of the Schwerme- used - * tal3®raplej; it, and the organic complexing agents, the required stability ratios of the complexes are adjusted easily. Since there are countless serious

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Metal complexes with inorganic and organic ligands are described, it is possible for the average person skilled in the art without difficulty to put together suitable combinations.

The three essential for the method according to the invention Components are listed below:

1) Heavy metals: subgroup elements of the periodic system of the elements, especially the 1st, 6th, 7th and 8th subgroups, e.g. copper, chromium, manganese Iron, cobalt, nickel, palladium and platinum. For economic reasons and because of the appropriate color tones their complex compounds are particularly suitable. Copper, iron, cobalt and nickel.

2) As ligands for the heavy metal complex used suitable for example: cyano, rhodanide or thiosulfate ions, aliphatic and heterocyclic amines or polyamines, complexing aminocarboxylic acids, such as Ethylenediaminetetraacetic acid or nitrilotriacetic acid.

3) Complexing agents for the complex forming the image dye are listed in the following tables:

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Tabel Metal central atom; Nickel (II) ion

Organic complexing agent color

y- or syn-forra of dioximes of 1,2-diketones

f - benzil dioxime

y-methyldeeylglypxim

Diisonitrosoacetone and derivatives of that

MerkaptobenzthiazQl and its Derivatives

Dicyandiamidine_and Derivatives of that

yellow yellow

yellow

dark yellow

yellow

Dimethylglyoxime cyclohexanedione dioxime cC- or: anti-benzildioxime «C-purildioxime Nitrosoguanidine

Bis- (diacetylmonoxime-imino) propane-I, j5

Bis- (diacetylmonoxime-imino) ethane-1,2

Diphenyl carbazide purple purple purple purple purple

purple

purple purple to blue violet

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Continuation of Table 1 on next page 9 09831/1138

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Port setting tab »1 Organic complexing agent

colour

1,2-diamino-O-sulfo-anthrachlnone

Triethanolamln

o-aminobenzoic acid

S-chlorosalicylaldoxime Acetaldoxime Benzaldoxime

Phenylthi osemi carbazid O-oxyacetophenone oxime dark blue blue green green blue green blue green

dark green green

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Table 2

Elsen / Ill-ion colour Organic complexing agent yellow Pyridine-2-carbolic acid Red e6 «C-dipyridyl Red Dimethylglyoxime red-purple Thloglycolic acid Red Quinoline-8-carboxylic acid purple Nitrosoguanidine green 2-nitroso-1-naphthol-4-sulfonic acid green Triethanolamine blue green Phenane threnquinone monoxide blue Isonitrosoacetylacetone blue. 4-isonitroso-l-phenyl-3-
methyl-pyrazolone-5 green βί-Ni tvoso-ji-n & ph thol

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Hfl

Table 3

Iron (III) ion Organic Koßiplexbildner

Dye

Kojic acid

Acetylacetone.

1 - (thenoyl - / * /) -3,3,3-

trlfluoroacetone

yellow-orange red

ß- CO - CH ₂ - CO - CP, red

4-Dimethylamino-1 ~ phenyl-2,3 «dimethylpyrozolone- (5) blue

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• - -
Tabel Copper ( I) ion / 4
4th 1522418 colour Organic complexing agent brownish yellow Zinc diethyl dithiocarbamate purple 2.2 ^f -dichinolyl blue 1,10-phenanthrols

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Tabel Copper (II) ion

Organic complexing agent color

Antipyrine salicylaldoxime 5-chloro-sallcylaldoxime Mercaptobenzothiazole sodium diethyldlthiocarbaminate diethylamine diethyldlthiocarbaminate Dicyandiamidine Phthalic Acid Monoethersers Phthalic acid monooctyl ter Glycine

Diethanolamine triethanolamine phenylthiosemicarbazide quinoline

o6-benzoin oxime Diisonitrosoacetone acetaldoxime acetone dicarboxylic acid oxime

1,2-diaminoanthraquinone-3-sulfonic acid

Quinaldic acid phenylglyoxalic acid oxime lemon yellow yellowish yellow-brown pale orange-yellow yellow yellow red blue-green blue-green blue blue blue deep blue indigo blue green dark green bright blue green

blue bluish green bright green

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J3

Table 6

Cobalt ill) ion colour Organic complexing agent orange 1- (Thenoyl ^ y) -3, -J /> - trifluoroacetone Red 2-nitroso-1-naphthol-4-sulfonic acid Red oC-benzil monoxime Red Dilsonitrosoacetone Red Phenylglyoxalic acid oxime green Blue 1,2-diamino-anthraquinone-3-sulfone
acid ".. blue Quinoline green 5-nitrosalieylaldoxime green Acetone dicarboxylic acid oxime cornflower blue Acetone oxime green Mercaptobenzfchiazole green Phenylthioseraicarbazide blue green 1- (2-pyridyl-azo) -2-naphthol

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St.

Table 7

platinum

Organic complexing agent color

2-mercaptobenzethlazole Thionalide

OO canary yellow

-NH-CO-CH ₂ -SH yellow

Rubeanhydrogen

Benzidine

purple green

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Table 8

palladium

Organic complexing agent color

Phenoxthin yellow-brown

Mercaptobenzolindazole orange

Salicylaldoxlm egg yolk

DimethyIglyoxime orange-yellow

Cyclohexanedione dioxime orange yellow

oCi-Hltroso-a -naphthol violet

p-Dimethylaminobenzylidenrhodaniri red-violet

suitable subst. Formazane blue-green

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Compared to the known toning process, the one according to the invention Process by the simultaneous use of metal ions and the organic forming the image dye Characterized complexing agents. The metal ions are always offered in the form of a complex. From what, as explained above, figuratively then the free metal ions arise.

The organic complexing agents can now be used as a joint solution with the dissolved heavy metal complex will. The method is then carried out in a manner similar to that known from conventional color photography Development process. In the case of multi-layer materials, the Processing then in a known manner by controlled diffusion can be carried out, whereby the second exposure is omitted here in the practically practiced reversal process. The correct procedure is much simpler, if the organic complexing agent is in the form of a non-diffusible silver halide emulsion or possibly is also added to an adjacent layer. This can be done in the same way as it is from the conventional one Color photography in relation to the diffusion-resistant inclusion the color coupler is known. The organic complexing agents can either by long-chain alkyl radicals with about 12 to 18 carbon atoms and a solubilizing group be substituted or they can be dissolved in an organic solvent and emulsified into the photographic layer will. In the case of ffeT, an embodiment can be used

high boiling points in a known manner
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Solvents, so-called oil formers, are added.

The present invention is preferably used for construction of multi-layer materials that work according to the subtractive color principle. Such materials are constructed similarly to the known multi-layer color photographic materials, whereby instead of the conventional coloring system consisting of the color coupler and the coloring developer, the system according to the invention consisting of the heavy metal complex and the organic complexing agent occurs »Such a material consists of a blue-sensitive halogen silver emulsion layer that contains an organic complexing agent In a diffusion-proof form, which, together with the heavy metal ion, provides a yellow dye, a green-insensitive halide silver emulsion layer, which is in a diffusion-proof form contains an organic complexing agent, which with the Heavy metal ions provide a purple dye and finally a red-sensitive halogen silver emulsion layer which contains an organic complexing agent in a non-diffusible form which, together with the heavy metal ion, produces a blue-green color.

Among the organic complexing agents mentioned above, especially those that have a purple or blue-green dye deliver, there are some that have a yellow to red color of their own. These complexing agents are special

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Meaning in that they are used as built-in masks Masking unwanted secondary densities of the purple or blue-green dye work. The principle of masking is known in conventional color photography.

The invention in the form illustrated above using nickel as the heavy metal ion, is based on the fact that the resistance of the silver cyanide complex higher or, in other words, the dissociation constant is lower than that of the nickel cyanide complex. Hence are Silver halides are able to displace nickel ions from the cyanide complex. Now there are numerous combinations of heavy metal ions, inorganic and organic complexing agents (= dye-forming agents) known that relate to of the dyes formed would be suitable whose use for the process according to the invention in the simple form described, however, fails because of this! that the dissolved, inorganic or organic heavy metal complex is more stable " than the silver complex in question, so that in this process stage the silver is not able to displace the heavy metals from the soluble complex. this applies e.g. to the elsenoyanide complex, which has a higher resistance than the silver cyanide complex. Therefore, at normal temperature, silver halide is not able to set free iron ions from the cyanide complex. However, since Iron ions would be suitable per se, especially because numerous organic complexing agents are known that interact with Si

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senions result in the dyes of the subtractive color triple, the use of these heavy metal ions would in itself be quite desirable. In fact, it succeeds a slight modification of the method according to the invention to use this system as well. The modification exists in the fact that the silver halide image is conventional in itself is converted into a mercury salt image. Since the mercury cyanide complex The process can have a significantly lower dissociation constant than the iron cyanide complex can now be carried out further in the manner described.

Without the detour described, namely to convert the silver halide image into a suitable heavy metal salt image. suitable heavy metal complexes can only be used directly if the complexing agent is selected in such a way that the silver ion can displace the heavy metal from the complex.

In general, any visual metal ion is suitable for this color process, which is made with appropriately selected organic Complexing agents the color triple QeIb, purple and blue-green gives. This heavy metal ion must first be in a complex present that is stable enough not to interfere with the organic To be able to react complexing agents. Only after releasing cd

° by a second metal ion, which has a higher tendency,

CD ''

_{ω to} enter the complex, the heavy metal ion is released • ^ and delivers the desired dye with the organic complexing agent. A few numbers may serve as examples. The dissociation constant of the mercury cyanide complex is 4 χ 10, that of the ferrocyanide complex is 10 ^.

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Mercury chloride therefore displaces iron (II) ions from the F.errocyanidkompiex. The released iron (II) ions can give the appropriate dyes with the organic complexing agents.

The dissociation constants of the organic dye complexes are much larger and should be of the order of magnitude from lo "^ to 10. Another example is given some numerical values for the simplest example, the displacement of the nickel ions from the nickel cyanide complex by silver ions. The dissociation constant of the various silver

-21 cyanide complexes is on the order of 10 to

10 '. The nickel cyanide complex has a dissociation constant

-20
te of about 10, so the silver salt can get nickel out of its

Displacement of the cyanide complex? then nickel reacts with the organic Complexing agents, whereby the dissociation constants of the corresponding complexes are likely to be 10 * ^ to 10 ".

The advantage of the process described is that compared to dye formation by the chromogenic process a plentiful selection of heavy metal salts is available. Every heavy metal salt comes with suitable components a color triple. The organic heavy metal complexes are known to be very lightfast. Like the simplest examples show, the light fastness properties achieved are those obtained by conventional color photographic processes outperform many times over. The process still allows a negative process or a very simple one

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To carry out positive process. Colored by the use Components can be automatically masked negatives.

Another variant, automatically masked negatives Obtained, consists in adding organic complexing agents not reacted for image formation with a suitable heavy metal salt solution to the mask dye. E.g .: a Diffusion-resistant embedded dicyandiamidine derivative forms the purple image dye with copper, which is not consumed After treatment with a NicJcelsalz solution, complexing agent supplies the yellow in the unexposed areas Mask dye.

The concentration of the organic complexing agent in the silver halide emulsion layer can vary according to requirements the reproduction method and the properties of the photographic material vary within wide limits. In general, there is a concentration ratio of the organic complexing agent to the silver present from about 1 mole to 1 mole has been found advantageous. The valence of the heavy metal cation has only a minor influence, since monovalent cations are mostly coordinatively bivalent, bivalent coordinatively tetravalent and trivalent coordinative are hexavalent. The prerequisite for this is, of course, that the organic complexing agent has two coordination points of the heavy metal central atom, which is practically always the case. .

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The silver content of the emulsion layers depends on the to a certain extent according to the valency of the cation used for the preparation of the image dye. So become two moles In order to set a divalent cation free, silver needs three moles of silver to set a trivalent cation in Freedom to sit, etc. '

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Example Is

Creation of a negative yellow image. A silver bromide emulsion layer exposed behind a step wedge, which is placed on a paper support, is developed in a developer of the following composition for 3 minutes?

per liter
Rebrauchsf. solution ε 1 G 13th G 3 G 26th G 1

p-methylaminophenol sodium sulfite sicc. Hydroquinone Soda, Anhydrous Potassium Bromide

After developing the paper becomes 1/2 minute in one 2 f & lgen acetic acid bath stopped. Then 2 minutes in fixed in an acid fixer and then thoroughly watered. The silver picture is now in a bleach bath that 10 g of potassium bromide and 50 g of potassium hexacyanoferrate III per liter contains, bleached for 5 minutes and then rinsed thoroughly. The picture so bleached and well watered is shown in a mixture consisting of a solution of 2 g of methylbutyldiketodioxime in 500 ecm of methanol and 5 g of potassium nickel cyanide in 500 ecm of water exists, bathed.

It is advantageous to add a few ecm of concentrated ammonia solution to the solution in order to accelerate the reaction. At

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A yellow dye image is produced in the areas that contain almost all silver halide. After 10 - 15 min. The dye image is no longer intensified for the duration of the treatment. That Paper is thoroughly watered and fixed and watered again to remove unreacted silver halide.

Example 2: Production of a positive oil painting

A photographic material is, as in Example 1, behind exposed on a step wedge and developed in the same developer. Now it is not fixed but the remaining silver halide is converted into a yellow dye image, after just watering well after development. The paper is then mixed in the same way as treated in example 1. The remaining silver halide converts to a positive yellow dye image. To this treatment is thoroughly watered, the silver formed during the treatment and development by bleaching in the The above-mentioned bleaching bath and subsequent fixing removed. After a final wash, there is a positive yellow picture.

The yellow dye has an absorption maximum at 390 m / i and a weak secondary maximum at 490 n / i »'

The lightfastness of the yellow dye obtained is practically unlimited compared to the lightfastness of the dyes produced by chromogenic development. After an exposure time that is five times as long as the exposure

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time sufficient for a chromogenic development destroy received dye image to make it unbearable, no change can be seen in the oil dye.

Example 3:

Preparation of a negative magenta dye image As in the previous examples, a silver image is obtained developed, bleached and watered. The silver halide image is in a mixture consisting of a solution of 2 g Dimethylglyoxine in 500 ecm of methanol and 4 g of potassium nickel cyanide consists of 500 ecm of water plus 5 ecm of concentrated ammonia, bathed. A red to violet-red dye image forms. The paper is treated in the same way as in Example 1 further. .

Example 4;

Production of a purple positive image The procedure is the same as in Example 2, except that instead of the yellow dye-former, the magenta dye-former is used. The resulting purple dye has an absorption maximum of 554 m »a secondary maximum is at 420 m.

coUnder the same conditions and after the same exposure

^ω processing time as the yellow dye produced in Examples 1 and 2 was subjected to a lightfastness test and not

cover changed, the purple dye becomes lesser in places oo

Dye density somewhat faded. , - »

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Example 5:

Creation of a negative blue-orange image. The procedure in example 1 and 3 is repeated. To produce the dye formed a solution is used which consists of a Mixture of 5 g salicylaldoxini in 500 ecm methanol and 4 g potassium nickel cyanide in 500 ecm water plus 5 ecm concentrated Ammonia consists * A green pigment is formed.

Example 6;

Production of a blue-green positive image. It is as in Examples 2 and 4 using the Proceed with the color-forming solution of Example 5.

The lightfastness corresponds completely to that of the example 1 and 2 mentioned yellow dye.

Example 7:

Production of a positive or negative yellow image with a "yellow component" embedded in the emulsion layer Methyl undecyl ketone is known in catfish with amyl nitrite nitrosated with the addition of a small amount of hydrochloric acid. The obtained methyldecylisonitrosoketone is in alcoholic Solution reacted with hydroxylamine to methyldecyldiketodioxime. The product obtained has after recrystallization from methanol a melting point of 149 ° C.

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20 g of the methyldecyldiketodioxime obtained in this way are in

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Dissolve 300 ecm of methanol and slowly add 300 ecm of a 4% gelatin solution containing 1/2 % wetting agent, for example oleyl polyglycol ether, in a mixer, advantageously with vigorous stirring. An emulsion of the organic dye former in the gelatin solution is obtained. This emulsion is added to a photographic silver bromide gelatin emulsion in such a ratio that there is a silver complexing agent ratio of 1 mol of silver to 1 mol of complexing agent. This ready-to-pour solution is drawn onto barite-coated paper. ί

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The cast is exposed behind a step wedge and processed according to example 1 or 2. Only for color development only an aqueous solution of potassium nickel cyanide is used. The solution contains 10 g of potassium nickel cyanide per liter. Further treatment is carried out as given in Example 1 or Example 2. The result is a negative or positive yellow Dye image.

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Claims (6)

Patent claims 3t « 1) Process for producing color photographic prints images, which consist of heavy metal complex compounds, characterized in that nan a photographic Layer which contains silver halide in an image-wise distribution, with a solution of complex compounds of heavy metals of the subgroups of the periodic system of elements with such complexing agents, which result in a more stable complex with silver than with the heavy metals, and this conversion is carried out in the presence of other organic complexing agents, which image-wise with the in the implementation the free ions of the heavy metals produced, which provide the image dye, provide colored complex compounds, the dissociation constant of these colored complexes being greater than or essentially equal to that of the reaction inorganic heavy metal complex compounds used is. , 2) Method according to claim 1, characterized in that the heavy metal is copper, chromium, manganese, Elsen, cobalt or nickel is used. 3) The method according to claim 1, _ characterized in that Cyano, thiocyano, arain, polyamine, aminocarboxylic acid or thiosulphate complexes of heavy metals are used will. 909831/1138 AG 188 - 28 · "_ T522418 4) Method according to claims I - 3, characterized in that that the organic complexing agents in the light-sensitive silver halide layer are more diffusion-resistant Are stored in the form 5) Process according to claims 1-4, characterized in that nickel cyanocomplexes as Complexes are used. 6) Photographic light-sensitive materials having at least one silver halide emulsion layer described in diffusion-proof form contains an organic complexing agent which, with the heavy metal ions copper, Chromium, manganese, iron, cobalt or nickel a colored one Complex compound supplies. 8AD ORfGiNAL 909831/1138
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