DE1288912B - Process for producing color images by color development - Google Patents

Description

The invention relates to a method for producing a "color image by developing a bleached silver image, which still contains silver nuclei, by means of hydrazones.

This method is based on the finding that a silver image, as described below - has been oxidized to form a silver salt, certain weakly reducing hydrazone compounds can oxidize and that due to the oxidizing power of this silver salt image in alkaline Medium an oxid / itive coupling between the hydrazone compound and one to form a Azino dye suitable coupling component occurs.

The photographic material developed according to the invention can optionally be sensitized be.

A development process is known from German patent specification 963 297, with negative produce colored images by developing with hydrazones with the formation of azo dyes and the bleaching of the silver image can occur after color development.

The disadvantage of this is that the developer solutions described there are not very durable and - Due to the low solubility of the hydrazones used there - the reduction of the Silver image takes place relatively slowly.

The object of the invention is a method for producing color images by color development, ensures fast development and smooth coupling.

The invention is based on a method for producing a color image by development of a bleached silver image that still contains silver nuclei by means of hydrazones and is characterized by that the color development by oxidative coupling of a color coupler with a hydrazone compound of the general formula dissolved in an alkaline aqueous medium

τ Ri

1 ^{- z} - i · ι

N C = N-N

5- or 6-membered homocyclic ring required atoms, whereby the solubility product of the silver salts, which have arisen from the bleached silver image, must not be below 10 ⁿ at 25 C.

The hydrazones substituted with sulfonyl or carbonyl groups used according to the invention show a greater solubility in the alkaline medium and can therefore in greater Concentration. This ensures faster color development. They are also available as a developer solution more durable, and the controlled bleaching of the silver image to such an extent, that silver nuclei are still present in the exposed and developed areas fast developing and smooth coupling.

If there are aliphatic chains, these are short, e.g. B. methyl or ethyl, and / or there will be various groups of an ionic nature, such as carboxyl groups or sulfo groups, are introduced therewith the compounds can be used in the dissolved state.

The following is a detailed description of the preparation of some compounds according to the above given general formulas (I) and (II) explained for use in the process of Invention are suitable.

Production example 1

3-methyl-2-benzthiazolone-4'-carboxyphenylsulfonylhydrazone

= N - NHSO, -

COOH

45

r Z- 1 ^ ¹

N-C = C-C = N-N

111 ί

R3 R4 Rs R2

carries out, in which Z denotes the non-metal atoms of a 5- or 6-membered heterocyclic, optionally substituted ring or a condensed ring system which contains a 5- or 6-membered ring, Ri is hydrogen or an acyl radical, R> a CONH2- or SOiX group, in which X is a hydroxyl group, an amino, an alkyl, an aryl radical or a heterocyclic radical Radical, Ra is a hydrogen atom, an alkyl or an aryl radical, optionally through Solubilizing groups are substituted, Ri and R5, which are identical or different, each have a hydrogen or halogen atom or a dialkylamino, carboethoxy, cyano, alkoxy, alkyl or aryl group or together to close a one leaves 3.07 g (0.01 mol) of 1-methyl-2-methylthio-benzthiazolium methyl sulfate, produced after R. Riemschneider, MONTHSH. Chem., 91 (1960), 626, and 2.16 g (0.01 mol) of 4-hydrazinesulfonylbenzoic acid React in 50 ml of pyridine at 20 ° C. for 12 hours. The precipitate formed is filtered off and first with water and then with washed warm acetonitrile. F. over 260 C.

Production example 2

1,4-Dimethyl-2-chmolon-3'-carboxy-4'-hydroxyphenyl sulfonyl hydrazone

NHSO,

OH

55

60 is made as follows:

a) Preparation of 3-carboxy-4-hydroxyphenylsulfonyl hydrazide:

To 15 ml (0.3 mol) of hydrazine hydrate in 120 ml of dioxane is added dropwise a solution of ⁵ 14.2 g (0.06 mol) of 3-carboxy-4-hydroxyphenylsulfonylchlorid added in 200 ml of dioxane. The mixture

is stirred at 20 C for 2 hours. An oily layer forms, which is separated off and then washed for 2 hours in the presence of 5 B hydrochloric acid. The hydrazide. that has solidified is first washed with water and then with acetonitrile and then filtered off with suction. F. = 230 C (decomposition).

Recrystallization from water does not change the melting point.

b) Preparation of L4-dimethyl-2-quinoion-3'-carboxy-4'-hjiJroxyphenylsulfonyI-hydrazone:

2.32 g (0.01 mail of the above hydrazide and 3.3 g (0., Oi Moli K4-dimethyl-1-methyl-mercaptoquinolinium iodide allowed to react for 4 days at 20 ° C. in 20 ml of pyradine. The pyridine is then distilled at 40 C in a vacuum. The residue is washed first with cold acetonitrile and then with warm acetone and then sucks it off. F. = 250X (decomposition).

The 1,4-dimethyl-2-methyl mercaptoquinolinium iodide used is made from the corresponding thioquinolone and methyl iodide in acetone solution Reflux. Cooling, suction of the precipitate formed and washing with dry Acetone obtained.

Production example 3

3- \ lethyI-2-ben4Eiiazo! On-3'-carboxy-4'-hydroxyphenyfs [[ifonyl-hydrazone

COOH

Γ ( C = M- NHSO ₂ - /

v \ _N /

Heated at 40 C for 24 hours. After the solvent has been distilled off, the residue is washed with water and finally boiled with acetonitrile. Yield: 1.3 g of the sodium salt of 3-carboxymethyl-2-benzthiazolone-semicarbazone.
Decomposition point at about 230 C.

Production example 5

lO-MethyW-acridon ^ '- earboxyphenylsulfonyl-hydrazone

N -NH-SO,

COOH

CH ₃

is made like photo:

A mixture of 3.07 g (0.01 mol) of I-methyl-2-methylthiobenzthiazoItum methyl sulfate and 2.32 g (0.Oi mole) of 5- (Hydrazinosuifonyi) -saHcylsäure for 30 minutes bd "40 C in 100 ml of pyridine was stirred After the substances have dissolved, the reaction is allowed to proceed for 12 hours at 20 ° C. The precipitate formed is washed first with water and then with 1η hydrochloric acid and finally again with water. The hydrazone obtained is purified by washing with acetonitrile F. = 260 C (decomposition).

Production example 4

Sodium salt of 3-carboxymethyl! -
2-beozthiazoIoa-semicarbazons

is made as follows:

3.67 g (0.01 mol) 9-methylthio-10-methyl-acridinium iodide, that according to Preparation Example 7 of

ag German Auslegeschrift 1 146 751, and 2.16 g (0.01 mol) of 4- (hydrazinosulfonyl) benzoic acid are allowed to react in 35 ml of pyridine at 20 ° C. for 7 days. The mixture is poured onto ice and the precipitate formed is filtered off with suction and then washed with water. The product is recrystallized from a mixture of ethyl acetate and η-hexane. Melting point: 195 C (with decomposition).
The melting point remains after a further l 'crystallization from isopropano! unchanged.

Production example 6

l-Methyl ^ -phenyl ^ -quinolone ^ '- carboxy-4'-hydroxyphenylsulfonyl-hydrazone

N - NH - SO,

COOH

OH

/ A

¹ ^

is made as follows:

a) Production of ^ -phenylamino-ethyl-einnamate:

A mixture of 261 ml (1.5 moles) of benzoyl ethyl acetate. 140 ml (1.5 moles) of aniline and 5 ml of one concentrated hydrogen chloride solution is 10 days at 2.0 C in the presence of concentrated sulfuric acid kept as a desiccant. The precipitate formed is filtered off and washed with methanol washed. The product is converted from methanol

(κ) crystallizes. Melting point: 71 C.

b) Production of 2-phenyl-4-quinolinol:

195 g (0.73 mol) of the above / -i-phenylamino-ethyl will prepared as follows: cinnamats are stirred to 2.2 1 diphenyl

3.2 g (0.0! MoH 2-methylmercapto- (3-carboxy- (> 5 ether added, which is heated to 250 ° C. After MethyO-benzthiazoiitimbroniid, prepared after stirring for a further 10 minutes at 250 ° C., is left Example 7. 1.1 g of sodium carbonate and 1.2 g of the reaction mixture are allowed to cool. The educated (0.0! Mo!) SeiHÜcsrtrazitf are in. 75 ml of pyridine precipitate is suctioned off and washed with ether

= N-NHCONH,

CH ₂ COONa

to wash. The melting point of 2 ~ phenvl-4-quinolinol is 250 C.

c) Production of 2-phenyl-4-chloro-quinolifi:

260 g (1.2 mol) of 2-phenyl-4-quinolinol are added to 321 ml (3.6 mol) of phosphorus oxychloride and heated to 80 ° C. for 2 hours. After cooling, the reaction mixture is poured onto ice. The precipitate formed is filtered off with suction and washed with water. After recrystallization 2-phenyl-4-chloro-quinoline is obtained from dilute ethanol. that melts at 60 C.

Production example 7

3-carboxymethyl-2-benzothiazolone methvlsulfonvl-hvdrazone

d) Production of l-methyl-2-phenyl-4-chloro-quinolinium-methylsulfal:

47.8 g (0.2 mol) of 2-phenyl-4-chloro-quinoline and 56 ml (0.6 mol) of dimethyl sulfate are 2 hours heated to 120 C. After cooling, the reaction mixture is washed thoroughly with ether. The remaining oil is used as such in the following reaction stage.

e) Preparation of l-methyl-2-phenyl-4-quinolone-3 '-carboxy-4' -hydro xyphenylsulfonyl-hydrazone:

102.7 g of this oil and 46.4 g (0.2 mol) of 5- (hydrazinosulfonyD-salicylic acid are refluxed in 500 ml of ethanol for 8 hours. After filtering off, the reaction mixture is dissolved in water poured. The precipitate formed is filtered off and first with water and then with Acetonitrile washed. After the product had been boiled with ethylene glycol monomethyl ether it has a melting point of 210 C (with decomposition).

I i

\ ^s \

35

40

= N- NHSOXH,

CH ₁ -COOH

is made as follows:

a) Production of 2-methylmercapto- (3-carboxymethyl) -benzothiazolium-broniid:

10 g (0.055 mol) of 2-methylthio-benzothiazole. prepared according to R. Riemsehneidcr. Monthly Chem. 91 (1960). 626. and 22.8 g (0.165 mol) bromoacetic acid are refluxed in 50 ml of dry benzene for 70 hours. The precipitate formed is suctioned off and washed first with ethanol and then with ether. The received Quaternary salt melts at 180 C (with decomposition).

b) Preparation of 3-carboxymethyl-2-benzothiazolon-methylsulfonyI-hydrazone:

8 g (0.025 mol) of this quaternary salt and 2.75 g (0.025 mol) of methylsulfonylhydrazide are used Heated at 60 ° C. in 100 ml of pyridine for 18 hours. After evaporation in vacuo, the mixture becomes mixed with water and then acidified with hydrogen chloride. The precipitate formed is suctioned off and recrystallized twice from a mixture of equal parts of ethanol and water. The hydrazone obtained melts at 200 ° C. (with decomposition).

Production example 8

3-methyl-2-benzothiazolone-4-sulfophenylisulfonylhydrazone

C = N-NHSO,

SO ₃ H

CH ₃

is made as follows:

a) Preparation of 3-methyl-2-benzothiazolon-4 ^/ -fluoiO-sulfonylphenylsulfonyI-hydrazone:

8.95 g (0.05 mol) 3-methyl-2-benzothiazoionhydrazone. prepared according to R. Riemschneider. Monthly Chem. 91 (1960). 626. 12.5 g (0.05 mol) 3 - fluorosulfonyl - benzene - sulfonyl chloride and 7.5 g (0.09 mol) of zinc oxide are refluxed in 250 ml of acetonitrile for 90 minutes. After cooling down the reaction mixture is poured onto ice, and the resulting precipitate is with Washed 1 η-hydrochloric acid and recrystallized from acetonitrile. Melting point: 198 ° C

45

b) Preparation of 3-methyl-2-benzothiazolone-4-sulfophenylsulfonyl-hydrazone:

20.5 g (0.05 mol) of this fluorosulfonyl compound are dissolved in 250 ml of 1N sodium hydroxide by heating dissolved on a water bath. The reaction mixture is filtered and then with hydrogen chloride acidified. The precipitate is filtered off with suction and washed with water and then removed recrystallized a mixture of equal parts of ethylene glycol monomethyl ether and water. Melting point: over 260 C.

Production example 9

3-Melhvl-6-methox> -2-benzothiazolone-3'-carboxy-4'-hydrox \ '- phenyIsulfonylhydrazone monohydrochloride

COOH

H, CO

N-NHSO ₂ OH · HCl

CH ₃

will come here like IbIet "

a) Preparation of 2-amino-3-methyI-6-metho.xybenzoihiazi) i! um-iodide:

10.8 g (0.06 mol!) Of 2-amino-6-methoxybenzothiazole, 15 ml of methyl iodide and 60 ml of acetone are refluxed for 1 hour. The quaternary salt formed begins to separate out during the reaction. After cooling, the precipitate is filtered off with suction and washed with acetone. Yield 19.2g. Melting point: over 260 C. _ί0

b) Preparation of 2-NJt: Osimino-3-methyI-6-methoxybenzothiazole:

From the iodide produced under a) is the

Base set free and extracted by adding 21 g (0.065 Mo!) Of this iodide in a mixture of lüüni! concentrated amniotic hydroxide and 100 ml of ether to be stirred. After evaporation of the ether is the resulting Dl in 160 ml of acetic acid solved. The nitrosation is then at 15 '"C In a solution of 39 g of sodium nilrite in 80 ml Water carried out. After stirring in liquid form the precipitate formed is filtered off with suction and washed with ether. Yield 14.5g. Decomposition point: 190 C.

c) Production of S-methyl-ö-methoxybenzothiazolthione <2>:

145 s of the above nitroso compound are at M) C in single portions to a mixture of 2! g of phosphorus pentasulfide. 250 ml pyridine and 60 ml Piperidine entered. The reaction mixture is then refluxed for 3 hours to reduce the temperature Finalize reaction. Finally the reaction mixture is poured onto ice. To After suctioning off, the precipitate formed is recrystallized from Pctroieumnaphtha. Yield: 10.8 g. Melting point: 118 C.

40

d) Production of 2-methyl mercapto-3-methyl-6-methoxybenzothiazole iodide:

From this benzothiazolthione (2) 10.8 g (0.051 mol) heated under reflux in 75 ml of ethanol and 20 ml of methyl iodide for 2 hours. After cooling down the precipitate formed is filtered off with suction in ice. Yield: 16.5 g. Decomposition point at about * 165 C.

e) Production of 3-methyl-6-methoxy-

2-benzotl ^ iazolon-3'-carboxy-4'-hyd ^ Όxyphenyl-

sulfonyl hydrazone monohydrochloride:

35.3 g (0.1 mol) of the above methyl mercapto compound and 23.2 g (0.1 mole) of S-carboxy- ^ hydroxyphenylsulfonyl hydrazide. which was prepared here under 2 a) is allowed to react in 150 ml of pyridine at 60 ° C. for 24 hours. The reaction mixture is then poured into a mixture of 500 g of ice and 150 ml poured strong hydrochloric acid. The precipitate formed is filtered off with suction, with water boiled and washed with ethanol. Yield 24g. Decomposition point at about 230 C.

In contrast to other known developers of the aromatic primary amino compound type, the hydrazones used here not only show greater solubility in aqueous alkaline media and greater stability against atmospheric oxidation, but can also be used in the form of secondary amines, since the otherwise fogging property of such compounds is not here disturbs. They are nevertheless oxidized by a bleached silver image, the silver salts of which have a solubility product of not less than 10 ^u at 25 ^° C. and which still contain silver nuclei. Good results have been obtained with silver images. the bleaching of which was stopped at the moment when no more silver can be seen with the naked eye.

These silver salts preferably have a solubility product of no more than 10 ⁷ at 25 ^° C.

Preferably CuCfe. FeCb. KgFe (CN) H, a mixture of "Na ₂ Cr ₂ Or and HCI, a mixture of K ^ SaO _1. And HC! Or a mixture of CuSO-i and HCl used as an oxidizing agent in the color development process according to the invention for bleaching the silver image .

The color development is carried out in an alkaline medium, preferably at a pH value not below 8, carried out.

According to one embodiment of the invention, the process for producing a lightfast color image comprises the following steps: A colored original is recorded with a photographic material which contains light-sensitive silver halide. This material comes in a black. white developer, the resulting silver image is faded to such an extent that silver nuclei are also present along with the "formed silver salts and silver salts have formed whose solubility product is not less than 10 ⁿ and not greater than 10 'at 25 ° C The bleached silver image is then developed in an alkaline aqueous solution containing a suitable color coupler and a hydrazone compound in one of the above general forms, and the developed material is fixed and rinsed.

According to a preferred Ausfüfariingsform is located However, the color coupler is in diffusion-proof form in the silver halide emulsion schicfate. So it is possible to produce a color reproduction in the complementary colors of a colored original, by using a multilayer photographic material which has a red-sensitive silver halide layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, the red-sensitive emulsion layer in diffusion-proof form contains a color coupler which, when developed can form a blue-green dye with a hydrazone compound of the aforementioned type, while the green-sensitive emulsion layer contains a color coupler in a non-diffusible form. which can form a bluish-red dye upon development of the same hydrazone compound, and the only blue-sensitive emulsion layer in diffusion-proof form contains a color coupler that can form a yellow dye with the same hydrazone compound. According to the last-mentioned embodiment color images that are very lightfast can therefore be generated from color negatives will. In the multilayer color photographic material, a yellow filter layer may be interposed the blue-sensitive and the green- or red-sensitive emulsion layer can be arranged.

909 * 06/1478

After the black and white development and fixing, the processing of the material can be interrupted after which the further treatments can be carried out in full daylight, without the quality being impaired (see Example 3).

If the method according to the invention is also particularly useful for producing color reproductions in complementary colors, real, direct-positive color reproductions can also be made are, for example, by using the positive silver images produced by the method of Generation of photographic black and white reversal images by William L. J ο 11 y, J. Chem. Educ, 39, 83 (1962). This procedure can be summarized as follows:

A multilayer paint material as described above is exposed to a colored original and developed in black and white. Dissolve the silver metal of the negative silver image in a aqueous bleach solution which concentrated 1 percent by weight potassium dichromate and 1 percent by volume Contains sulfuric acid without attacking the unexposed silver halide. After treatment with a 10 weight percent sodium sulfite solution is used to remove the unexposed silver halide an ordinary black and white developer, the one with sodium hydroxide and hydrazine sulfate was moved.

The metallic silver obtained in this reduction is then treated with an oxidizing agent, as described above, and the bleached silver image is made by the method of Invention color developed.

Although the method for generating colored images according to the invention is preferably under Use of a color photographic multilayer material is carried out in different sensitized silver halide emulsion layers each contain a suitable color coupler, the method according to the invention can also be used for color photographic materials with mixed emulsions are used, for example, in German Patent 1 040 899 and the German Auslegeschrift 1 086 122 are described, -fs

It was also found that the dyes produced by oxidative coupling according to the invention be obtained, can be metallized, d. H. as a complexing agent for metal salts, e.g. B. cobalt, Nickel, chromium or iron salts, can be used, so that one can see color shifts in this way can achieve.

Any black and white developer can be used to form the silver metal image, however one uses preferably a combination of p-methylaminophenoI and hydroquinone or a developer containing I-phenyl-3-pyrazolidinone.

Bleach solutions, which are preferably used, have the following composition: 50 g copper (II) chloride and 10 ml of acetic acid in 1000 ml of water or 15 g of potassium hexacyanoferrate (IN) in 1000 ml of water.

The color developing compositions according to the invention for the development of the bleached Silver image are used, contain preferably 1 to 10 g hydrazone per liter and preferably have a pH between 8 and 12.

example 1

To 280 g of a light-sensitive silver halide emulsion, ^5/6 moles of silver bromide and 8 percent by weight of gelatin, are gradually 45 ml of a color coupler solution is added, consisting of a solution of 4.5 g of N- (2'-n-HexadecyIsuIfonyl-5 ' -sulfophenyl) -l-hydroxy-2-naphthoic acid amide sodium salt in a mixture of 40.5 ml of water and 4.5 ml of 2N sodium hydroxide.

This emulsion is acidified to pH 6 with acetic acid and with 1 ml of a 10% aqueous Chromium (III) sulphate solution hardened. Then the emulsion is mixed with distilled water, which is a small Amount of common wetting agent, made up to a total of 500 ml. This emulsion is so on a barite-coated paper carrier is painted on so that 0.5 g of color coupler is present per square meter.

The dried emulsion layer is exposed behind a gray wedge and then for 10 minutes at 20 ° C in a developer bath with the following composition black and white developed:

p-MethySaminophenoI hemisulphate .. 0.5 g

Sodium sulfite (anh.) 20 g

Hydroquinone Ig

Borax 0.5 g

Water up to 1000 ml

The sample material is then rinsed for 1 minute in running water at 20 C and for 3 minutes in a solution of 15 g of potassium hexacyanoferrate (III) in 1000 ml of water. After a short rinse the bleached silver image is 7 minutes at 20 C in a color developing solution of the following composition developed:

S-Melhyl ^ -benzothiazolone-3'-carboxy-4'-hydroxyphenyl- sulfonyl hydrazone

(after manufacture 3) 4 g

Sodium sulfite (anh.) 4 g

Sodium carbonate (app.) 50 g

Water up to 1000 ml

The developed material is rinsed for 2 minutes in running water at 20 C and in a Bath of the following composition fixed the same:

Sodium iron (III) salt of

Ethylenediamine tetraacetic acid 37.5 g

Sodium salt of

Ethylenediamine tetraacetic acid 12.5 g

Ammonium thiosulphate (appendix) 110 g

Ammonium thioeyanate (appendix) 5 g

Sodium sulfite (anh.) 10 g

Water up to 1000 ml

After the material has been rinsed for 15 minutes in running water at 20 C, a negative blue-red image of the wedge is obtained with an absorption maximum at 530 ταμ.

The following table shows the absorption maxima that were obtained by the method of Example 1 by developing silver halide emulsion layers with the specified color coupler under Use of various hydrazone compounds have been achieved.

Table A.

Color coupler

OH

-CO-NH - (,

H ₃ C- (CH ₃ ) I ₅ -N-

SO ₂ - (CH ₂ J ₁₅ -CH ₃

■)

SO ₃ H

OH

I X
■ NH-CO V ^V '^

Absorptioiismaxima in nvx with
Hydrazone compound after manufacture

530

SO ₃

OH

540

SO, - NH - (CH,) ₁₅ - CH ₃ 520

SO ₃ H

455

-N,
O = CN

H ₂ CC - (CH ₂ | _ttT . - CH ₃

Example 2

A photographic material which was prepared as described in Example 1 is exposed as in Example 1! and developed in black and white. After development, the material is rinsed for 1 minute in running water at 20 ° C. and bleached in an aqueous solution containing 50 g of copper (II) chloride per liter and! iöml contains acetic acid. The bleached material is rinsed in running water for 5 minutes and color developed for 5 minutes in a bath of the following composition:
l-Metliy] -2-pheiiyI-4-diiiHoIon-3'-carbo ^i: y-4'-hydroxyphenyl-sulfonyl hydrazone

(after manufacture 6) 4 g

Namumsiilfit (appendix) 4 g

530

535

505

460

430 420 430

530

540

520

455

660

670

655

630

620

635

510

535

535

525

460

480 440 430

Sodium carbonate (app.) 50 g

1 η-aqueous sodium hydroxide .... 8 ml
Water up to 1000 ml

The color-developed material is rinsed for 2 minutes in running water at 20 C, and the rest Silver or the remaining silver salts are in a BSeichfixierbad as specified in Example 1 Composition removed. Obtained after 15 minutes of rinsing in running water at 2.0 ° C a negative blue image of the wedge with an absorption maximum at 630 ηΐμ.

, B e i s ρ i e I 3

A photographic material prepared as in Example 1 becomes as in Example 1 exposed and developed in black and white.

The developed material is fixed in a 20% aqueous sodium thiosulfate solution for 2 minutes and rinsed for 5 minutes in running water at 20 ° C.

Then the material is bleached for 2 minutes in a bath of the following composition:

Potassium hexacyanoferrate (III) 100 g

Borax 20 g

Boric acid 5 g

Water up to 1000 ml

After 5 minutes, rinse processing is interrupted days and then continued in broad daylight by the material is treated for 10 minutes indicated in the following solution. No impairment of the image quality can be determined.

i, 4-dimethyl-2-quinolone

S'-carboxy - ^ - hydroxyphenylsulfonyl-hydrazone

(after manufacture 2) 4 g

Sodium sulfite (anh.) 4 g

Sodium carbonate 50 g

Water up to 1000 ml

After rinsing for 5 minutes, the metallic silver is in a solution of the following for 5 minutes Composition bleached:

Potassium hexacyanoferrate (III) 50 g

Potassium bromide 15 g

Borax 10 g

Boric acid 13 g

Water up to 1000 ml

The material is then rinsed for 2 minutes fixed for 2 minutes in a 2O ^a / oiges aqueous solution of sodium thiosulfate, then rinsed once for 15 minutes in running water of 20 "C. This gives a negative blue red BiM of the wedge with an absorption maximum at 530 mp.

Example 4

ίο The following experiments show a possibility. achieve a wide variety of Farfosm ze.

A strip of film coated with silver chlorides media is exposed through a gray wedge and one after the other developed black and white, rinsed and treated with a potassium hexacjaEoferraffllli bleach bath, as described in example i.

The bleached SälberMM will last for 5 minutes 20 C in a solution of the following composition developed:

Hydrazone compound

according to the following table ...

Color coupler nacii foigäsder
Sodium sulfite (app.)

le

Ig
Ig
Ig

5 ⁽ equivalent aqueous NaSranam carbonate solution 250 ml

Then, the material] is prepared as described in Example 1, the same is fixed by 5 minutes in running water at 20 ~ C and sparged.

The following table shows the combination used, the fiber obtained and their absorption maxima.

/ ■
\ Vco Table B. CH, -C ^X N
Il II 1
SO ₃ H ■■■ - / Farfc Absorption
maximum Hydrazone
Connection
after manufacture Coupling component M P CH, - CN
"Ii! I .--> J GsIb 450 5 CH, -CO- - CH ₂ - CO - NH - ^ f IN C ^, V OH SO, - (CH,) ₁₅
-pCO -NH-Ij ⁷ ^ l Biauroi 515 5 \\
\
\ ~ -CH ₃ - co - BiaugrüE CH, 67 () 5 yellow 410 3

Hydrazone

Connection after production

15th

continuation

OH

CH

SO ₃ H

16

Red

Red

Red

Red

Yellow

Yellow

Yellow

Blue red

505

495

500

505

400

420

455

520

909 506/1478

17th

Continued 18

Hydrazone

link

after manufacture

Coupling component

Absorption maximum

ηΐμ.

OH

CO - NH - CH, - CH, - NH ₇ blue red

BJaurot

SSaurot

C ₂ H ₅

COOH
/ V NH-CO- CH ₂ - CO -Il J- NH - CO - (CH ₂ ) _{! 4} - CH ₃

COOH H

NH,

VV

SO ₃ H

OH

A,

KM

/ QH ₅

V ₂ H ₅ O, S -NH

yellow

Red

Ge! B

Blue red

520

560

555

615

470

505

605

470

5fO

535

If

Continuation

Hydrazone
Connection
after manufacture OH OH Inclusive component colour Absorption
maximum
in μ Vs 1 x> Blue red 525 ~> -NH - <^; ~ V- COOH Red 500

Example 5

A photographic material composed as described in Example 1 is exposed and developed black and white for 10 minutes in a developer bath with the following composition:

p-MonomeihylaniJnophenol 2.5 g

Sodium siiliit fanki 25 g

Hj ^r Jroehinon 6 g

Sodium. 40 g

Potassium bromide 0.5 g

Wasiffi- up to 1000 ml

The metallic formed during this development Silver becomes unaffected by treatment in a solution of the following composition of the undeveloped SHfoerhalide removed:

Kiiiium Dichromate Ig

Strong sulfuric acid 1 ml

Water up to 1000 ml

After this treatment, the silver halide is treated with a hydrazinbsitigec solution of the following composition reduced:

p-aminophenol-heniisylfate 2.5 g

Hydroquinone 6 g

Potassium bromide 0.5 g

Sodium sulfate fanli ... * 25 g

Sodium carbonate iaae.l 40 g

Hvdraziisulfal 2.4 g

Water up to 1000 ml

and then rinsed with running water for 5 minutes

These stages of treatment are described by W. JoHy in J. Cfaeni. Educ, 39 (1962). 83.

By bleaching the positive silver image obtained and further processing as in Example 1 one obtains a positive blue-red image with an absorption niaxJraiiQi at 530 πΐμ.

Example 6

A silver halide emulsion which is identical to red is produced as follows:

5 ml of a Farbkuppkriösung from Ig Np-Methylsuifonylaniinoäthy] - N - η - hexadecylaniün, 5 ml of 0.5 n-NatriumhydroAyd and 10 ml of ethanol to 35 ml of a 4 ^e _'B aqueous gelatin solution zugesexzi, the previously a small amount of a conventional Wetting agent? had been admitted.

The solution thus obtained is brought to pH 6 by adding acetic acid and then with 50 g a light-sensitive silver halide emulsion, the 1 / .so mol of silver bromide and 8 percent by weight Contains gelatin. This emulsion is then made by adding a solution of a red sensitizer sensitized.

A silver halide emulsion sensitized for green is prepared in an analogous manner by using as Color coupler 1 g of the sodium salt of N- (2'-n-hexadecylsulfonyl-5'-sulfophenyl) -1 -hydroxy-2-naphthoic acid amide is used.

A blue sensitive silver halide emulsion is prepared in an analogous manner, adding 1 g of l-p-silfophenyl-3-pentadecylpyrazolone as the color coupler is used.

On a cellulose acetate carrier with an antihalation layer on its back and on its front side is provided with an adhesive layer, the above are red-sensitized one after the other Silver halide emulsion layer, the above green-sensitized silver halide emulsion layer Yellow filter layer composed of colloidal silver dispersed in gelatin and the above blue sensitive Silver halide emulsion applied.

The multilayer photographic material obtained is passed through a multicolor negative exposed and then developed at 20 C for 5 minutes in a bath of the following composition:

p-methylaminophenol hemisulfate 0.75 g

Sodium sulfate anhydrous 25 g

Hydroquinone 3 g

Sodium carbonate anhydrous ... 16 g

Potassium bromide 1g

Water up to IQQO ml

This material is then rinsed in running water for 1 minute and in a solution for 3 minutes of 15 g of potassium hexacyanoferrate (III) in 100 ml of water. After a short rinse it will partially bleached silver image for 10 minutes at 20 C in a color developing bath of the following composition developed:

_6y . 3-methyl-6-methoxy

2-benzothiazolone-3'-carboxy-

4 '~ hydroxypheny! Su! Fonyl-

hydrazone (preparation 9) 4 g

Claims (1)

21 22 Anhydrous sodium sulfite 4g _{D t} """··" *, ". Anhydrous sodium carbonate 50 g claims. Water up to 1000 ml 1- Process for producing a color image by developing a bleached silver image, The developed material is rinsed for 5 minutes in 5 that still contains silver nuclei using hydra-flowing water and for 2 minutes in a zone, characterized in that Bath bleached with the following composition: color development by oxidative coupling Copper sulfate hydrate 100 g ¹¹ Ji ¹ p. ^ei " ^{es F} .f ^ ^kup ^. ^with ,? ^ner ^ _A ^a Sodium chloride 100 | alkaline aqueous medium dissolved hydrazone Conc. Sulfuric acid 25 ml ^I0 compound of the general formula Water up to 1000 ml After the material has been poured in flowing 1 — Z — 1 1 ¹ Water has been rinsed, it will be 2 minutes in j ^ q = NN 20 ^!) / Oiger aqueous sodium thiosulphate solution fixed 15 1 j and another 10 minutes in running water ο r flushed. A positive multicolor image is obtained, ^{3 2} that from the complementary colors of the negative or Originals exists. ^ Example? ²⁰ I ^Z i 1 * N- C = C- C = N-N A photographic material produced as described in item III i game 1 is made, after exposure, RRR R development and bleaching, as in the case of 345
game 2, color developed by adding 10 Mi- 25 grooves in a bath of the following composition, in which Z denotes the is dealt with: permanent necessary non-metal atoms of a 3-carboxymethyl-2-benzthiazolone 5- or 6-membered heterocyclic, given semicarbazone, as described ^for ? ^IIs substituted ring or a condensate in preparation example 4 4 g of ³ ° ^{siert Rin} § ^s y ^stems . ^{the one 5} " ^or 6ghedrigen Sodium sulfite anhydrous . '.'. '.'. '.'. '. ^4g '£ ⁱⁿ S. ^ SS ^ g ^{1 W} ^ sser J ^ ° ^{the dn Acy- lres} *' Anhydrous sodium carbonate 50 g ^R - ^ei " ^e CONH ₂ - or SO, X group, worm X Aqueous 1 n-sodium hydroxide - a hydroxyl group, em Ammo em alkyl, 8 ml solution is ^an aryl residue or a heterocyclic residue, Water up to 1000 ml ^{35 R :! e} ' ⁿ hydrogen atom, an alkyl or an aryl rest, possibly by solubilizing After rinsing the material for 2 minutes, groups are substituted, Ri and R5, which has the same. it is treated for 3 minutes in the bleach-fix bath or different, one hydrogen each or one of Example 1. The purple image obtained with a halogen atom or a dialkylamino, carbo-absorption maximum at 525 m; x is still 15 mi-thoxy. Rinsed cyano, alkoxy, alkyl or aryl grooves. group or together to close an _R. . . “5- or 6-membered homocyclic ring requires 8 such atoms, with the soluble wedge product have arisen, not less than 10 ⁿ in the development and bleaching, as in the case of 25 C may be. spat! 2 described, color developed by adding 10 Mi- 2. The method according to claim 1, characterized in grooves in a bath of the following composition indicates that a hydrazone is used, is treated: in which according to the general formula (II) 3-ethyl-2-benzthiazolon- ⁵ ° ^the substituent R ₁ and or R-, a trifluoro (N-piperidinosulfonyl) hydrazone 4 ε means methyl group. Anhydrous sodium sulfite 4 g J ^{"Vcrfah. Reindeer,"} f ^ f '* ~ ^{characterized} Anhydrous sodium carbonate 50 for Γ Γ £ JT ^PP T '" Aqueous 1N sodium hydroxide ^ u / i- 'man ^{m 4} · The method according to claim 1 to 3 thereby ^{water DIS ιυυυ ml} characterized that one with the help of an aqueous After rinsing the material for 2 minutes, the solution bleaches the hexacyanoferrate (III) ions Has. it is treated in the bleach-fix bath for 3 minutes. of Example 1. The purple image obtained with a 60 5. The method according to claim 1 to 3, characterized Absorption maximum at 535 ma is still 15 Mi- characterized that one with an aqueous grooves rinsed. Solution that contains copper (II) chloride is bleached.