DE1928554B2 - Color development process for producing color photographic images - Google Patents

Description

N = CR ¹

R-N

C-CH ₂

C = C-R '

R —N

J
\

C - CH - Y

Il ο

30th

where R denotes an alkyl or aryl group or heterocyclic group, R ¹ denotes an alkyl, carbamyl, amino or amido group and Y denotes a group which is split off during the coupling reaction, and optionally a further silver halide emulsion layer contains a non-diffusing color coupler for the production of a blue-green image dye , color-developed, bleach-fixed and watered after imagewise exposure, characterized in that a recording material is used with the combination of the following features: (A) the layers of the recording material are hardened with a vinyl sulfone hardener and free from aldehyde hardeners or hardeners which set free aldehydes , (B) the recording material contains a yellow image dye-forming 2-equivalent color compound having the following structural formula:

R - C - CH - Y ¹

O X

55

in which R denotes an alkyl group, X denotes a cyano or substituted carbamyl group and Y ¹ denotes a group which is split off during the coupling reaction.

2. The method according to claim 1, characterized in that a recording material is used which as a yellow dye-supplying "color coupler" - fluoro - a - pivalyl- 5 - [y - (2,4 - ditert. - amylphenoxy) butyramido] - 2 - fluoroacetanilide, «- pivalyl - a - stearyloxy - 4 - sulphamylacetanilide or« -pivalyl - «- [4- (4-benzoyloxyphenylsulfonyl) phenoxy] - 2 - chloro - 5 - [y - (2,4 - di - tert-amylphenoxy) butyramido] - acetanilide contains.

3. The method according to claim 1, characterized in that that one uses a recording material in which the hydrophilic colloid of the layers is hardened with a hardening agent consisting of a divinyl sulfone

4. The method according to claim 3, characterized in that a recording material is used in which the hydrophilic Kolloi ^: -ier layers with bis (2-vinylsulfonylmethyl); 4i. τ is hardened

5. The method according to claim 1, characterized in that that a bleach-fix bath is used which contains as a silver oxidant:

a water-soluble ferricyanide,

a water-soluble quinone,

a water-soluble ferric salt,

a water-soluble cupris salt,

a water soluble cobalti salt or

a complex salt of an alkali metal

and a polyvalent cation

with an organic acid

one of the following formulas:

Il Il

HO - C - R ⁷ - X - R ⁸ - C - OH

or

HO - C - R ⁹ - N - R ¹⁰ - C - OH

O R "O

Il I Il

HO - C - R ⁹ - N - R ¹⁰ - C - OH

in which X denotes a hydrocarbon radical, an oxygen or sulfur atom or a radical of the formula = NR ¹² , in which R ^{12 is} a hydrogen atom or a hydrocarbon ^{radical, and R 7} , R ⁸ , R ⁹ , R ¹⁰ and R "are hydrocarbon radicals, where that the polyvalent cation is a ferric, cobalt or cupric ion.

6. The method according to claim 5, characterized in that a bleach-fix bath is used, in which the silver oxidizing agent is made up of sodium ferric ethylenediamine tetraacetic acid, sodium cobalt diethylenediamine tetraacetic acid, Sodium cuprinitrilotriacetic acid or cobalt ammonium nitrate.

7. Process according to Claims 1 and 5, characterized in that there is a bleach-fix bath used in which the silver oxidizing agent is made up of quinone and the silver halide solvent 3,6-dithia-1,8-octanediol.

The invention relates to a color development process for producing color photographic images, in which one imagewise exposed color photographic recording material, consisting of

a support and hardened super halide emulsion layers, who are sensitized to different areas of the visible spectrum, one of which uses a non-diffusing 2-equivalent color coupler for producing a yellow Image dye, another a non-diffusing color coupler for the production of a magenta One of the following formulas:

N = CR ¹

IO

R —N

(D

C-CH ₂

Il ο

C = CR ¹

R-N

20th

(II)

C-CH —Υ

Il

ο ² p

where R denotes an alkyl or aryl group or heterocyclic group, R ¹ denotes an alkyl, carbamyl, amino or amido group and Y denotes a group which is split off during the coupling reaction, and optionally a further silver halide emulsion layer contains a non-diffusing color coupler for the production of a blue-green image dye , color developed, bleach-fixed and watered after imagewise exposure.

It is known, for example from US-PS 22 52 798, for the production of multicolor photographic Images to use multilayer color photographic recording materials. Usually these recording materials consist of a layer support on one side of which selectively sensitized Emulsion layers are applied. As a rule, the outermost layer is sensitive to blue, the next layer is green-sensitized and the layer closest to the support is red-sensitized. A bleachable yellow filter layer is often arranged between the blue-sensitive and the green-sensitized layer, which serves the purpose serves to absorb blue radiation that can pass through the blue-sensitive layer. Recording materials of the type described may further include interlayers for special purposes as well Have cover layers. Of course, the arrangement of the individual layers can also depend on the described arrangement differ. As a rule, the blue-sensitive layer, the green-sensitized one Layer and the red sensitized layer for forming a yellow dye image, one magenta dye image and a cyan dye image, respectively. To create these dye images are usually so-called open-chain ketomethylene color couplers, pyrazolone color couplers as well as phenolic and naphtholic color couplers are used.

A distinction is made between so-called 4-equivalent and so-called 2-equivalent color couplers. Most of the couplers are 4-equivalent couplers. The use of yellow dyes left Fernden 2-equivalent color couplers is for example from US-PS 27 28658, 2436130 and 225392 ' as well as the JA-PS 2838/64 known.

It is also known e.g. B. from DT-AS 11 24 356 to develop color photographic recording materials according to a developing process disclosed in essentially consists of four process stages, namely the color development, a bleaching step, a fixing step and a stabilizing step. This as a 4-step process A designable development process was later made known by one from DT-AS 11 27 715 Modified process in which the bleaching step and the fixing step are combined. Durct the combination of bleaching and fixing steps significantly shortened the color development process achieved with the one from the DT-AS 11 27 715 known methods were doing the same color photographic Recording materials used, as in the case of that known from DT-AS 11 24 356 Procedure, d. H. Recording materials with so-called 4-equivalent color couplers were used for development for generating the yellow dye images and 5-pyrazolone color couplers for generating of the purple dye images were used.

However, the disadvantage of the method known from DT-AS 11 27 715 is that the intensity of the generated yellow dye images is reduced and that the intensity of the generated magenta dye Dye images leaves much to be desired. By shortening the color development process thus certain disadvantages in the color quality of the developed color images are accepted.

In view of the disadvantages of the method described in DT-AS 1127715, another Color development process known, which is described in US Pat. No. 3,189,452. This method differs from the method known from DT-AS 11 27 715 in that, in addition, according to is bleached again after the bleach-fix. It was found that by the additional bleaching again yellow dye images and purple dye images of full intensity can be obtained. By the inclusion of a special bleaching bath, however, had to be accepted that the whole Color development process was again extended by one process step.

The object of the invention was to provide a shortened color development process for the production of color photographic images with a combined bleaching and fixing stage, in which a reduction the intensity of the yellow dye and magenta dye images produced, as in the case of the one from the DT-AS 11 27 715 known procedure no longer occurs.

The invention is based on the knowledge that such a shortened color development process can be achieved by using recording materials with special color couplers and also recording materials which do not contain an aldehyde hardener or an aldehyde-releasing agent Connection included.

The invention relates to a color development process for producing color photographic images, in which one imagewise exposed color photographic recording material, consisting of a support and hardened silver halide emulsion layers facing different areas of the visible spectrum are sensitized,

one of which is a non-diffusing 2-equivalent color coupler for the production of a yellow image dye, another a non-diffusing one Color coupler for the production of a magenta image dye of one of the following formulas:

N = CR ¹

R —N

(I) ίο

R-N

(H)

C-CH ₂

Il ο

C = CR ¹

C-CH - Y

Il ο

where R denotes an alkyl or aryl group or heterocyclic group, R ¹ denotes an alkyl, carbamyl, amino or amido group and Y denotes a group which is split off during the coupling reaction, and optionally a further silver halide emulsion layer contains a non-diffusing color coupler for the production of a blue-green image dye , color-developed, bleach-fixed and watered after imagewise exposure, which is characterized in that a recording material is used with the combination of the following features: (A) the layers of the recording material are hardened with a vinyl sulfone hardener and free from aldehyde hardeners or aldehydes releasing hardening agents, (B) the recording material contains a 2-equivalent color coupler which forms a yellow image dye with the following structural formula:

R - C - CH - Y ¹

Il I ο χ

(III)

45

in which R denotes an alkyl group, X denotes a cyano or substituted carbamyl group and Y ¹ denotes a group which is split off during the coupling reaction.

For example, a recording material is suitable for carrying out the method of the invention, Consists of a conventional substrate on which are applied: a first silver halide emulsion layer, which is sensitive to one region of the visible spectrum and which itself is not diffusing open-chain ketomethylene color couplers of the specified ones which produce a yellow dye Contains formula or is associated with a layer with such a color coupler, which with the oxidation products of common color developing agents consisting of primary aromatic amines reacts to form a yellow dye and does not form a non-colored form of the yellow dye which is not in can be transferred to the yellow dye by a bleach-fix bath after color development, and a second silver halide emulsion layer !, the is cm-sensitive to a second region of the visible spectrum and either itself contains a non-diffusing 5-pyrazolone coupler of the formula given or that has a layer is in contact with such a color coupler, the color coupler with the oxidation products of primary aromatic amine color developing agents to form a magenta Dye reacts and the recording material of aldehyde hardeners and Aldehyde-releasing hardeners is free.

According to a further embodiment of the method of the invention, a recording material used, a third in addition to the two described silver halide emulsion layers Silver halide emulsion layer containing opposite to a third region of the visible spectrum is sensitive and which either itself or in a layer adjacent to it does not diffuse phenolic or naphtholic color couplers, which with the usual, from primary aromatic Color developer compounds exist in amines to form a blue-green dye reacted.

According to a particularly advantageous embodiment of the method of the invention, a recording material is used is used, which consists of a substrate on which are applied: a red-sensitive silver halide emulsion layer with a phenolic or naphtholic coupler, a green sensitized silver halide emulsion layer with a 5-pyrazolone coupler of one of the formulas given and a blue-sensitive silver halide emulsion layer with an open-chain ketomethylene color coupler which forms a yellow dye given formula.

Advantageously, there is between the green-sensitized Layer and the top blue-sensitive layer a bleachable yellow-colored, blue Light absorbing filter layer arranged.

The sequence of the photosensitive layers applied to the support can also be at the same time other than the one described.

According to a further embodiment of the method of the invention, a recording material with a single photosensitive layer in which the three sensitized differently Dispersed silver halide emulsion layers with the corresponding color couplers in the form of packets are present. For example, the blue-sensitive silver halide emulsion with one yellow dye-providing couplers are incorporated into yellow dye-providing packages, whereas the green sensitized silver halide emulsion and the magenta dye forming coupler may be contained in a crimson image delivering packages and whereas furthermore the red-sensitized ones Silver halide emulsion containing the cyan dye forming coupler in cyan dye image forming packets could be. Recording materials of this structure are disclosed, for example, in US Pat. No. 2,284,877 known.

If appropriate, the recording material can, when carrying out the method of the invention, between Color developing and bleach-fixing watered

IOt-
; i! t'i-. CHlC

'CIIC Il

enid-
"material
ϊ animal

jriin-

vcr-. ■ r! cn

will. The developed, bleach-fixed and watered material can then be dried or after Soak in water and treated with a stabilizer solution (stabilizing bath) before drying.

By practicing the method of the invention, images of excellent quality are obtained, wherein no or practically no non-colored leuco forms of yellow in the developed recording material or purple dyes are present.

The recording materials leaving the bleach-fix bath when the process of the invention is carried out in other words, do not have leuco forms of yellow dyes and purple dyes so that there is no need to remove the recording materials after the treatment In the bleach-fix bath still to be treated with a bleach solution to obtain the required yellow and purple dye densities. This is in contrast to the known methods which the recording materials either in separate bleaching and fixing baths have been treated or in a special bleach bath following the bleach-fix bath in order to achieve the to achieve desired and required dye densities.

To carry out the method of the invention, recording materials with the most varied customary known layer supports are used, for example layer supports made of foils Cellulose nitrate, cellulose acetate, polyacetals, polystyrene, polyterephthalate and polyethylene as well made of paper and glass.

To produce the silver halide emulsion layers of the recording materials, the common known hydrophilic colloids are used, for example gelatin, colloidal albumin, Cellulose derivatives or synthetic resins, for example polyvinyl compounds. Except for the ones mentioned Substances are suitable for the production of the emulsion layers, for example, also polyvinyl alcohol as well hydrolyzed polyvinyl acetate (cf. US Pat. No. 22 86 215), hydrolyzed cellulose esters, e.g. B. on an acetyl group content from 19 to 26% hydrolyzed cellulose acetate (cf. US Pat. No. 23 27 808), water-soluble ethanolamine cellulose acetates (See. US-PS 23 22 085), polyacrylamides with a combined acrylamide group content from 30 to 60% and a specific viscosity from 0.25 to 1.5 as well as imidized polyacrylamides with the same acrylamide group content and corresponding viscosities (see US Pat. No. 25 41 474), Zein (see US Pat. No. 2,563,791), VinylaJkdiolpolymensate with urethane carboxylic acid groups (cf. US Pat. No. 2,768,154), vinyl alcohol polymers with cyanoacetyl groups, e.g. B. vinyl alcohol-vinyl cyanoacetate copolymers (see. US-PS 28 08 331) and polymers. » obtained by polymerizing a protein or a saturated acylated protein with a monomer with vinyl groups (cf. US Pat. No. 2,852,382).

The silver halide emulsion layers of a recording material processable by the method of the invention can contain the usual silver halides, for example silver bromide, silver bromoiodide, Silver chloride. Silver chlorobromide and silver bromochloroiodide. fts

The individual emulsion layers of the recording materials can be used in a known manner Be wise chemically sensitive. So can the emulsions for example, they may have been digested with natural active gelatin, or they may be sulfur compounds contain, as known for example from US Pat. Nos. 15,74944, 16 23 499 and 24 10 689 are.

The emulsions can also have been pretreated with noble metal salts, for example Salts of ruthenium, rhodium, palladium, iridium and / or platinum, for example from the U.S. Patents 2,448,060, 25 66 245 and 25 66 263 is known.

The emulsions can furthermore be optically sensitized in the usual way, e.g. B. with cyanine and merocyanine dyes, as described, for example, in US Patents 1846301, 1846302, 1942854, 19 90 507, 21 12 140, 2165 338, 2493 747, 27 39 964, 24 93 748, 25 03 776, 25 19 001, 26 66 761, 27 34 900, 27 39 149 and GB-PS 4 50 958 are known.

The emulsion layers can furthermore contain customary sensitivity-increasing compounds contain, for example quaternary ammonium compounds, as they are from US Patents 22 71623, 22 88 226 and 23 34 864 are known and also polyethylene glycols, such as those from US-PS 27 08 162 have become known.

The emulsion layers can also have been chemically sensitized with gold salts, such as it is known, for example, from US Pat. Nos. 23 99 083, 25 97 856 and 25 97 915. Particularly suitable for this Gold compounds are, for example, potassium chloroauril, potassium aurithiocyanate, potassium chloroaurate, auritrichloride and 2-aurosolobenzothiazole methochloride.

In the case of the non-diffusing, open-chain ketomethylene yellow dye couplers used according to the invention, whose active carbon atom is substituted by a removable group, it is z. Cyanoacetyl couplers, acylacetyl couplers, e.g. Acylacetanilide couplers, for example alkoylacetanilide couplers, pivalylacetanilide couplers, acylacetamide couplers, for example alkoylacetamide couplers and pivalylacetamide couplers.

In the given structural formula III can the radicals R and / or X represent ballast groups or by such ballast groups which make the coupler compound non-diffusing, be substituted. Advantageously, the Couplers containing ballast groups also contain solubilizing groups or residues. The meaning and the structure of ballast groups is known, so that this will not be discussed in more detail needs.

^{The radical represented by Y 1} in the formula HI and splitting off in the coupling reaction can be, for example, a chlorine or fluorine atom, a thiocyano radical or an acyloxy radical, for example an optionally a'koyloxy radical, an optionally substituted aroyloxy radical or an optionally substituted heterocycloyloxy radical. Y ¹ can also, for example, be a cyclooxy radical, e.g. B. an aryloxy radical, for example a phenoxy or a naphthoxy radical or a heterocyelooxy radical, λ be a pyridmyloxy, a tetrahydropyranyloxy or a tetrahydroquinolyloxy radical. Finally, Y ¹ can also be, for example, an alkoxy radical, an alkylthio radical or arylthio radical.

Advantageous for the production of a for implementation of the method of the invention suitable

509 518/157

Ketomethylene couplers suitable for drawing material are, for example:

1. a-Fluoro-a-pivalyl-5 - [) '- (2,4-di-tert-amylphenoxy) butyramido] -2-chloroacetanilide,

2. a-pivalyl-a-stearoyloxy- ^ sulfamylacetanilide,

3. a-Pivalyl-a- [4- (4-benzyloxyphenylsulfonyl) -phenoxy] -2-chloro-5-iy- (2,4-di-tert-amylphenoxy) butyramido] acetanilide,

4. a- [4- (N-Methyl-N-octadecylsulfamyl) phenoxy] -a-pivalyl-4-sulfoacetanilide, Potassium salt,

5. «-Pivalyl-a- (4-sulfophenoxy-4- (N-methyl-N-octadecylsulfamy ^ -acetanilide, Potassium salt and

6. <i- [4- (4-Hydroxyphenylsulfonyl) phenoxy] -a-pivalyl-2-chloro-5- [y- (2,4-di-tert-amylphenoxy) butyramido] acetanilide.

From the US-PSs 27 28 658, 24 36 130 and 22 53 924 as well as the JA-PS 2838/64 known »ο 2-equivalent couplers of the formula

R - C - CH - Y ¹

Il I ο χ

15th

the 2-equivalent couplers producing yellow dyes used according to the invention differ in particular by various substituents R and X. Thus, in the known couplers, R is an optional substituted phenyl radical and X is a different from a cyano or substituted carbamyl radical Rest.

In the formulas I and II given for the non-diffusing 5-pyrazolone ^{color couplers, R 1} , if it has the meaning of an amido radical, can be, for example, a benzamido or alkamido radical. The usual radical represented by Y, which splits off in the coupling reaction, can be, for example, a thiocyano, acyloxy, aryloxy, alkoxy, alkylthio, arylthio or Sulfor radical or a chlorine or fluorine atom.

The radicals R and / or R ^{1 of} the specified structural form can be substituted by the customary known radicals, including by customary known ballast groups, in order to make the color couplers in the hydrophilic colloid layers non-diffusing, as well as solubilizing groups.

Typical recording material suitable for making a recording material suitable for carrying out the method of the invention suitable color couplers which produce a magenta dye are, for example:

1. 1 -p-sec.-amylphenyl-S-n-amyl-S-pyrazolone,

2. 2-cyanoacety! -5- (p-sec.-amylbenzoylamino) -coumarone,

3. 2-Cyanoacetylcoumarone-5- (N-n-amyl-p-tert-amylsulfanilide).

4. 2-cyanoacetylcoumarone-5-sulfone-N-n-butylanilide.

5. 2-cyanoacetyl-5-benzoy ^ amino-cumaΓon,

6. Z-cyanoacetylcoumarone-S-sulfondimethylamide,

7. 2- <~ yanoacrtylcoumarone-5-sulfone-N-methylanilide,

8. 2-Cyanoacetylcutnaroti-5- (N -> '- phenylpropyl - (- p-tert.-amylsulfonaniltd,

9. l-p-Laurylphenyl-S-methyl-S-pyrazolone,

10. l - ^ - naphthyl-S-amyl-S-pyrazolone,

11. l-p-nitrophenyl-S-n-amyl-S-pyräzolön,

12. 1 -p-phenoxyphenyl-S-n-amyl-S-pyrazolone,

13. l-PhenyW-n-amyl-S-pyrazolone,

14. l, 4-phenylene-bis-3- (l-phenyl-5-pyrazolone),

15. 1 -Phenyl-S ^ aeetylamino-S-pyrazolone,

16.l-phenyl-S-n-valerylamino-S-pyrazolone,

17.l-phenyl-S-chloroacetylamino-S-pyrazolone,

18. 1-phenyl-S-benzoylamino-S-pyrazolone,

19. l-phenyl-3- (m-aminobenzoyl) amino-5-pyrazolone,

20. l-phenyl-3- (p-sec.-amylbenzoylamino) -5-pyrazolone,

21. l-phenyl-S-diamylbenzoylamino-S-pyrazolone,

22. 1 - Pheny! -3- / f-naphthoy lamino-5-pyrazolone,

23. 1-phenyl-S-phenylcarbamylamino-S-pyrazolone,

24. l-phenyl-S-palmitylamino-S-pyrazolone,

25. l-phenyl-S-benzenesulfonylamino-S-pyrazolone,

26. l- (p-phenoxyphenyl) -3- (p-tert-amyloxybenzoyl) amino-5-pyrazolone,
l- (2 ', 4', 6'-trichlorophenyl) -3-benzamido-

55

60 5-pyrazolone,
! ^^ 'o'Tri

27

5-pyrazolone,

29. l- (2 ', 4'-dichlorophenyl) -3- [3 "- (2'", 4 '"- di-tert-amylphenoxyacetamido) benzamido] -5-pyrazolone,

30. l- (2 ', 4', 6'-Trichlorophenyl) -3- [3 "- (2" '- (2 "\ 4"' - di-tert-amylphenoxyacetamido) benzamido] 5-pyrazolone,

31. l- (2,4-Dimethyl-6-chlorophenyl) -3- [3 - (- (mpentadecylphenoxy) butyramido) benzamido] - 5-pyrazolone,

32. 1- (2 ', 5'-dichloro) -3- [3 "- (4'" - tert-amylphenoxy) benzamido] -5-pyrazolone,

33. 1- (2 ', 4', 6'-tribromophenyl) -3- [3 "- (4 '" - tert-amylphenoxy) benzamido] -5-pyrazolone,

34. l- (2 ', 5'-dichlorophenyl) -3- [3 "- (2'", 4 '"- di-tert-amylphenoxyacetamido) benzamido] -5-pyra- zolon,

35.1 - (2,4,6-Trichlorophenyl) -3- (4-nitroanilino) -4-stearoyloxy-5-pyrazolone,

36. 1 - (2,4,6-Trichlorophenyl) -3- (3 - [«- (2,4-di-tert-amylphenoxy) acetamido] benzamido) -4-acetox; 5-pyrazolone,

37.1 - ^ Ao-TrichlorophenylH-pentadecyl- ^ thiocyano-5-pyrazolone,

38. H2,4,6-trichlorophenyl) -3- [3- (2,4-di-tertamylphenoxyacetamido) benzamido] -4-thiocyano-5-pyrazolone,

39.1 -ip-tert-ButylpfaenoxyphenylJ-S-ij-tp-tert-butylphenoxyJ-propionamido - ^ - thiocyano-5-pyrazolone,

40. l-ii ^ ö-TrichlorophenylJ-S-pentadecyl - ^ - sulfo-5-pyrazolone,

41st! - (14.6-Trichlorophenyl) -3-pentodecyl-4-cnlorc 5-pyrazoion,

42nd! - [4- (34-Dicarboxylbenzamido) phenyl] -3-ethoxy ^ S-octadecylcarbamylphenylthioi-S-pyrazolone.

If recording materials are used to carry out the process of the invention, they contain a non-diffusing phenolic or naphthic, blue-green dye-forming dyes Couplers are included, the usual means can be used for this Color couplers of this type can be used. Vorzuj wise can be such, a blue-green fat

Substance forming couplers are represented by one of the following structural formulas:

OH

(IV)

(V)

R ³

R ⁴

R ³

OH

(VII)

wherein R ² denotes a hydrogen atom, an alkyl or aryl radical, or a heterocyclic radical, or an amino radical, e.g. B. an amino, alkylamino, arylamino or heterocyclic amino radical, a substituted carbonamido radical, for example an alkylcarbonamido or arylcarbonamido radical or a heterocyclic carbonamido radical; a substituted sulfonamido radical, e.g. B. an alkylsulfonamido, arylsulfonamido or heterocyclic sulfonamido radical; a substituted sulfamyl radical, e.g. B. an alkylsulfamyl, arylsulfamyl or a heterocyclic sulfamyl radical; a substituted carbamyl radical, e.g. B. an alkylcarbamyl, arylcarbamyl or a heterocyclic carbamyl radical and the like; R ³ , R ⁴ and R ⁵ each represent a radical ^{as defined for R 2} and also optionally a chlorine atom or an alkoxy radical, where R ² , R ³ , R ⁴ and R ^{5 are} optionally advantageously substituted by one or more conventional ballast groups can; Y ^{2 is} a radical as defined for Y with the exception that Y ^{2 is} not an aryloxy radical; Y ^{3 is} one of the ^{radicals specified for Y 2} , but Y ^{3 can} additionally be a cyclic imido radical, e.g. B. a maleimido, a succinimide, a 1,2-dicarboxyimido or a phthalimido radical.

Typical such cyan dye-forming couplers are, for example:

1. 5- (p-Amy] phenoxybenzenesulfonamino) -I-naphthol,

2. 5- (N-Benzyl-N-naphthaImsulfonamino) -1-naphthol,

3. -Ήη-Benzyl-N-n-valerybmrnoH-naphthol.

4. 5-caproylamino-1-naphthol.

5. 2-chloro-5- (N-n-valeryl-N-p-isopropylbenzylamino) -1-naphthol,

6. 2-chloro-5- (p-nitrobenzoyl- / S-o-hydroxyethylamino) -1-naphthol,

7. 2-chloro-5-palmithylamino-1-naphthol,

8. 2,2'-dihydroxy-5,5'-dibromostilbene,

9. 5-Diphenyläthersulfonamido-1-naphthol,

10. l-hydroxy-2- (N-isoamyl-N-phenyl) naphthamide,

11. l-hydroxy-2- (N-p-sec.-amylphenyl) naphthamide,

12. 8-Hydroxy-1 - «- naphthoyl-1,2,3,4-tetrahydroquinoline,

13. 1-naphthol-2-carboxylic acid-a-naphthalide,

14. 1-naphthol-S-sulfo-cyclohexylamide, 15. 5-phenoxyacetamino-1-naphthol,

16. 5-ß- phenylprbpionylamino-1-naphthol,

17. Monochlor-S-iN-y-phenylpropyl-N-p-secamylbenzoylaminoH-naphthol,

18. 2-acetylamino-5-methylphenol,

19. 2-BenzoyIamino-3,5-dimethylphenol,

20. 2 - «- (p-tert-amylphenoxy) -n-butyrylamino- (VI) 5-methylphenol,

21. 1-Hydroxy-2- [a-2,4-di-tert-amylphenoxyn-butyl] naphthamide,

22. 2- (4 "-tert.-amyl-3'-phenoxybenzoylamino) -3,5-dimethyl-1 -phenol,

23. 2 (4'-phenoxybenzoylamino) phenol,

24. 2 (4 "-tert-amyl-3'-phenoxybenzoylamino) -phenol,

25. 2 - [<i- (4'-tert-butylphenoxy) propionylamino] phenol,

26. 2- [N-methyl-N- {4 "-tert.-amyl-3'-phenoxybenzoylamino)] phenol,

27. 2- (4 "-tert.-amyl-3'-phenoxybenzoylamino) -3-methyl-1 -phenol,

28. 2- (4 "-tert-amyl-3'-phenoxybenzoylamino) -6-methyl-1 -phenol,

29. 2- (4 "-tert-amyl-3'-phenoxybenzoylamino) -3,6-dimethylphenol,

30. 2,6-di (4 "-tert-amyl-3'-phenoxybenzoylamino) -1-phenol,

31. 2-a - (% '- tert-amylphenoxy) butyrylamino-1-phenol,

32. 2 (4'-tert-AmyW-phenoxybenzoylamino) -3,5-dimethyl-1 -phenol,

33. 2- [u- (4'-tert-Amylphenoxy) -n-butyrylamino] -5-methyl-1 -phenol,

34. 2 (4 "-tert-amyl-3'-phesoxybenzoylamino) -4-chloro-1 -phenol,

35. 3- [fj- (4'-tert-Amylphenoxy) -n-butyrylamino] -6-chlorophenol,

36. 3- (4 "-tert-amyl-3'-phenoxybenzoylamino) -phenol,

37. 2- £ «- (2,5-Di-tert-aniylphenoxy) butyraiiiido] -4,6-dicnioro-S-methylphenol,

38. 3 - [«- (4'-tert-Amylphaioxy) -n4) otyrylamino] -S-chlorophenoi,

39. 3- [(i- (4 ^r -terL-amylphenoxy) -n-4} utyrylainino] -2-chlorophenol,

40. 2 - «- (4'-tert-Amylphenoxybutyrylamnio) -5-chlorophenol,

41. 2- (4 '-tert.-Amyl-S'-plienoxybenzoylainmo) -3-chlorophenoL,

42. 5-Bcn / olsulfonamino-1-naphthol,

6s 43. 2-chloro-5-benzenesalfonaiiimo-l-naphthoi

44. 2-Chloro-5- (p-tolBolsulfonammo) -l-naphthoi

45. 5- (1,2,3,4-tetrahydronaphthalene-6-suifammo) -1-naphthol,

46. 2-chloro-5- (4'-bromodiphenyl-4-sulfonamino) -1-naphthol,

47. 5- (quinoline-5-sulfamino) -1-naphthol,

48.1 -hydroxy ^ -stearoyloxy ^ -naphthoic acid,

49. 1-Hydroxy-4-acetoxy-N- [o- (2,4-di-tert-amy 1-phenoxy) butyl] -2-naphthamide,

50. l-Hydroxy ^ acetoxy-N-octadecyW.S'-dicarboxy-2-naphthanilide,

51.1-Hydroxy-4-thiocyano-N- [a-2,4-di-tert-amy 1-phenoxy) butyl] -2-naphthamide,

52. 1-Hydroxy-4- (pentafluorophenoxy) -N- {/?- Genealogie4-[-(2,4-di-tert.-amylphenoxy)acetamido] phenyl)-ethyl )-2-naphthamide,

53. 1-Hydroxy-4- (4-nitrophenoxy) -N- [α-2,4-di-tert-amylphenoxy) butyl] -2-naphthamide,

54.1-Hydroxy-4- (4-chlorophenoxy) -2'-tetradecyloxy-2-naphthanilide,

55.1-Hydroxy-4-phthalimido-N- [d- (2,4-di-tert-amylphenoxy) butyl] -2-naphthamide,

56.1-Hydroxy-4- (dodecenylsuccinimido) -N- [<V (2,4-di-tert-amylphenoxy) butyl] -2-naphthamide,

57. 2-a- (p-tert-amylphenoxy) -ia-butyrylamino-4-chloro-5-methylphenol,

58. 1-Hydroxy-4-phenylthio-N - [«i- (2,4-di-tert-amylphenoxybutyl] -2-naphthamide,

59. 1-Hydroxy-S '^' - dicarboxymethoxy ^ -dodecyloxy-2-naphthanilide.

The color couplers can be incorporated into the hydrophilic colloid layers by customary methods will. The color couplers are preferably used in high-boiling, so-called crystalloidal compounds dispersed by the method known from US Pat. No. 2,322,027. The couplers in advantageously using low-boiling or water-soluble auxiliary solvents according to the from US-PS 28 01 171 known methods are incorporated into the layers or using of natural solvents of the resin type, such as those known from US Pat. No. 2,284,879 are. Finally, the couplers can also be dissolved in a solution of monomers, whereupon they are polymerized in the presence of gelatin, dispersions of the color coupler in a polymer can be obtained, as is known, for example, from US Pat. No. 2,825,382. Fischer-type color couplers are advantageously incorporated into the solution of a hydrophilic colloid.

Vinyl sulfone hardeners suitable for hardening the colloids are, in particular, those with 2 viryl sulfonylalkyl radicals, interconnected by a hetero atom, for example a nitrogen or oxygen atom or another radical are connected and which, for example, aas bis (4-vmyfeulfönylbutyl) ether, Bis (2-vinylsulfonylethyl) ether, bis (vmylsulfony! Methyl) ether, N, N-bis (2-vinylsulfonylethyl) -n-propylamine, N, N-bis (2-vinylsulfonyfoethyl) -N-ethy1-N-propylammonium tetrafluoroborate or bis (1-vinylsulfonylethyl) ether exist.

Other suitable vinyl alcohol hardeners can be represented by the following general formula VIII:

(VIII)

[CH ₂ = CHSO ₂ - ^ - CH
in which m = 1, 2, 3 or 4, Z is a heteroatom.

z. B. a nitrogen or oxygen atom, and R ^{6 is} a hydrogen atom or a short-chain alkyl radical, e.g. B. a methyl, ethyl or isopropyl radical, which may optionally be substituted.
Further suitable vinylsulfone hardeners are those which have two or more vinylsulfonylalkyl radicals with preferably 1 to 4 carbon atoms, which are bonded to a plurality of tertiary or quaternary nitrogen atoms and / or to a plurality of ether oxygen atoms, in which case the hardeners consist, for example, of:

1. N, N'-bis (2-vinylsulfonylethyl) piperazine,

2. N, N '-Bis ^ -vinylsulfonyläthyljpiperazin-bis- (methoperchlorate),

3. N, N'-bis (2-vinylsulfonylethyl) -N, N'-dimethyl-2-butene-1,4-diamine-bis (metho-p-toluenesulfonate)
and the corresponding bis (methofluoborate),

4. N, N -Bis (2-vinylsulfonylethyl) -N, N-dimethylethyl-bis (metho-p-toluenesulfonate),

5. 1,2-bis (vinylsulfonylmethoxy) ethane,

6. 1,4-bis (2-vinylsulfonylethoxy) ethane,

7. bis [2- (2-vinylsulfonylethoxy) ethyl] suirone,

8. N, N -Bis [2- (2-vinylsulfonylethoxy) ethyl] urea and

9. 1,14-bis (vinylsulfonyI) -3,6,9,12-tetraoxatetradecane.

Such compounds are for example from BE-PS 6 86 440 and US-PS 29 64 404,29 50 197, 30 17 280, 33 16 095 and 33 21 313 are known.

Conventional alkaline developer solutions can be used to carry out the process of the invention which contain color developing agents consisting of primary aromatic amines

th and are also characterized in an advantageous manner by a content of benzyl alcohol. Silver halide developer compounds suitable for preparing the developer solutions are, for example Phenylenediamines, e.g. diethyl-p-phenylenedi-

amine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl - ρ - phenylenediamine hydrochloride, 2 - amino - 5 - diethylaminotoluene hydrochloride, 2 - amino - 5 - (N - ethyl - N - laurylamino) toluene, N - ethyl - N, N - (p - methanesulfonamidoethyl) - 3 - me-

ethyl 4-aminoaniline sulfate, ethyl N-ethyl-N - (/ i-methylsulfonamidoethyl) -4 - aminoaniline and 4 - [N-ethyl-N- (i- hydroxyethyl) amino] aniline. Suitable developer compounds are also those derived from p-aminophenols and their substitution products

exist, the amino group being unsubstituted. The developer solutions can be advantageous Way conventional and known additives contain, for example alkali metal sulfites, carbonates, bisulfites. Bromides and iodides.

Ss For the preparation of the process of the invention applied bleach-fix baths, common known silver halide solvents can be used, for example ThiosuHate, potassium thiosulfate. Sodium thiosulfate and AnnnnonhnnthiosnOät as well as waste soluble thiocyanates, e.g. B. sodium thiocyanate, Ka lium thiocyanate and ammonium thiocya bat, as well as what water-soluble fixatives consisting of organic diols with sulfur aad / or sarstomes (cf. the US-PS 2748000), through which the carbon

6s chains of diols are interrupted, e.g. B. 3-Thia 1,5-pentanediol, 3,6-dithia-1,8-octanediol, 3,6,9-tri thin-1.11 -undecandioL 3A9,12-Tetrathia-1, 14-tetra decandiol.

837

candiol and 3,6,9,12 ^ U0,33,36,39-Nonaoxa-15,18, 24,27-tetrathia-1,41-hentetracontanediol, also water-soluble sulfur-containing organic dibasic acids, e.g. ethylene-bis-thiogiycolic acid, 3,6,9-trithiahenedecanedioic acid, 3,6,9,12-tetrathiatetradecandioesäare and their water-soluble salts, for example Sodium salt or potassium salt; also imidazolidinthione, z. B. Methylimidazolidinthione and Äthylünidazolidinthion.

For making the bleach-fix solutions used in practicing the method of the invention suitable silver halide oxidizing agents are those which, as silver halide, oxidize compounds are known. Thus, for example,

IC

wise water-soluble ferricyanides, e.g. sodium Potassium and ammonium ferricyanide, water-soluble quinones, e.g. B. quinone, sulfophenylquinone, chlorine quinone, methoxyquinone, 2,5-dimethoxyquinone um Methylquinone, simple water-soluble ferric salts, e.g. Ferric chloride, ferric nitrate, ferric sulfate, ferritiocyana and Ferrioxalai, as well as simple water-soluble ' Cupris salts, e.g. B. cuprichloride, cuprinitrate and Capri sulfate and simple water-soluble cobalti salts, ζ. Ε Cobalt dichloride and cobalt ammonium nitrate. There are also oxidizing compounds as silver halide genes, for example, complex salts of an alkali metal: and a polyvalent cation with an organic « Acid of one of the following structural formulas is suitable

O

W. W.

HOCR "- X - R ⁸ - C - OH OO

Il Il

HO - C - R "- NR ¹ " - C - OH

O R "

Il i Il

HO - CR * - N - R ¹⁰ - C - OH

wherein X denotes a hydrocarbon radical, an oxygen or sulfur atom or a radical of the formula = NR ¹² , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R "each an optionally substituted hydrocarbon radical and R ¹² a hydrogen atom or an optionally substituted hydrocarbon radical, wherein the polyvalent cation consists of a ferric, cobaltic or cupric ion.

Such connections are known from DT-PS 8 66 605, for example.

The organic acids can be converted into, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, Malonic acid, ethylmalonic acid, tartaric acid, maleic acid, fumaric acid, diglycolic acid, ethyliminodipropionic acid, Ethylenedithioglycolic acid or dithioglycolic acid exist.

Conventional additives can advantageously be incorporated into the bleach-fixing solutions, for example wise alkali metal bromides, e.g. B. ammonium bromide. Alkali metal iodides, e.g. B. ammonium iodide, hydrazine, so Hydroxylamine salts, amines and mercapto derivatives of 5-membered heterocyclic ring compounds, z. B. mercaptotriazole and formamidine cuffinic acid.

Conventional aqueous, acidic stabilizer solutions can be used to stabilize the recording materials developed normally used in color photographic development processes be used. A suitable stabilizer solution can, for example, be citric acid as the acid contain.

The following examples are intended to illustrate the invention in more detail.

example 1

(Comparative example)

Fs were 2 recording materials 1 and 2, each consisting of a paper support and gelatin-silver chlorobromide emulsion layers applied thereon manufactured.

The silver halide emulsion layer of the material 1 contained a dispersion of the yellow dye-forming 4-equivalent coupler α-pivalyl-2-chloro - 5 - [} - (2,4 - di - tert - amylphenoxy) buty ramido] acetanilide the formula

C - C - CH ₂ - C - NH

NHCO (CH ₂ h-O

in dibutyl phthalate in a ratio of coupler to coupler solvent of 1: 1.

The material 2 contained in the silver halide emulsion layer a dispersion of the one according to the invention useful yellow dye-providing 2-equivalent coupler <i-Pivaiyl-u-f_4- (4-benzyloxyphenylsulfonvl) -

phenoxyJ ^^ MorcHS-rjK ^^ Kii-tert-amylphenoxyJbutyramidolacetanaid of the formula

(CH ₃ Jr C-C-CH-C-NH

NHCO (CH ₃ ) TO

Ο —CH, -

in dibutyl phthalate as the coupler solvent, the ratio of coupler to coupler solvent Was 10: 1.

Samples of the two recording materials were then exposed sensitometrically in a step wedge and then in a customary color developer solution containing benzyl alcohol, sodium sulfite, N-ethyl-iimethanesulfonamidoethyl-3-methyl -4-aminoaniline sulfate as color developer compound and alkali to achieve a pH Value of about 10, contained, developed. The recording material was then ^{fixed for 2 minutes at 30 °} C. in a fixing bath of the following composition:

Sodium thiosulfate 240 g

Sodium sulfite 15g

Acetic acid, 28% 48 ml

Boric acid 7.5 g

Potassium aluminum sulfate 15g

Filled up with water to 11 * °

It was then rinsed and dried.

The developed recording material 1 had only a small amount of developed yellow dye whereas the recording material 2 showed a vigorously developed yellow dye image. the The cause for the lack of a strong, visible yellow dye image in material 1 is evident on the formation of a colorless form of the yellow dye during color development the color coupler that is not one of the color couplers suitable for carrying out the method of the invention heard. In contrast, it is the one used to produce the recording material 2 Color coupler to one which is suitable for carrying out the method of the invention.

Additional samples of the two recording materials produced were exposed sensitometrically and color developed in the manner described, whereupon it for 2 minutes at 30 ⁰ C in a solution of the following composition:

Sodium bromide 21.5 g

Potassium ferricyanide 100 g

Sodium phosphate 7g

Filled up with water to Il

bleached and in that already for 2 minutes at 30 "C Fixing bath described were fixed.

The two recording materials 1 and 2, after color development in the manner described bleached and fixed showed excellent developed yellow dye images.

The experiments described show that the colorless leuco form of the yellow dye obtained from the im Color coupler containing recording material 1 was developed during color development, the treatment of the recording material made necessary with a strong oxidizing agent (bleach bath), so that the leuco form of the dye is converted into the visible, colored form.

The recording material 2, however, has a yellow dye image of maximum density already after Color development on, and the treatment of this recording material in the bleaching solution is used only for the purpose of oxidizing the image silver.

Example 2

(Comparative example)

I. Recording material for its production

gelatin hardened with formaldehyde

was used

A multilayer color photographic recording material was produced by clicking on a usual, a polyethylene layer having paper backing in the following order Layers were applied:

a blue sensitive gelatin-silver chlorobromide emulsion layer, as a yellow dye-forming coupler "-pivalyl-" - [4- (4-benzyloxyphenylsulfony!) phenoxy] -2-chloro-5 - [;-( 2,4-di - tert. - amylphenoxy) butyramido] acetanilide, d. H. one that can be used according to the invention 2 equivalent coupler in dibutyl phthalate as a coupler solvent at a ratio of Contained coupler to a coupler solution ratio of 10: 1,

an intermediate gelatin layer,
a green-sensitized gelatin-silver chlorobromide emulsion layer which, as a purple dye-providing color coupler l- (2,4-dimethyl 1-6 - chlorophenyl) - 3 - [3 - («- (m - pentadecylphenoxy) butyramido) benzamido] - 5 - pyrazolone, ie a coupling that can be used according to the invention

contained in tricresyl phosphate as a coupler solution of 1: 1,
a gelatin interlayer, a red sensitized gelatin-silver chlorobromide emulsion layer containing, as a blue-green dye-providing color coupler, 2- [a- (2 ^ di-tert-amylphenoxy) butyramido] - 4,6-dichloro-5-methylphenol in dibutyl phthalate as a coupler solvent at a ratio of coupler to coupler solvent of 2: 1 and a gelatin coating layer

Two samples of the recording material obtained were then sensitometric in the usual way exposed and then developed according to processes A and B, which are described in more detail below.

Procedure A

Procedure using 5 baths **

(Bleach and fix bath), temperature: 30 C

Color development (developers like

described in example 1) 6 minutes

Interrupt fixer bath 2 minutes

Soak for 2 minutes

Bleach bath (as in example 1

described) 2 minutes

Soak for 2 minutes

Fixing bath (as in example 1

described) 2 minutes

Soak for 4 minutes

Stabilizer bath 2 minutes

Procedure B

3 bath process (bleach-fix bath), temperature: 30 ^° C

Color development (developers like

described in example 1) 6 minutes

Bleach-fix bath 2 minutes

Soak for 4 minutes

Stabilizer bath 2 minutes

45

The bleach-fix bath of method B had the following composition:

Sodium ferriethylenediamine tetraacetic acid 45 g

Ammonium thiocyanate 10 g

Sodium sulfite 10 g

Ammonium thiosulfate
(60% aqueous solution) 100 ml

Ethylenediaminetetraacetic acid,

Tetrasodium salt 5 g

Topped up with water to 11

pH adjusted to 6.7 to 7

The stabilizer baths used in processes A and B were conventional A stabilizer bath consisting of an aqueous citric acid solution with a pH of 3.5.

Of the recording materials obtained, the densities of the produced became yellow, magenta and cyan dye images were determined. Sensitometer curves were recorded in the usual way, in which the determined densities were plotted as a function of the logarithm of the exposure.

Results

1. The density of the yellow image dye of the recording material, developed according to method B was as high as the density of the yellow image dye of the recording material produced according to Method A was developed. This result confirms that in the blue-sensitive layer had not formed a colorless form of the yellow dye when this layer was one of those according to the invention useful color coupler providing a yellow dye.

2. The density of the magenta dye image in the record material developed according to Method B was found to be about 20% lower in the shoulder portion of the curve than the density of the magenta image dye in the record material developed according to Method A. This shows that the colorless form of the magenta dye developed in the size-sensitive layer could not be converted into the colored form of the magenta dye due to the relatively low oxidation potential of the bleach-fix solution.

3. The cyan dye image was not affected by either A or B process.

II. Recording material, for the production of which gelatin hardened with a divinyl sulfone, however no yellow dye forming coupler useful in the present invention was used

Another multilayer color photographic recording material was produced which differs from that described under 1. in that a) used gelatin for its production which has been hardened with a divinyl sulfone, and that b) a blue-sensitive gelatin-silver chlorobromide emulsion layer the yellow dye forming coupler α-pivalyl-2 - chloro - 5 - [j - (2,4 - di - tert - amylphenoxy) - butyramidojacetanilide, d. H. no coupler to be used according to the invention, in dibutyl phthalate as a coupler solvent at a coupler to coupler solvent ratio of 2: 1.

Two samples of the recording material were exposed sensitometrically, whereupon one of the exposed Samples according to method Λ and a sample according to method B has been developed.

Of the recording materials developed, the densities of yellow, magenta and cyan dye images are determined, whereupon the determined densities as a function of the logarithm the exposure were plotted in a diagram.

Results

1. In the sample developed by method A. a strong yellow dye image was produced. In contrast, the density of the yellow was There is very little dye in the sample developed using method B. This results in that with the bleach-fix bath, which has a lower oxidation potential than the bleach bath, the non-colored form of the yellow dye from the color coupler, which does not belong to the invention used color couplers belongs, can not be converted into the colored form of the dye.

2. The density of the magenta dye image of the sample developed by Method B,

corresponds to the density of the purple dye image, which was developed according to method A. As a result, the divinyl sulfo curing agent not with the 5-pyrazonone color coupler to form a non-colored form of the magenta The dye reacts during color development.

3. There were no differences in the blue-green dye image.

III. Recording material, for the production thereof

a gelatin hardened with a divinyl sulfone and

a yellow one which can be used according to the invention

Dye donating coupler was used

Another recording material was produced which differs from that described under I. only differed in that gelatin was used for its production which was hardened with a divinyl sulfone was used.

Two samples of the recording material were taken exposed sensitometrically and then developed according to methods A and B, but this time the Stabilization was omitted.

In turn, curves were recorded by dividing the density values as a function of the logarithm applied after exposure.

Results

Both curves recorded for the yellow and magenta dye images corresponded to each other. The maximum density values were the same in some cases.

It follows that when used at the same time certain color couplers which provide a yellow dye and hardeners which do not Aldehydes are that prevent the formation of non-colored yellow dyes in the blue-sensitive layer and that further in the green-sensitive layer of the recording material a formation of a non-colored purple dye is avoided.

Due to the absence of non-colored dyes after color development, it is not necessary to the color-developed recording materials either in separate bleaching and fixing baths or to treat in an additional bleach bath following the bleach-fix bath. According to the invention it is thus possible to achieve the desired magenta dye and yellow dye densities simply by / u achieve that the recording materials are developed in a 2-step process, d. H. one Process in which the color development is followed by the treatment of the recording material with a Bleach-fix bath follows. In contrast, it is when using recording materials. which do not meet the requirements of the invention are required to develop a 4-step process apply, in which the recording material is fixed, bleached and after color development is fixed again, in order to achieve the desired yellow and magenta dye densities two additional rinsing stages are required.

A stabilization of the recording material developed according to the method of the invention hct proved to be advantageous because this overcomes the stability of the developed dye images is maintained for a relatively long period of time. $ 6

Correspondingly favorable results have been obtained when one meets the requirements of the invention Sufficient recording material is developed by a process that differs from process B differs only in that the recording material is between color development and treatment rinsed with water in the bleach-fix bath.

Example 3

Another multilayer color photographic recording material was used as in Example 2 described under I., but this time gelatin was used, which does not contain formaldehyde contained, but much more bis (2-vinyisulfonylethyl) ether.

A sensitometrically exposed sample of this recording material was then developed according to Procedure A described in Example 2

A second sensitometrically exposed sample of the same recording material was used in the same However, with the exception that after the bleach-fix bath, the material is developed in one special ferricyanide bleach bath of the composition described in Example I was treated.

The densities of the magenta dye images were determined from the two treated film samples. whereupon the obtained densities in a diagram as a function of the logarithm of the exposure were applied.

The curves obtained were practically the same, from which it follows that a green-sensitive layer produced according to the invention does not form a non-colored purple dye leads.

Example 4
(Comparative example)

Line sensitometrically exposed sample of a multilayer photographic recording material of the structure described in Example 2 under I., ie a recording material with formaldehyde as hardening agent, was developed according to method B described in Example 2.

line second sensitometrically exposed sample of the same recording material became the same W; ise developed, with the exception, however, that after the treatment with the bleach-fix bath, a treatment took place in a special bleaching bath of the composition given in Example 1.

Is the magenta dye densities of the developed Images determined and the dependence on the logarithm of the exposure in a diagram wear out.

I in comparison of the curves obtained showed that the pyrazolone color coupler in the presence of formaldehyde provided a dye image with a dye density that was approximately 27% at a density of 0.48 and was about 24% lower at a density of 1.7 and that the use of a special bleach bath with an oxidation potential higher than the oxidation potential of the bleach-fix bath, around the non-colored form of the purple dye in the visible colored form of the to transfer purple dye.

Example 5

In example 2 under III. The procedure described was repeated, but this time for production of the recording material gelatin was used, which is mixed with other vinyl sulfone hardening

medium hardened. The hardening agents used were:

Bis (4-vinylsulfonylbutyl) ether, bis (2-vinylsulfonylmethyl) ether, N, N-bis (2-vinylsulfonylethyl) -n-propylamine, N, N-bis (2-vinylsulfonylethyl) -N-ethyl-N-propyl-

ammonium tetrafluoroborate and Bis (1-vinylsulfonylethyl) ether.

In all cases results were obtained which correspond to those in Example 2 under III. described results if the recording materials were color-developed in a bleach-fix solution, if appropriate after an intermediate wash with water.

Example 6

That in example 2 under IH. described procedure was repeated, but this time using recording materials, their gelatin has been hardened with the following hardening agents:

N, N-bis (2-vinylsulfonethyl) piperazine, N, N'-bis (2-vinylsulfonylethyl) piperazine-

bis (methoperchlorate),
N, N'-bis (2-vinylsulfonylethyl) -N, N'-dimethyl-2-butene-1,4-diamine-bis (metho-p-toluenesulfonate) or the corresponding

Bis (methofluoborate),
N, N'-bis (2-vinylsulfonylethyl) -N, N'-dimethyl-

ethylene bis (metho-p-toluenesulfonate), 1,2-bis (vinylsulfonylmethoxy) ethane, 1,4-bis (2-vinylsulfonylethoxy) ethane, Bis [2- (2-vinylsulfonylethoxy) ethyl] sulfone, N, N'-bis [2- (2-vinylsulfonylethoxy) ethyl] -

urea or
U4-Bis (vinylsulfonyl) -3,6,9,12-tetraoxatetradecane.

In all cases, the same favorable results as in Example 2 under HI. received described, if the recording materials after color development, optionally after an intermediate one Water wash with the bleach-fix solution described above.

Example 7

In example 2 under III. described procedure was repeated except that recording materials were used this time which respectively contained one of the following color couplers:

Color couplers producing yellow dyes

1. «-Fhioro -« - fMva! YI-5- [3 '- (2,4-di-tert-ainylpfaeaoxyJb «tyraHHdo] -2-chkmjacetaBiItd,

2. "-Prvatyl -" - stearoyloxy-4-sulfamylacetanilide.

3.> i-Prvalyi-n- [4- (4-benzyloxyphenylsiifonyl) -

2. 1- (2,4-Dimethyl-6-chlorophenyl) -3- [3- {a- (m-pentadecylphenoxy) butyramido} -benzamido] -5-pyrazolone,

3. 1 - (2,4,6-TrichIorophenyl) -3- (4-nitroanilino) -4-stearoyloxy-5-pyrazolone,

4.1 - (2 ₎ 4,6-Trichlorophenyl) -3- {3 - [«- (2,4-di-tertamylphenoxyjacetamidojbenzamidöj ^ -acetoxy-5-pyrazolone,

5.

amylphenoxyacetamido) benzamido] -4-thiocyano-5-pyrazolone.

Color couplers providing cyan dyes

1. 2- [u- (4'-tert-Butylphenoxy) propionylamino] phenol,

2. 2- (4 "-tert-amyl-3'-phenoxybenzoylamino) -3,6-dimethylphenol,

3. 2- [fi- (2,5-Di-tert-amylphenoxy) butyramido] -4,6-dichloro-5-methylphenol,

4. 1-Hydroxy-4- {4-chlorophenoxy) -2'-tetradecyloxy-2-naphthanilide.

In all cases the results obtained were those of Example 2 under III. described result When the recording materials have been color-developed as described in Example 2 were then treated in a bleach-fix bath of the specified composition.

Example 8

In example 2 under III. described processors was repeated, this time using a bleach-fix bath containing 45 g of sodium cobalt diethylenediamine tetraacetic acid contained in place of sodium ferriethylenediamine tetraacetic acid. The results obtained corresponded to those in Example 2 below III. described results.

Example 9

In example 2 under III. The procedure described was repeated, but this time a bleach-fix bath was used in which instead of sodium ferricethylene diamine tetraacetic acid an equivalent Amount of sodium cupric ethylenediaminetetraacetic acid was used. There were corresponding Results as in example 2 under III. described received.

Example 10

y] [H
phenoxy) bntyramido] acetaniitd, 4. "-Rvalyl-2>dH" oro-4-fN '- <B-octadecyl) -N' - <methyI) saifernvl3acetanHTd

Color couplers providing purple dyes

• M2 ', 4'-KcW «-opheiiyl} -H3" - (2' ", 4" '- di-tert-amylpheooxyacelaraidoft) enzamido] -5-pyrazokm.

In example 2 under III. The procedure described above was repeated except that a bleach-fix bath was used in which sodium ferriethylenediamine tetraacetic acid was replaced by an equivalent amount of sodium cuprinitriolotriacetic acid and in which further the tetrasodium salt of the ethylenediamine tetraacetic acid was replaced by an equivalent sodium ferric methylene acetate of the triacetic acid. In all cases, results were obtained, ate the results of Example 2 corresponded.

6s example H

In example 2 under IiI. described procedure was repeated, but this time erae Bkich-

509518/157

r ~

837

Fixing solution used, which had the following composition:

Sulfuric acid, concentrated 7.5 g

Ferric chloride (6H ₂ O) 12g

Ethylenediaminetetraacetic acid,

Trisodium salt 55 g

Sodium sulfite (dehydrated) 50 g

Ammonium thiocyanate 10 g

S.o-Dithia-l.S-octanediol 10g

Topped up with water on 11

pH adjusted to 5.5

The results obtained corresponded to the results described in Example 6.

Example 12

In example 2 under III. described procedure was repeated, but this time instead of the bleach-fix solution used, such a folto gender composition was used:

Potassium ferricyanide 35 g

3,6-dithia-1,8-octanediol 25 g

Ammonium thiocyanate 25 g

Filled up with water to II

Between color development and exposure to the bleach-fix solution, the recording material became rinsed briefly with water. The results obtained were the same as those obtained in Example 2 Results.

Example 13

In example 2 under III. The procedure described was repeated, but this time using a bleach-fix solution was used, which was manufactured shortly before its use and the following composition owned:

Potassium ferricyanide 50 g

Sodium thiosulphate 200 g *

Topped up with water to 11

pH adjusted to 8

The results obtained corresponded to the results described in Example 2.

OO ^C1

Il Il

R — C - CH-C -

Example 14

In example 2 under III. The procedure described was repeated, but this time a bleach-fix solution of the following composition was used:

Sodium thiosulfate 150 g

Cobalt ammonium carbonate nitrate ... 30 g

Topped up with water to 11

pH adjusted to 7

The results obtained corresponded to the results obtained for Example 2.

Example 15

The procedure described in Example 12 was repeated, but this time using a bleach-fix solution was used, which consisted of:

3,6-dithia-1,8-octanediol 50 g

Quinone 4 g

Topped up with water to 11

pH adjusted to 1.5

The results obtained corresponded to the results described in Example 2.

The method of the invention can also be successfully developed for the development of others use multilayer color photographic recording materials. Furthermore, others can Color developer solutions and bleach-fix baths with compositions other than those in given in the examples.

Example 16
(Comparative example)

Two different color photographic recording materials were produced. This was done first of all the color couplers Λ and B given below, each dissolved in di-n-butyl phthalate, obtained These solutions are dispersed in two portions of a gelatin silver halide emulsion, the disperser applied in the usual way to the substrate unc dried

The color couplers had the following structure:

NH

NHCO (CH

C ₅ H _n (I)

C ₅ H ₁₁ (I)

OCH-

Coupler A (according to the prior art): R =

R = -QCH ₃ ),

27 28

Sections of the recording material obtained - the specimens were exposed for 21 days in an exposure

Lien were in the usual way a test object with processing device with a xenon arc lamp, the

graduated density levels and thereafter like radiation of the composition of northern

follows developed: corresponded to daylight, with an illuminance

ic-utn "mon", n .. · "" 5 of 5380 Ix exposed. The acceptance was determined

2. F?; Sen- 5 ^ng ^. ^. [ !! ['. \ \ '? ES ^ ^{color density} * ^h " ^{the fade out iö density} "

SerbPeichbad ***) ' \ \ \'. [[\ \] \] \ 5 ES _ "« » ^received * f * ™" ^{are in the following} 8 ^ends

S. Watering 5 minutes, _n ^ belle compiled:

6. Fixation **) 5 minutes ^I0 _{color clearer color} . _acceptance

7. Soak 10 minutes of developer- the color-

8. Drying solution density

in density

*) There were two different color developer I units

and II used. The color developer solution used I 15

had the following composition:

Water 800 ml A (prior art) I 0.72

Polymetaphosphate 0.5 g Π 0 72

Na ₂ SO ₃ 2 g

^ Amino-S-melhyl-N.N-diethylaniline-β (according to the invention) I 0.26

hydrochloride 2 g 20 ^e '

Na ₂ CO ₃ · H ₂ O 20 g ^ll ", LL

50% NaBr solution 3.46 ml

Filled up with water to 11 _. ,,,. . . . ..

pH value = 10 86 The experiments were carried out with two recording

The color developer solution used π differed materials repeatedly, in a corresponding manner

of the color developer solution I only in that they ^{were prepared on 2} 5, but the color couplers

Place of ^ amino-S-methyl-N.N-diethylaniline hydrochlo- not using the high-boiling solution

rid 4-amino-3-methyl-N-ethyl-N- / 9- (methanesulfonamido) - by means of di-n-butyl phthalate, but using

Ethylaniline sulfate hydrate contains. _{dung y (? n Athy} , _{acetate m the} silver halide

* ·) The fixer used had the following combinations.

setting: 30 This time the following results were obtained:

Water, about 60 C 600 ml Sodium thiosulfate 240.0 g color coupler color decrease Sodium sulfite dehydrates 15.0 g of developing color Acetic acid, 28%, 48.0 ml _{lo dense} Boric acid crystalline 7.5 g _{in density} . Potassium aluminum sulfate 15.0 g · »units Topped up with cold water to 11

***) The silver bleaching bath consisted of a usual long-distance, _,.,, _ _ ,,

cyanide bleach. A (prior art) B 0.61

B (according to the invention) B 0.21

The test specimens were then determined sensitometrically
tests. Here, the density values of a level

of the H and D curves having a density of about 1.2. From the results obtained, for the

recorded. The test specimens then became almost the color coupler used according to the invention

Subjected to the light fading test: three times greater light resistance.

Γ.

Claims (1)

Patent claims: 1. Color developing method for manufacture color photographic images in which an imagewise exposed color photographic recording material is used, consisting of a support and hardened silver halide emulsion layers, who are sensitized to different regions of the visible spectrum, from one of which uses a non-diffusing 2-equivalent color coupler for the production of a yellow Image dye, another a non-diffusing color coupler for the production of a purple image dye is one of the following formulas