US3723117A

US3723117A - Method for developing silver halide emulsions

Info

Publication number: US3723117A
Application number: US00078914A
Authority: US
Inventors: J Willems
Original assignee: Agfa Gevaert AG
Current assignee: Agfa Gevaert NV; Agfa Gevaert AG
Priority date: 1969-10-27
Filing date: 1970-10-07
Publication date: 1973-03-27
Anticipated expiration: 1990-03-27
Also published as: NL7015733A; GB1327033A; CA987942A; FR2065921A5; DE2052693A1; BE757902A; JPS513219B1

Abstract

A photographic developing method is described which comprises developing an exposed silver halide emulsion layer of a photographic material with an aqueous alkaline composition in the presence of a hydroxylamine developing agent and a p-phenylene diamine or p-aminophenol derivative corresponding to one of the formulas

WHEREIN:

WHEREIN: R1 stands for an alkyl group, R2 stands for alkyl or for ethylene, substituted ethylene, propylene or substituted propylene attached to the adjacent ortho-carbon atom of the benzene ring, R3 stands for alkyl, and R4 stands for an alkyl group, AT MOST ONE OF R1 and R4 being substituted alkyl;

WHEREIN:

WHEREIN: EACH OF R5 and R6 stands for an alkyl group, and X1 stands for an electron-donating group; and

WHEREIN: EACH OF X2 and X3 stands for hydrogen, halogen or an electrondonating group, Y stands for OH or NH2, and R7 stands for ethylene, substituted ethylene, propylene or substituted propylene attached to the adjacent ortho-carbon atom of the benzene ring, and R8 stands for hydrogen, an alkyl group or has the same significance as R7, or R7 together with R8 and the N-atom to which they are attached from a pyrrolidine ring. The p-phenylene diamine or p-aminophenol derivative has a superadditive developing affect with the hydroxyl amine developing agent.

Description

United States Patent 1 1 Willems 1 51 Mar. 27, 1973 [54] METHOD FOR DEVELOPING SILVER HALIDE EMULSIONS [75] Inventor: Jozef Frans Willems,

' Belgium [30] Foreign Application Priority Data Oct. 27, 1969 Great Britain ..52,565/69 52 Us. 01. ..96/29, 96/66, 96/66.3 51 Int. Cl. ...G03c 5/54, G036 5/30 [58] Field 61 Search ..96/66, 66 T, 55, 29

[56] 7 References Cited UNITED STATES PATENTS 3,489,566 1/1970 Anselm ..96/22 2,857,274 10/1958 Land ..96/29 2,857,275 10/1958 Land ..96/29 3,113,866 12/1963 Land ..96/29 3,406,064 10/1968 Land ..96/29 3,576,631 4/1971 Archambault.... ..96/66 3,265,499 8/1966 Willems 96/66 3,265,502 8/1966 Willems ..96/66 3,549,364 12/1970 MOlSB ..96/66 Primary Examiner--J. Travis Brown Assistant Examiner-M. F. Kelley AttorneyBrufsky, Staas, Breiner and Halsey [57] ABSTRACT A photographic developing method is described which comprises developing an exposed silver halide emul sion layer of a photographic material with an aqueous alkaline composition in the presence of a hydroxylamine developing agent and a p-phenylene diamine or p-aminophenol derivative corresponding to one of the formulas I211 R1 N wherein:

R stands for an alkyl group,

R stands for alkyl or for ethylene, substituted ethylene, propylene or substituted propylene attached to the adjacent ortho-carbon atom of the benzene ring,

R; stands for alkyl, and

R stands for an alkyl group,

at most one of R and R being substituted alkyl;

wherein:

each of R and R stands for an alkyl group, and X stands for an electron-donating group; and

wherein:

each of X and X stands for hydrogen, halogen or an electron-donating group, Y stands for OH or NH,, and R, stands for ethylene, substituted ethylene, propylene or substituted propylene attached to the adjacent ortho-carbon atom of the benzene ring, and R stands for hydrogen, an alkyl group or has the same significance as R or R together with R and the N-atom to which they are attached from a pyrrolidine ring. The p-phenylene diamine or p-aminophenol derivative has a super-additive developing affect with the hydroxyl amine developing agent.

10 Claims, No Drawings METHOD FOR DEVELOPING SILVER HALIDE EMULSIONS This invention relates to the development of photographic materials containing exposed silver halide, to new developing combinations and to photographic materials and solutions containing such combinations.

It is known that certain chemical compounds, which used alone are poor developers for photographic silver halide emulsions, become much more effective when used in conjunction with other developers, the effect being known as superadditivity. Thus, for example it is known that p-phenylene diamine derivatives and paminophenol derivatives show the phenomenon of superadditivity when used in conjunction with developing agents the ionized forms of which in alkaline medium carry two or more negative charges such as hydroquinone, hydroquinone sulphonate, ascorbic acid, etc.

It has now been found that these p-phenylene diamine and p-aminophenol derivatives also exhibit a superadditive character when used in conjunction with the at most singly ionized developer anions of hydroxylamine and derivatives thereof.

The use of hydroxylamine and derivatives thereof, of which the oxidation products have the favorable property of leaving no residual stain in the silver image obtained has been disclosed amongst others in U.S. Pat. No. 2,857,276 of Edwin H. Land and Helen J. Tracy issued Oct. 21, 1958. Hydroxylamine itself and the mono-alkyl derivatives are less suitable because they can give rise to fog but the N,N-dialkylhydroxylamines such as N,N-diethylhydroxylamine and the heterocyclic N-hydroxylamines such as N-hydroxymorpholine, N-hydroxypiperidine'and N-hydroxypyrrolidine disclosed in the above United States Patent Specification are particularly suitable. Other hydroxylamine derivatives that have been proposed for use as silver halide developing agents and of which the development activity is higher than that of the N,N-dialkyl hydroxylamines include for example aminoalkyl hydroxylamines, more especially N,N-dialkylhydroxylamines having in at least one of the N-alkyl groups an intralinear amino nitrogen atom, either cyclic or acyclic, examples of which can be found in U.S. Pat. No. 3,287,125 of Milton Green, Adnan A.Sayigh and Henri Ulrich issued Nov. 22, 1966, alkoxyhydroxylamines, more especially N,N-dialkylhydroxylamines of which at least one of the n-alkyl groups is substituted by alkoxy or alkoxyalkoxy, examples of which can be found in U.S. Pat. No. 3,293,034 of Milton Green, Adnan A.Sayigh and Henri Ulrich issued Dec. 20, 1966 and sulphone hydroxylamines, more especially N,N-dialkylhydroxylamines having in at least one of the N- alkyl groups an intralinear sulphonyl (SO,--) group, examples of which can be found in U.S. Pat. No. 3,287,124 of Milton Green, Adnan A.Sayigh and Henri Ulrich issued Nov. 22, 1966. Further N,N-dialkylhydroxylamines having in at least one of the N-alkyl groups a quaternary ammonium group either cyclic or acyclic which excel by their high development activity have been proposed for use as silver halide developing agents in the copending application filed for Novel Photographic Developers" (=U.K. Pat. Application No. 52,564/69 filed Oct. 27, 1969 by Gevaert-Agfa N.V.).

The p-phenylene diamine and p-aminophenol derivatives having a superadditive development effect with hydroxylamine developing agents can be represented by the following general formulae:

wherein:

each of R and R stands for alkyl including substituted alkyl e.g., alkyl substituted as above, and

X, stands for an electron-donating group such as alkyl, alkoxy, amino, monoalkylamino, kylamino, acylamino and sulphonamido,

dial- III.

wherein:

each of X, and X stands for hydrogen, halogen such as chlorine or an electron donating group, e.g., as exemplified for X,,

Y stands for OH or NH,, and

R stands for ethylene, substituted ethylene, propylene or substituted propylene attached to the adjacent ortho-carbon atom of the benzene ring, and

R stands for hydrogen, alkyl including substituted alkyl for instance substituted as exemplified above for R or has the same significance as R, above, or

R together with R and the N-atom to which they are attached form a pyrrolidine ring.

The following are representative examples of pphenylene diamine and p-aminophenol derivatives suitable for use as superadditive developing agents in conjunction with hydroxylamine a. compounds corresponding to general formula 1 l. 6-diethylamino-l ,2,3,4-tetrahydroquinoline dichlorohydrate 2. l-ethyl-6diethylamino-l,2,3,4-tetrahdroquinoline dichlorohydrate 3. l-(4-sulphobutyl)-6-diethylamino-l ,2,3 ,4- tetrahydroquinoline 4. l-( 2-hydroxyethyl)-6-dimethylamino-l ,2,3 ,4- tetrahydroquinoline dichlorohydrate 5. 1-ethyl-6-( N-ethyl-N-3-sulphopropylamino 1,2,3 ,4-tetrahydroquinoline dichlorohydrate 6. ll(3-sulphopropyl)-6-(N-ethyl-N-methylamino)- 1,2,3 ,4-tetrahydroquinoline dichlorohydrate 7. l-(2methylsulphonylaminoethyl)-6-diethylamino- 1,2,3 ,4-tetrahydroquinoline dichlorohydrate 8. l-( 3-carboxypropyl )-6-dimethylamino-l ,2,3 ,4- tetrahydroquinoline dichlorohydrate 9. N,N-diethyl-N',N-dimethyl-p-phenylene diamine dihydrochloride l0. N,N,N', N'-tetramethyl-p-phenylene diamine dihydrochloride l1. N,N,N', dihydrochloride l2. N,N-diethyl-N'-2-hydroxyethyl-N'-ethyl-p-phenylenediamine disulphate 13. N,N-diethyl-N'-4-sulphobutyl-N'-ethyl-p-phenylene diamine b. compounds corresponding to general formula ll 14. 2-amino-4-diethylamino-aniline sulphate l5. 2-methylamino-4-diethylamino-aniline sulphate 16. 2-methylsulphonamido-4-diethylamino-aniline sulphate l7. 2-ethoxy-4-diethylamino-aniline hemisulphate compounds corresponding to general formula Ill 18. l-(4-hydroxyphenyl)-pyrrolidine l9. l-(3-chloro-4-hydroxyphenyl)-pyrrolidine 20. 1-(3-methyl-4-hydroxyphenyl)-pyrrolidine 21. l-(3,5-dimethyl-4-hydroxyphenyl)-pyrrolidine 22. l-(3-amino-4-hydroxyphenyl)-pyrrolidine 23. l-(3-methoxy-4-hydroxyphenyl)-pyrrolidine 24. l-( 3-methylsulphonamido-4-hydroxyphenyl)- pyrrolidine 25. l-(3-acetylamino-4-hydroxyphenyl)-pyrrolidine 26. 6-amino-l ,2,3,4-tetrahydroquinoline 27. 6-hydroxy-1,2,3,4-tetrahydroquinoline 28. l-ethyl-6-hydroxy-1,2,3,4-tetrahydroquinoline chlorohydrate 29. 1-(4-sulphobutyl)-6-hydroxy-l ,2,3 ,4- tetrahydroquinoline 30. 9-amino-julolidine sulphate N'-tetraethyl-phenylene diamine 31. l-methyl-6-amino-l ,2,3,4-tetrahydroquinoline oxalate 32. l-(2-methylsulphonylamino-ethyl)-6-hydroxy- 1,2,3 ,4-tetrahydroquinoline 33. 1-(2-hydroxyethyl)-6-hydroxy-1,2,3 ,4- tetrahydroquinoline 34. 1-(4-sulphobutyl)-6-amino-l ,2,3 ,4-

tetrahydroquinoline 35. 9-hydroxy-julolidine.

The p-phenylene diamine and p-aminophenol compounds of use according to the present invention can be prepared as known in the art, e.g. as described in U.S. Pat. No. 3,265,499 of Jozef Frans Willems,

George Frans Van Veelen and Louis Maria De Haes issued Aug. 9, 1966 and U.S. Pat. No. 3,265,502 of Jozef Frans Willems and George Frans Van Veelen issued July 8, 1966, in United Kingdom Pat. specifications, No. 928,671 filed Feb. l9, 1960 by llford Ltd. and No. 858,432 filed Mar. 5, 1958 by Imperial Chemical lndustry and in Belgian Pat. specification No. 715,500 filed May 22, 1968 by Gevaert-Agfa N.V.

In accordance with the present invention there is provided a process of making photographic records which comprises treating a photographic material having layers containing developable silver salts with an aqueous alkaline solution in the presence of a hydroxylamine developing agent and a p-phenylene diamine or p-aminophenol compound as described above. The invention also includes developer compositions comprising in addition to a hydroxylamine developing agent, a p-phenylene diamine or p-aminophenol compound as described. By hydroxylamine developing agent it is intended to embrace hydroxylamine itself as well as derivatives thereof as described above. The pphenylene diamine and p-aminophenol derivative of use according to the present invention may be added to the developing bath or to the emulsion or to both simultaneously, the processing bath being preferred, however.

Developer compositions that comprise the superadditive developing agents according to the present invention may comprise in addition thereto any of the common ingredients employed in developing compositions, e.g., alkalies such as sodium hydroxide, potassium hydroxide, sodium carbonate, trisodium phosphate etc., silver halide solvents such as sodium thiosulphate, sodium thiocyanate and cyclic imides such as barbiturates or uracils, preservatives such as sulphites, bisulphites, metabisulphites and acids such as boric acid and citric acid. Further the developer composition may comprise potassium bromide and water-softening agents such as polyphosphates and derivatives of ethylene diamine tetraacetic acid, antifoggants such as benzotriazole, S-nitrobenzotriazole and 6- nitrobenzimidazole and wetting agents as well as other compounds known in the photographic development technique such as development restrainers and development accelerators.

The ratio of hydroxylamine developing agent to pphenylene diamine or p-aminophenol compound used in the present invention can be chosen in such a way that the combination is suited for the development of all kinds of materials including materials having silver chloride emulsion layers of low sensitivity as well as materials having highly sensitive silver bromo-iodide emulsion layers. This ratio may vary within wide limits and also depends on the particular hydroxylamine developing agent used. In most cases the ratio is chosen in such a way that the amount of the hydroxylamine developing agent strongly outweighs the p-phenylene diamine or p-aminophenol compound.

A strong superadditive effect is obtained by using an amount of 0.05 to 10 millimole preferably from 0.3 to 6 millimole of p-phenylene diamine or p-aminophenol derivative to an amount of 10 to millimole of hydroxylamine developing agent, per liter of developing composition. Of course larger amounts of said pphenylene diamine or p-aminophenol compounds can be used, although the superadditive effect obtained with higher concentrations is not more considerable.

The novel combination of developing agents of the invention may be used in conventional or wet development of silver halide emulsions, in diffusion transfer processes, both dye and silver, in such photographic processes known as stabilization processing wherein it is desired to eliminate or minimize the need forwashing or stabilizing operations in liquid baths subsequent to the formation of the silver print, etc.

In diffusion transfer processes, as is well known in the art, an exposed silver halide emulsion is treated with a liquid processing composition while in superposed relationship with an image-receiving material. By this treatment the exposed silver halide is developed to silver and the unexposed silver halide is converted into a complex silver salt which is transferred to the imagereceiving material and there reduced to silver to form a positive print. The processing composition normally includes a silver halide solvent, such as sodium thiosulphate, sodium thiocyanate and cylic imides such as barbiturates or uracils, which forms with silver halide a soluble complex as is well known in the art of forming silver images by transfer, and may also include a film-forming material such as sodium carboxymethylcellulose and hydroxyethylcellulose, starch or gum for increasing the viscosity of the composition as, for'instance, in the case of in-camera silver complex diffusion transfer processing.

In stabilization processing the time-consuming fixing and washing operations are eliminated in order to produce the photographic record in the least possible time by converting after development, with the aid of stabilizing agents such as ammonium thiocyanate, the unexposed and undeveloped silver halide of the photographic emulsion into colorless light-insensitive compounds that need not be removed by washing.

The developing agents of use according to the invention may be employed in solution or they may be initially incorporated in a layer of the photosensitive material, e.g., a silver halide emulsion layer or an other colloid layer in water-permeable relationship therewith. in silver complex diffusion transfer processes they may also be incorporated in a layer of the image-receiving material which, during processing, is in superposed relationship with the photosensitive silver halide material.

The following examples illustrate the present invention.

Example 1 sodium sulphite 100 g sodium hydroxide g S-nitro-benzotriazole 80 mg potassium bromide 1g hydroxylamine hydrochloride 0.06 mole water to make 1 liter The other strips are developed in baths having the same composition as bath A but containing moreover one of the compounds listed in the table below in the amount given.

The densities obtained are listed in the following table.

Densities obtained after a Developing bath development time of Osec 20sec 1min 3min 5min Bath A 0.04 0.05 0.34 0.95 1.43 Bath A mg (0.31 mmole) of compound 3 0.04 0.07 0.79 1.97 2.68 Bath A 66 mg (0.31 mmole) of compound 28 0.04 0.12 0.86 2.17 3

Example 2 This example is analogous to example 1 with the only difference that now a developing bath B is used which only differs from bath A in that the hydroxylamine hydrochloride has been replaced by 0.06 mole of N- methylhydroxylamine hydrochloride.

The following results are attained.

Developing bath Densities obtained after a development time of Osec 20sec 1min 3min 5min Bath B 0.05 0.05 0.07 0.60 1.09 Bath B +105 mg(0.31mmo1e) of compound 3 0.04 0.04 0.19 1.83 2.61 Bath 13 66 mg (0.31 mmole) of compound 28 0.04 0.04 0.18 1.66 2.72

Example 3 This example is analogous to example 1 with the only difference that now a developing bath C is used which only differs from bath A in that the hydroxylamine hydrochloride has been replaced by 0.06 mole of N,N- diethylhydroxylamine oxalate.

The following results are attained.

This example is analogous to example 1 with the only difference that now a developing bath D is used which only differs from bath A in that the hydroxylamine hydrochloride has been replaced by 0.06 mole of N- methyl-N-(2-hydroxy-3-diethylaminopropyl) hydroxylamine.

The following results are attained.

Developing bath Densities obtained after a development time of sec 20sec 1min 3min 5min Bath D 0.04 0.04 0.04 0.1 l 0.56 Bath D +105 mg (0.31 mmole) of compound 3 0.04 0.04 0.17 1.33 2.15 Bath D 66 mg (0.31 mmole) of compound 28 0.04 0.04 0.12 1.01 1.97

Example 5 This example is analogous to example 1 with the only difference that now a developing bath E is used which only differs from bath A in that the hydroxylamine hydrochloride has been replaced by 0.06 mole of the hydroxylamine derivative corresponding to the formula:

according to the co-pending application filed on even date herewith for Novel Photographic Developers.

This example is analogous to example 1 with the only difference that now a developing bath F is used which only differs from bath A in that the hydroxylamine hydrochloride has been replaced by 0.06 mole of the hydroxylamine derivative with formula:

zmcQ-s 01' according to the co-pending application filed on even date herewith for Novel Photographic Developers."

The following results are attained.

Developing bath Densities obtained after a development time of Osec 20sec 1min 3min 5min Bath F 0.04 0.50 1.13 2.19 3 Bath F +105 mg (0.31 mmole) of compound 3 0.04 0.71 1.35 2.91 3 Bath F 66 mg (0.31 mmole) of compound 28 0.04 0.73 1.35 2.60 3

Example 7 A photosensitive element was prepared comprising on a paper support a propylene, bromoiodide emulsion layer containing per kg an amount of silver halide corresponding to 60 g of silver nitrate.

After exposure, the photosensitive element and an image-receiving element, which comprises a silver receptive layer containing development nuclei dispersed in a matrix of colloidal silica coated on a water-impervious support according to the practice described in US. Pat. No. 2,823,122 of Edwin H.Land issued Feb. 11, 1958, were advanced in superposed relationship between a pair of pressure applying rollers to spread between them in a thin layer the following processing composition:

water ml sodium carboxymethylcellulose 5 g sodium hydroxide 15 g uracil l 1.25 g 30 ammonium hydroxide 3.5 ml N,N-diethylhydroxylamine oxalate 0.06 mole l-phenyl-2-tetrazoline-5-thione 0.2 g compound 3 mg After a contact period of 36 seconds the emulsion together with the layer of processing liquid was stripped from the image-receiving element to uncover the positive print.

When using a same developing composition but comprising no compound 3 the density of the positive print obtained was markedly lower. Moreover, in the presence of compound 3 better quality transfer images are obtained at lower illumination levels than is the case when using N,N-diethylhydroxylamine alone.

We claim:

1. Photographic developing method which comprises the black and white development of an exposed silver halide emulsion layer of a photographic material with an aqueous alkaline composition comprising a hydroxylamine developing agent and a p-phenylene diamine or p-aminophenol derivative having one of the formulas l, 11 and 111:

wherein:

R stands for an alkyl group,

R, stands for alkyl or an ethylene group, or a propylene group attached to the adjacent orthocarbon atom of the benzene ring,

R: stands for alkyl, and

R stands for an alkyl group,

at most one of R and R being substituted alkyl,

wherein:

each of R and R stands for an alkyl group, and X, stands for an electron-donating group selected from the group consisting of alkyl, alkoxy, amino, monoalkylamine, dialkylamino, acylamino, and sulphonamido,

m. 1 1 Rs wherein:

each of X and X stands for hydrogen, halogen or an electron-donating group selected from the group consisting of alkyl, alkoxy, amino, monoalkylamine, dialkylamino, acylamino, and sulphonamido,

Y stands for OH or NH,, and

R stands for an ethylene or propylene group attached to the adjacent ortho-carbon atom of the benzene ring, and

R stands for hydrogen, an alkyl group or has the same significance as R,, or

R together with R and the N-atom to which they are attached from a pyrrolidine ring.

2. Photographic developing method according to claim 1, wherein said method is used for making images according to the silver complex diffusion transfer process.

3. Photographic developing composition for the black and white development of an exposed silver halide emulsion layer of a photographic material comprising in aqueous alkaline solution an hydroxylamine developing agent and a p-phenylene diamine or paminophenol derivative having one of the formulas I, ll and Ill:

II. R

wherein:

each of R, and R, stands for an alkyl group, and X stands for an electron-donating group selected from the group consisting of alkyl, alkoxy, amino, monoalkylamine, dialkylamino, acylamino, and sulphonamido,

III. R: R5

wherein:

Y stands for OH or NH,, and

R stands for hydrogen, an alkyl group or has the same significance as R or R together with R and the N-atom to which they are attached from a pyrrolidine ring said p-phenylene diamine or p-aminophenol derivative being present in an amount of from 0.05 to 10 millimoles per 10 to millimoles of hydroxyl amine developing agent per liter of developing composition.

4. Photographic developing method according to claim 1, wherein one of said hydroxylamine developing agent and said p-phenylene diamine or p-aminophenol derivative is initially present in said photographic material and transferred to said aqueous alkaline composition therefrom.

S. The photographic developing method of claim 1 wherein said p-phenylene diamine or p-aminophenol derivative has the formula:

wherein:

R, stands for an alkyl group,

R, stands for alkyl, and

R, stands for an alkyl group,

at most one of R and R being substituted alkyl.

6. The photographic developing method of claim 1 wherein said p-phenylene diamine or p-aminophenol derivative has the formula:

II. R5 Rs l K l, N111 wherein:

each of R and R stands for an alkyl group, and X, stands for an electron-donating group selected from the group consisting of alkyl, alkoxy, amino, at most one of R and R being substituted alkyl. monoalkylamine, dialkylamino, acylamino, and 9. Photographic developing composition of claim 3 sulphonamido. wherein said p-phenylene diamine or p-aminophenol 7. The photographic developing method of claim 1 derivative has the formula: wherein said p-phenylene diamine or p-aminophenol derivative has the formula: II.

III R1 Ra in -Xa wherein: wherein:

each of X and X stands for hydrogen, halogen or an h f R nd R st nds f r an lk l roup, and

electron-donating group l t d fr t g p X stands for an electron-donating group selected consisting of alkyl, alkoxy, amin m from the group consisting of alkyl, alkoxy, amino, kylamine, dialkylamino, acylamino, and monoalkylamine, dialkylamino, acylamino, and sulphonamido, sulphonamido. Y stands for OH 01' NH and 10. Photographic developing composition of claim 3 R stands for an ethylene 0r pr pyl n g p wherein said p-phenylene diamine or p-aminophenol tached to the adjacent ortho-carbon atom of the d i i h h f l benzene ring, and R stands for hydrogen, an alkyl group or has the R7 R8 same significance as R or R together with R and the N-atom to which they are attached from a pyrrolidine ring.

8. Photographic developing composition of claim 3 wherein said p-phenylene diamine or p-aminophenol X derivative has the formula:

I. R1 R9 3 -wherein:

each of X and X stands for hydrogen, halogen or an electron-donating group selected from the group consisting of alkyl, alkoxy, amino, monoal- N kylamine, dialkylamino, acylamino, and 40 sulphonamido, Ra Y stands for OH or Nl-l and wherein: R stands for an ethylene or propylene group at- R stands for an alkyl group, tached to the adjacent ortho-carbon atom of the R stands for alkyl or an ethylene group, or a benzene ring, and

propylene group attached to the adjacent ortho- R stands for hydrogen, an alkyl group or has the carbon atom of the benzene ring, same significance as R,, or R stands for alkyl, and R together with R and the N-atom to which they are R stands for an alkyl group, attached from a pyrrolidine ring.

t k k 1!

Claims

2. Photographic developing method according to claim 1, wherein said method is used for making images according to the silver complex diffusion transfer process.
3. Photographic developing composition for the black and white development of an exposed silver halide emulsion layer of a photographic material comprising in aqueous alkaline solution an hydroxylamine developing agent and a p-phenylene diamine or p-aminophenol derivative having one of the formulas I, II and III:
4. Photographic developing method according to claim 1, wherein one of said hydroxylamine developing agent and said p-phenylene diamine or p-aminophenol derivative is initially present in said photographic material and transferred to said aqueous alkaline composition therefrom.
5. The photographic developing method of claim 1 wherein said p-phenylene diamine or p-aminophenol derivative has the formula:
6. The photographic developing method of claim 1 wherein said p-phenylene diamine or p-aminophenol derivative has the formula:
7. The photographic developing method of claim 1 wherein said p-phenylene diamine or p-aminophenol derivative has the formula:
8. Photographic developing composition of claim 3 wherein said p-phenylene diamine or p-aminophenol derivative has the formula:
9. Photographic developing composition of claim 3 wherein said p-phenylene diamine or p-aminophenol derivative has the formula:
10. Photographic developing composition of claim 3 wherein said p-phenylene diamine or p-aminophenol derivative has the formula: