DEVELOPER SOLUTION FOR EXPOSED SILVER HALIDE CONTAINING AN ORGANIC THIOL OR THIONE COMPOUND AND A BUNTE SALT

REVELATEUR EN SOLUTION POUR LES HALOGENURES QUI ONT REAGI ET CONTENANT UN THIOL ORGANIQUE OU UN COMPOSE THIONE ET UN SEL DE BUNTE

English Abstract

8-11657/TEL 186/+
Process for the prevention of darkening
and the formation of a sediment in
photographic developer solutions
Abstract of the Disclosure
A process is described for the prevention of
darkening and the formation of a sediment in photographic
developer solutions which contain a
silver halide developer, a water-soluble silver halide
solvent and organic sulfur compounds. The organic
sulfur compounds are a combination of (a) an organic
thiol compound or thione compound capable of tautomerism
and (b) a Bunte salt which contains groups conferring
solubility in water. Developer solutions which contain
the indicated combination of sulfur compounds are out-
standingly stable.

Claims

- 32 -
WHAT IS CLAIMED IS:
1. A process for the prevention of darkening and the
formation of a sediment in photographic developer solutions
which contain a compound which develops silver halide, a
water-soluble silver halide solvent and organic sulfur
compounds, which comprises adding to the developer solution,
as organic sulfur compounds, a combination of (a) an organic
thiol compound or thione compound which is capable of
tautomerism and (b) a Bunte salt containing groups which-
confer solubility in water.
2. A process according to claim 1, wherein the organic
sulfur compounds added to the developer solution are a
combination of: (a) a compound of the formulae
HS-D-(W) or <IMG>
and (b) a Bunte salt of the formula
(Z)m-E-(B)r-1-SSO3M
in which formulae A is a nitrogen atom, a carbon atom
bonded via a double bond (=?-) or <IMG> and B is <IMG> or
<IMG> , R2 is hydrogen, substituted or unsubstituted alkyl,
substituted or unsubstituted phenyl or a substituted or
unsubstituted, saturated or unsaturated 5-membered or 6-
membered heterocyclic radical containing nitrogen, oxygen
and/or sulfur atoms and R1 has the meaning defined for R2
with the exception of hydrogen, or R1 and R2 together with
the atoms to which they are bonded form a 4-membered, 5-
membered or 6-membered heterocyclic ring, containing

- 33 -
nitrogen, oxygen and/or sulfur atoms, D and E are each a
substituted or unsubstituted aliphatic, araliphatic, cyclo-
aliphatic, aromatic or heterocyclic radical and W and Z are
each a radical of the formulae -COOM, -SO3M, -SSO3M,
<IMG> , -OH, <IMG> , <IMG> , <IMG> , <IMG> ,
<IMG> , -SO2-X or -SO2M or a polyoxyethylene radical
which has 2 to 20 oxyethylene units, a polyoxyethylene
radical which has 2 to 20 oxyethylene units and is sulfon-
ated, in which formulae G, X and Y are each hydrogen or
are alkyl having 1 to 6 carbon atoms which is substituted
by hydroxyl, carboxyl or -SO3H and Y is also phenyl, phenyl-
sulfonic acid, alkylsulfonyl having 1 to 5 carbon atoms,
phenylsulfonyl or tolylsulfonyl, and A1? is a monovalent
anion and M is a monovalent cation, and n and m are each
an integer from 1 to 4 and r is 1 or 2.
3. A process according to claim 2, wherein the
Bunte salt has the formula (Z)m-E-SSO3M, in which E,
M, Z and m are as defined in claim 2.
4. A process according to claim 2, wherein component
(a) is a mercaptan of the formula
<IMG>
and component (b) is a Bunte salt of the formula
<IMG>

- 34 -
in which formulae D1 in each case is an aliphatic, arali-
phatic or aromatic radical having not more than 40 carbon
atoms or a heterocyclic 5-membered or 6-membered ring which
contains 1 to 4 nitrogen atoms, one oxygen atom and/or one
sulfur atom and can be fused with a benzene ring, W1 is
-COOM, -SO3M, -OH or <IMG> and Z1 is -COOM, -SO3M ,
-SSO3M , -OH , <IMG> or <IMG> , n1 and m1 in each
case are an integer from 1 to 3 and M, X and Y are as
defined in claim 2.
5. A process according to claim 4, wherein component
(a) is a mercaptan of the formula
<IMG>
in which D2 is an aliphatic or araliphatic radical having
not more than 20 carbon atoms or a substituted or unsub-
stituted benzene radical and n2 is 1 or 2 and W1 is as
defined in claim 4.
6. A process according to claim 5, wherein component
(a) is a mercaptan of the formula
<IMG>
and component (b) is a Bunte salt of the formula
<IMG>
in which formulae D2 in each case is an aliphatic or
araliphatic radical having not more than 20 carbon atoms

- 35 -
or a substituted or unsubstituted benzene radical, W2 is
-COOH or -SO3M, Z2 is -COOM, -SO3M, -SSO3M , -NH2 or -OH
and M is a monovalent cation and n2 and m2 are each 1 or
2.
7. A process according to claim 6, wherein compon-
ent (a) is a mercaptan of the formula HS-D3-COOM, in
which D3 is phenylene which is unsubstituted or substitu-
ted by alkyl having 1 to 4 carbon atoms, halogen or amino
and M is a monovalent cation.
8. A process according to claim 6, wherein D2 is a
straight-chain or branched alkylene having 1 to 10 carbon
atoms or a straight-chain or branched alkylene having 1 to
10 carbon atoms which is interrupted by -O-, -SO2-, -NH-
or -NR-, in which R is alkyl having 1 to 4 carbon atoms.
9. A process according to claim 2, wherein
component (a) is a mercaptan of the formula
<IMG>
and component (b) is a Bunte salt of the formula
<IMG>
in which formulae R3 is hydrogen, alkyl having 1 to 5
carbon atoms, carboxyl 7 carboxyalkyl having 1 to 3 car-
bon atoms in the alkyl moiety, phenyl, which is unsubsti-
tuted or substituted by alkyl having 1 to 4 carbon atoms,

- 36 -
halogen, hydroxyl, amino, -SO3H, -COOH or -SO2NH2, or
furyl, thienyl, pyrimidyl, pyridyl or 2-benzimidazolyl,
R4 is hydrogen, alkyl having 1 to 5 carbon atoms,
hydroxy- and mercapto -alkyl each having 1 to 3 carbon
atoms, phenyl which is unsubstituted or substituted by
alkyl having 1 to 4 carbon atoms, halogen, hydroxyl,
amino, -SO3H or -SO2NH2, or benzyl, R5 is alkylene or
alkylidene having not more than 6 carbon atoms, which is
unsubstituted or substituted by alkyl having 1 to 4
carbon atoms, phenyl, halogen, hydroxyl, mercapto or
amino, phenylene, which is unsubstituted or substituted
by alkyl having 1 to 4 carbon atoms, halogen, hydroxyl,
amino, -COOH, -SO3H or -SO2NH2, or .alpha.,2-, .alpha.,3- or .alpha.,4-
benzylene or - if p is 1 - a direct chemical bond, R11 is
hydrogen, alkyl having 1 to 5 carbon atoms, carboxyalkyl
having 1 to 3 carbon atoms in the alkyl moiety, phenyl,
which is unsubstituted or substituted by alkyl having 1
to 4 carbon atoms, halogen, hydroxyl, amino, -SO3H or
-SO2NH2, or benzyl, R12 is alkylene or alkylidene having
not more than 6 carbon atoms, which is unsubstituted or
substituted by alkyl having 1 to 4 carbon atoms, phenyl,
halogen, hydroxyl or amino, phenylene or aralkylene,
which are unsubstituted or substituted by alkyl having 1
to 4 carbon atoms, halogen, hydroxyl, amino, -COOH, -SO3H
or -SO2NH2 or -(CH2)s-1-CONH-CH2)t-? or - if q is 1 - a
direct chemical bond, Z2 is -COOM, -SO3M, -SSO3M, -NH2 or
-OH, W2 is -COOM or -SO3M, M is a monovalent cation and m2,
p and q are each 1 or 2 and s and t are each an integer from 1 to 3.
10. A process according to claim 9, wherein component
(a) is a mercaptan of the formula
<IMG>

- 37 -
in which R6 is hydrogen, methyl, ethyl or phenyl, R7 is
hydrogen, methyl, phenyl, tolyl or carboxymethyl, R8 is a
direct chemical bond, -(CH2)u- , <IMG> ,
<IMG> or <IMG> , M is a monovalent cation and u is an
integer from 1 to 3.
11. A process according to claim 10, wherein compon-
ent (a) is a mercaptan of the formula
<IMG>
in which R13 and R10 are each hydrogen, methyl or phenyl
and u is an integer from 1 to 3.
12. A process according to claim 9, wherein component
(b) is a Bunte salt of the formula
<IMG>
in which R13 is hydrogen, methyl, ethyl, phenyl or car-
boxymethyl, R14 is a direct chemical bond, -(CH2)V-,
-CH(CH3)-, -C(CH3)2-, -CH2CH(CH3)-, -CH = CH-,
-CH2CH(CH3H7)-, -CH2CH(C6H5)-, -CH(NH2)-, <IMG>,
<IMG> or <IMG> , Z2 is -COOH, -SO3M,
-SSO3M, -NH2 or -OH, M is a monovalent cation and v is an
integer from 1 to 6.

- 38 -
13. A process according to claim 12, wherein component
(b) is a Bunte salt of the formula
<IMG>
in which R15 is hydrogen, methyl or phenyl, M is a mono;
valent cation, Z3 is -COOH or -NH2 and w is 1 or 2.
14. A process according to claim 9, wherein component
(a) is a mercaptan of the formula
<IMG>
and component (b) is a Bunte salt of the formula
<IMG>
in which formulae R9, R10 and R15 are each hydrogen,
methyl or phenyl, M is a monovalent cation, u is an inte-
ger from 1 to 3 and w is 1 or 2,
15. A process according to claim 1, 2, or 3,
wherein the developer solution contains, as the silver
halide solvent, a sulfite in a concentration of more than
20 g per litre or a water-soluble thiocyanate or thio-
sulfate.

- 39 -
16. A process according to claim 4, 5, or 6, wherein
the developer solution contains, as the silver halide solvent,
a sulfite in a concentration of more than 20 g per litre or
a water-soluble thiocyanate or thiosulfate.
17. A process according to claim 7 or 8, wherein the
developer solution contains, as the silver halide solvent, a
sulfite in a concentration of more than 20 g per litre or a
water-soluble thiocyanate or thiosulfate.
18. A developer solution, for developing photographic
recording material which contains silver halide and has been
exposed image-wise, which contains a compound which develops
silver halide, a water-soluble silver halide solvent and a
combination of (a) an organic thiol compound or thione compound
which is capable of tautomerism and (b) a Bunte salt con-
taining groups which confer solubility in water.
19. A developer solution according to claim 18 which
is aqueous.
20. A developer solution according to claim 18
which contains 0.1 to 20 g/l of the compound which develops
silver halide, 0.1 to 200 g/l of the silver halide solvent
and 0.05 to 10 g/l of the combination of components (a) and
(b), the molar ratio of (a):(b) being 5:1 to 1:100.
21. A developer solution according to claim 18, which
is prepared from a single concentrate or from separate con-
centrates of the compound which develops silver halide, the
silver halide solvent and the combination of components (a)
and (b), by diluting with water, which optionally can be
mixed with organic solvents.
22 A concentrate for the preparation of a developer
solution according to claim 21 in the form of a liquid or paste.

- 40 -
23. A liquid or pasty concentrate according to claim 22,
which contains the individual components, per litre of con-
centrate, in amounts which are 2 to 25 times the amounts
indicated in claim 20.
24. A developer solution according to claim 19, which
is prepared from a single concentrate or from separate con-
centrates of the compound which develops silver halide, the
silver halide solvent and the combination of components (a)
and (b), by diluting with water, which optionally can be mixed
with organic solvents.
25. A process according to claim 3, 4 or 5, wherein
component (a) is a mercaptan of the formula
<IMG>
and component (b) is a Bunte salt of the formula
<IMG>
in which formulae R3 is hydrogen, alkyl having 1 to 5
carbon atoms, carboxyl, carboxyalkyl having 1 to 3 car-
bon atoms in the alkyl moiety, phenyl, which is unsubsti-
tuted or substituted by alkyl having 1 to 4 carbon atoms,

- 41 -
halogen, hydroxyl, amino, -SO3H, -COOH or -SO2NH2, or
furyl, thienyl, pyrimidyl, pyridyl or 2-benzimidazolyl,
R4 is hydrogen, alkyl having 1 to 5 carbon atoms,
hydroxy- and mercapto-alkyl each having 1 to 3 carbon
atoms, phenyl which is unsubstituted or substituted by
alkyl having 1 to 4 carbon atoms, halogen, hydroxyl,
amino, -SO3H or -SO2NH2, or benzyl, R5 is alkylene or
alkylidene having not more than 6 carbon atoms, which is
unsubstituted or substituted by alkyl having 1 to 4
carbon atoms, phenyl, halogen, hydroxyl, mercapto or
amino, phenylene, which is unsubstituted or substituted
by alkyl having 1 to 4 carbon atoms, halogen, hydroxyl,
amino, -COOH, -SO3H or -SO2NH2, or .alpha.,2-, .alpha.,3- or .alpha.,9 4-
benzylene or - if p is 1 - a direct chemical bond, R11 is
hydrogen, alkyl having 1 to 5 carbon atoms, carboxyalkyl
having 1 to 3 carbon atoms in the alkyl moiety, phenyl,
which is unsubstituted or substituted by alkyl having 1
to 4 carbon atoms, halogen, hydroxyl, amino, -SO3H or
-SO2NH2, or benzyl, R12 is alkylene or alkylidene having
not more than 6 carbon atoms, which is unsubstituted or
substituted by alkyl having 1 to 4 carbon atoms, phenyl,
halogen, hydroxyl or amino, phenylene or aralkylene,
which are unsubstituted or substituted by alkyl having 1
to 4 carbon atoms, halogen, hydroxyl, amino, -COOH, -SO3H
or -SO2NH2 or -(CH2)s-1-CONH-(CH2)t-? or - if q1 is 1 - a
direct chemical bond, Z2 is -COOM, -SO3M, -SSO3M, -NH2 or
-OH, W2 is -COOM or SO3M, M is a monovalent cation and m2,
p and q are each 1 or 2 and s and t are each an integer from 1 to 3.
26. A developer solution according to claim 19, which
contains 0.1 to 20 g/l of the compound which develops silver
halide, 0.1 to 200 g/l of the silver halide solvent and
0.05 to 10 g/l of the combination of components (a) and (b),
the molar ratio of (a):(b) being 5:1 to 1:100.

Description

` ~
~l~5213C~
13-11657/TEL 186/+
Process for the prevention o~ darkening
and the ~ormation o~ a sediment in
photographic developer solutions
~ .
When photographlc materials containing silver
halide are processed9 developing is in the mai~ carried
out in an alkaline medium and o- or p_dihydroxybenzenes,
aminophenols, diaminobenzenes, pyrazolidinones, reductones
or hydrox~lamine derivatives are used as developer sub-
stances. Usually, the developer solution also contaLns
~urther additives, such as salts of sul~urous acid for
stabilising, ~nti-fogging agents and bu~fer substances.
Furthermore, it is also known to develop photographic
material in certain cases in th.~ presence o~ silve~ halide
solvents. Such silver halide solvents are 7 for
example, organic compounds of divalent sul~ur, such as
mercapto compounds, thioethers, thioamides or compounds
containing an acid -CH grouping, ~or example bis-methyl-
sul~onylmethane, and also salts o~ thiocyanic acid or
salts of sul~urous acid in high concentration, but especi-
ally salts o~ thiosul~uric acid~
Developers containing such additives are known as
fine-grain developers and in_grain developers. (cf.
E. Mutter, "Die Technik der Negativ- und Positi w er~ahren"
("The Techniques of Negative and Positive Processes"),
Springer 1955, page 158 to 159). The developing o~
latent silver nuclei inside the grains is o~ particular
importance in the case o~ reversal development processes,

~2~
in which salts of thiocyanic acid are frequently added to
the first developer. Further important embodiments
o~ this type are the monobaths, such as are described,
say, in U.SO Pate~t Specification ~,857,710 or by G.Haist
in "Monobath Manual", Morgan 1960 A further embodi-
ment of this type is a masking developer for the silver
dye-bleach process as described in German O~enlegungs-
sch~i~t 2,~479720.
However, ma~y of these developers have the dis-
advantage that they more or less rapidly reduce the silver
halide dissolved in the form o~ a complex from the photo-
graphic material. As a result of this a turbidity and,
a~te~ some time, a sediment of silver form in the develo-
per and this sediment can adhere both to the photographic
material and to parts of the developing equipment.
~his formation of a sediment proves particularly disadvan-
tageous in the case of equipment which operates continu-
ously~ There has been no lack of attempts to find
suitable measures against the formation of a silver sedi-
mentO
In German Offenlegungsschrift 2,437,353 it is
proposed to use derivatives of l-phenyl-5-mercaptotetra-
zole in developer for X-ray film to counter the deposition
of silver in developing equipment. In U.S, Patent
Specification ~,1739789 and in German Auslegeschrift
1,175,077 and German Offenlegungsschri~t 2,003,414 hetero-
cyclic mercapto compounds, a~d in German Offenlegungs-
schrift 1,909,743 aliphatic mercaptocarboxylic acids, are
described as additives to prooessing solutions to combat
the formation of a silver sediment. In U,S. Patent
Spscification 3,318,701,a-liponic acid , and in German
Offenlegungsschrift 2,040,801 4-acylami~o-1,2,3-tria201ine-
5-thiones, are proposed to counter the ~ormation of a
sediment. These substances are usually employed in
amounts of between 5 and 5,000 mg per litre o~ de~eloper
solution.
It has been found that the proposed additi~es c~n

-- 3 --
delay the formation of a silver sediment for a certain
period, but they have diverse undesired side effects.
Substances which have a good clarity-preserving effect
have a considerable influence on the characteristics of
the developer. In the case of multi-layer colour
materials, in particular the sensitivity of the uppermost
layer is reduced. When silver dye-bleach materials
are subjected to masking developing, disturbances in the
masking e~fect arise. Other substances are unstable
in the developer, lose e~fectiveness rapidly due to atmos-
pheric oxidation or decompose with the formation of
secondary products which are malodorous and/or harmful to
health. The practical application of the clarity-
preserving substances proposed hitherto is made consider-
ably more difficult and in many cases impossible as a
result of all o~ thesP disadvantages. Finally, in
German Of~enlegungsschrift 2,640,659 a developing process
is described in which speci~ic organic di- or tri-sulfides
are used to preserve the clarit~ o~ developer solutions.
These di- and tri-sulfides are indeed already very
suitable for preserving the clarity of, and for preventing
the forma-tion of a silver sediment in, photographic
developer solutions, but they have the disadvantage that
they are accessible by synthesis only with di~ficulty and,
~urthermore, that they have to be employed in relatively
large amounts in the developing bath in order to obtain
the desired effects.
The object o~ the present invention is, therefore,
to provide a novel process for the prevention of darkening
and the formation of a sedim~nt in photographic developer
solutions, with which process impairment of photographic
developing should be largely excluded.
It has now been found that this object c2n be
achieved if a combination of a mercapto compound and
a Bunte salt is added to the developer solutions.
It is true that German Offenlegungsschrift
1,768,400 already describes the use of Bunte salts in

oo
_ 4 --
the photo~raphic field, for example as stabilisers for
silver halide emulsions or for stabilising photographic
materials which have been developed. In contrast to
this, howe~rer, the Bunte salts according to the present
inventlon are employed in combination with a mercapto
compound in developer solutions and are used ~or a di~er
ent purpose.
The present in~ention relates to a process for
the prevention o~ darkening and the formation of a sedi-
ment in photographic developer solutions which contain a
compound which develops silver halide, a water-soluble
silver halide solvent and organic sulfur compounds, which
comprises adding to the developer solution, as organic
sulf~r compounds, a combination of (a) an organic thiol
compound or thione compound which is capable o~ tautomer-
ism and (b) a Bunte salt- containing groups which con~er
solubility in water.
The thiol compounds or thione compounds capable
o~ tautomerism are compounds o~ the ~ormulae
(1) HS - ~~(W)n or (2) S = C - A - H ,
Rl R2
whilst the Bunte .salts. have the ~ormula
) (Z)m E - (B)r_l - SS03M
in which formulae A is a nitrogen atom, a carbon atom
bonded via a double bond (=C-) or ~CH and B is -C- or
O
-CH2C-, R2 is hydrogen, substituted or unsubstituted alk~l,
o
substituted or unsubstituted phe~yl or a substituted or
unsubstituted, saturated or unsaturated 5-membered or 6-
membered heterocyclic radical containing nitrogen, oxygsn
and/or sulfur atoms and Rl has the meaning de~ined ~or R2
with the exception of hydrogen, or Rl and R2 together

~2
with the atoms to which they are bonded form a 4-membered,
5-membered or 6-membered heterocyclic ring, D and E are
each a substituted or unsubstituted aliphatic, araliphatic,
cycloaliphatic, aromatic or heterocyclic radical and W
and Z are each a radical o~ the formulae -COOM~ ~S03M,
~Y Y
03M, P~OM ~ -OH , -N - S03M , -S02N - Y ,
-N Y A ~ , -N \ , -CON ~ , -S02-X or -S02M
or a polyoxyethylene radical which has 2 to 20 oxyethylene
units and can be sulfonated, in which ~ormulae G, X and Y
are each hydrogen or are alkyl having 1 to 6 carbon atoms
which is substituted by hydroxyl, carboxyl or -~03H and Y
is also phenyl, phenylsul~onic acid, alkylsul~onyl having
1 to 5 carbon atoms, phenylsul~onyl or tolylsul~onyl~
M is a monovalent cation and ~ is a monovalent anion,
and n and m are each an integer from 1 to 4 and r is 1 or
2~ I~ r is 1, the Bunte- sc~t~ have the formula
(Z)m-E-SS03M, in which the symbols are as definedO
The invention also rela-tes to the developer solu-
tion for carrying out the process, the concentrates ~or
preparing the developer solutions, the use of the process
~hen developing photographic black-and-white, reversal,
chromogenic, X-ray or silver dye-bleach material and also
the use o~ the combination o~ components (a) and (b) as
the additive which suppresses darkening and the formation
of a sediment (silver sediment) in photographic de~eloper
solutions.
In the mercapto compounds of the formula (1), D is,
for example, a substituted or unsubstituted, saturated or
~nsaturated aliphatic radical having not more than 40 and
pre~erably not more than 20 carbon atoms, preferred radi-
cals being straight-chain (~(CH2)X-, x - 1 to 40) or
branched alkylene and alkylidene having not more than 10
carbon atoms, The alkylene and alkylidene bridge

~28010
~ 6 --
members can, if desired, also be interrupted by -O-,
-S02- or -MH- or -NR- (R= Cl-C4-alkyl). In addition
to alkyl (formation o~ the branched radicals), for
example alkyl having 1 to 5 carbon atoms - methyl, ethyl,
n-propyl, nbutyl, n-amyl and is~meric radicals -, sub-
stituents can be carboxyl 9 carboxyalkyl having 1 to 3
carbon atoms in the alkyl moiety, especially carboxy-
methyl, hydroxyl, mercapto (-SH) and also hydroxy- or
mercapto-alkyl each having~ for example, 1 to 3 carbon
atoms (hydroxymethyl, hydroxyethyl, hydroxypropyl and the
corresponding radicals containing mercapto groups).
If the substituents are mercapto or mercaptoalkyl groups,
the mercaptans o~ the ~ormula (1) are dimercaptans or
can also be polymercapta~s.
If the bridge member D is a substituted or unsub-
stituted aliphatic radical, which li~ewise can co~tain
not more than 40 carbon atoms, such radicals are, in par-
ticular, benzylene or phe~ylethylene radicals, which ca~
be substituted on the phenyl ring by halogen (~luorine,
chlorine or bromine), hydroxyl7 amino (-NH2), -S03H or
-S02NH2.
The cycloaliphatic radicals are in particular
derived from cycloalkyl ha~ing :L to 4 cycloalkyl rings and
5 to 10 carbon ~toms and preferably having 5 or 6 carbon
atomsO Examples are cyclopentyl 9 cyclohexyl, norbornyl
or l-adamantyl radicals.
The aromatic radicals are as a rule those which
are derived from mononuclear or polynuclear, substituted
or unsubstituted aromatic co~pounds ha~ing a total of not
more than 40 carbon atoms, but especially those derived
from benzene. Phenylene is pre~e~red and this can con-
tain, as substituents, al~yl, for example having 1 to 4
carbon atoms, halogen~ ~or example fluorine, chlorine or
bromine, hydroxyl, amino (-NH2), -COOH 9 -S03H or -S02NH2,
alkyl, halogen and amino being preferred.
I~ the bridge member D is a substituted or unsub-
stituted heterocyclic radical, these radicals are as a

-- 7 --
rule saturated or unsaturated 5-membered or 6-membered
radicals containing nitrogen, oxygen and/or sulfur atoms,
~or example pyridyl, pyrimidyl, pyridazyl, pyrazolyl,
pyrryl, triazinyl, imidazolyl, the triazolyl and tetrazol-
yl radicals, the oxazolyl and thiazolyl radicals, furyl or
thienyl; further radicals are morpholinyl, imidazolinyl,
imidazolidi~yl, pyrrolidinyl, pyrrolidinonyl, tetrahydro-
~uryl or piperidinyl.
The radicals can, thus, contain 1 to 4 nitrogen
atoms, one oxygen atom and/or one sulfur atom.
Examples o~ ~used systems are benzimidazoles, quinoxalines,
benzoxazoles and benzthiazoles.
In the mercapto compounds o~ the formula (1),
jOY
W is -COOM, -$03M, -5SO3M, -P \ , -OH, -N-SO~M,
2 ~ \ G ~ ' \Y ~ \y ' 2
-SO2M or a polyoxyethylene radical which has 2 to 20 oxy-
ethylene units and can be sulfonated. G, X and Y
independently o~ one another can be hydrogen or substit~-
ted alkyl havlng 1 to 6 carbon atoms, possible substitu-
ents being hydroxyl, carboxyl or -SO3H; Y can also be
phenyl, phenylsul~onic acid ( ~ SO3H), alkylsulfonyl
having 1 tQ 5 carbon atoms in the alkyl moiety (CH3-S02-,
C H ~ C ~ SO2~ C3~ SO~ , C4H9S2 or 5 ~1 2
phenylsul~onyl ( ~ SO2-) or tol~lsul~onyl
. ~
~CH3 ~ S2-)~ G, X ~Ld Y together with the nitro-
gen atom can, ~urthermore, also form a saturated or un-
saturated 5-membered or 5-membered ring, for example a
pyridinium ring. M is a monovalent cation, especially
the hydrogen cation ( ~ ), and al~o an alkali metal cation
(Na ~ or K ~) or ~L ammonium cation (NH4~9 ). A ~ is
a monovalent anion, ~or example Br ~ , Cl ~ , CH~ SO~
or CH3 ~ SO3

~5~
~ 8 --
The radicals W in the com~ounds o~ the formula (1)
are groups which confer solubility in ~Jater; the number
o~ such radicals can be up to 4 (n = 1 to 4) and the pre-
ferred compounds con~ain 3, ~ or especially only one of
the radicals W.
The compounds of the formula (2) contain a C-S
grouping which is capable o~ tautomerism and can therefore
be described as follows.
~ HS----C~=A
t
, Rl R2 g'l R2
For reasons of simplicity, in every case only one
tautomeric form is indicated in the present specification,
without, however 9 this excluding the other ~orm.
A is a nitrogen atom (-N-), a car~on atom bonded
Yia a double bond (=C-) or a -CH- ~rouping.
R2 is hydrogen or also substituted or unsubstitu-
ted alk~ or example ha~ing 1 to 10 carbon atoms and
containing, for example, the substituents hydroxyl, amino,
alkyl (Cl-C4)7 halogen (~luori~e, chlorine or bromine),
-S03M or -S02NH2, furthermore, R2 can be substituted or
unsubstituted phenyl, possible substituents being alk~l
(Cl-C4), halogen (fluorine, chlorine or bromine), h~droxyl,
i c~rboxyl -S03H or -S02NH2; Rl h
de~ined for R2 with the exception o~ hydrogen; if Rl and
R2 are the radicals o~ substituted (substitue~ts as ~or
phenyl) or unsubstituted, sa~urated or unsaturated 5-
membered or 6 membered heterocyclic compounds containing
nitroge~, oxygen and/or sul~ur atoms, the radicals of
heterocyclic compounds such as those mentioned under D can
also be used here. If desired, the radicals Rl and R2
together can be the atom grouping which is still required
to form a 4-membered, 5 membered or 6-membered hetero
cyclic ring with the grouping =C-A or -C=A. Hetero-
atoms are the nitrogen, oxygen and/or sulfur atom.
E in the Bunte salts o~ the ~ormula (3) has

- 9 -
the meaning defined for D in the mercapto compounds o~ the
formula (1) and D and E can be identical or different to
one another. In addition, however, E can also be a
bridge member of the formula -(CH2)S 1 CONH(CX2)t 1-
in which s and t are each an integer from 1 to 3.
Z has the meaning defined for W, and in this case also the
two symbols can have identical or dif~erent meanings.
B in the Bunte salts o~ the ~ormula (3) is
-C~ or CH2C-.
O O
The grouping -E-B- in -E-B-SS03M- (r=2) can addition-
ally be, ~or example, acetyl or benzoyl, ~hich axe unsubstitu-
ted or substituted by alkyl (Cl C3), preferably methyl,
or halogen, pre~erably chlorine, for example:
L
-CX2-C-SS03M or ~ C-SS03M 9 -CHCSS03M or
O -- O O
L
CSS03M
(L = substituent - alkyl or halogen).
The combination of (a) and (b) used in the process
according to the invention is pre~erably a combination in
which component (a) is a mercaptan o~ the ~ormula
(4) HS - Dl~(~)nl
and component (b) is a Bunte salt of the formula
1 ml 1 3
in which formulae Dl in each case is a substituted or un-
substituted aliphatic, araliphatic or aromatic radical
having not more than 40 carbon atoms or a heterocyclic
5-membered or 6-membered ring which contains 1 to 4
nitrogen atoms, one oxygen atom and/or one sul~ur atom
and can be fused with a benzene ring, Wl is -COOM, -S03M,

-- 10 --
x
-OH or CON / and Zl is -COOM, -S03M, -SS03M, -OH,
/x /x
CON \ or ~N \ , nl and ml in each case are an inte-
ger ~rom 1 to 3 and M, X and Y are as defined.
The symbols Dl in the formulae (4) and (5) can be
identical or dif~erent to one another,
Very suitable mercaptans of the ~ormula (4) have
the formula
(6) HS - D2 ~ (Wl)n
in which D2 is an aliphatic or araliphatic radical having
not more than 20 carbon atoms or a substituted or unsub-
stituted benzene radical and n2 is 1 or 2 and Wl is as
defined, and these mercaptans advantageously also have
the formula
(7) HS - D2 ~ (W2)n2
and are employed in combination with the B~nte salts
of the formula
(8) (Z2)m2-D2 ~ ~S3
in which formulae D2 is as defined, W2 is -COOH or -S03M~
Z2 is -COOM, SO~M, -SSO~M, -NH2 or -OH and M is a mono-
valent cation and n2 and m2 are each 1 or 2.
The substituents on the benzene radical are, for
example, alkyl having 1 to 4 carbon atoms, halogen (chlor-
ine or bromine), hydroxyl, amino, carboxyl, sulfo (-S03H)
or sulfonamide (-S02NHz), and one or more of these sub-
stituents can be present.
The symbols D2 in the formulae (7) and (8) can be
identical or different to one another.
I~ the mercaptans of the formula (7) contain an

~.52~30~
aromatic bridge member D2, particularly pre~erred mercap~
tans are -those of the formula
(9) HS - D3 - COOM
Xn this formula, D3 is phenylene, which can be unsub-
stituted or substituted by alkyl having 1 to 4 carbon
atom~, halogen, especially chlorine, or amino (-~H2),
whilst M is a monovalent cation, especially hydrogen ( ~ ),
A particularly valuable combination of components
(a) and (b) which can be used in the process according to
the invention co~tains, as component (a), a mercaptan of
the formula
HS L i ~ R5 - W2
and, as component (b), a Bunte salt o~ the formula
( 2)m2~12--~ CH -~ SS03M
Rll q
in which formulae R3 is hydrogen, alkyl ha~ing l to 5 car-
bon atoms, carboxyl, carboxyalkyl having 1 to 3 carbon
atoms in the alkyl moiety, phenyl, which is unsubstituted
or substituted by alkyl having 1 to 4 carbon atoms,
halogen, hydroxyl, amino, -S03H, -COOH or -S02NH2, or
~uryl, thienyl, pyrimidyl, pyridyl or 2~benzimidazolyl,
R4 is hydrogen, alkyl having 1 to 5 carbon atoms, hydroxy--
and mercapto-alkyl each having 1 to 3 carbon atoms,
phenyl which is unsubstituted or substituted by alkyl
having 1 to 4 carbon atoms, halogen, hydroxyl, amino,
-S03H or -S02NH2, or benzyl, R5 (if p is 1 or 2) is alkyl-
ene or alkylidene having not more than 6 carbon atoms,
which is unsubstituted or substituted by alkyl having 1 to
4 carbon atoms, phenyl, halogen, hydroxyl, mercapto or

- 12
amino, phenylene, which is unsubstituted or substituted
by alkyl having 1 to 4 carbon atoms, halogen, hydroxyl,
amino, -COOH, -S03H or -SO~NH2, or a,2-, ~,3- or a,4-
benzylene, Rll is hydrogen, alkyl having 1 to 5 carbon
atoms, carboxyalkyl having 1 to 3 carbon atoms in the
alkyl moiety, phen~l, which is unsubstituted or substitu-
ted by alkyl having 1 to 4 carbon atoms, halogen, hydrox-
yl, amino, -S03H or -S02NH2, or benzyl, or also - if p is
1 - a direct chemical bond. R12 (i~ q is 1 or 2) is
alkylene or alkylidene having not more than 6 carbon
atoms, which is unsubstituted or substituted by alkyl
having 1 to 4 carbon a-toms, phenyl, halogen, hydroæyl or
amino, phe~ylene or aralkylene (benzylene or phenyl
ethylene3, which are unsubstituted or substituted by
alkyl having 1 to 4 carbon atoms, halogen, hydroxyl,
amino, -COOH, -S03H or -~2NH2~ ~(CH2)s-l~CNH(CH2)t-l or
- if q is 1 - a direct chemical bond; if desired, R12 can
also be acetyl or benzoyl, whic,h are unsubstituted or sub-
stituted by alXyl having 1 to 3 carbon atoms or halogen;
W2 is -COOM or -S03M and M is a monovalent cation; m2,
p and q are each 1 or 2 and s and t are each an integer
from 1 to 3.
Particularly pre~erred mercaptans of the ~ormula
(10) have the ~ormulae
(12) R6
HS - C - R8 - COOM
R7
in which R6 is hydrogen, methyl, ethyl or phenyl, R7 is
hydrogen, methyl, phenyl, tolyl or carboxymethyl, R8 is a
direct chemical bond, -(CH2)U-, -CH-,
CH3 CH3
-C - or -CH- , M is a monovalent cation and u is an
CH3 NH2
integer from 1 to 3, and

~213~0
-- 13 --
Rg
tl3) HS C (CH2)u-l COOH
Rlo
in which Rg and Rlo are each hydrogen, methyl or phenyl
and u is an integer from 1 to 3, whilst particularly
suitable Bunte salts are the compounds o~ the formulae
(14) W2 - R14 CX - SS03M
R13
in which R13 is hydrogen, methyl, ethyl, phenyl or carboxy-
methyl, R14 is a direct chemical bond, -(CH2)V-,
-CH(~H3)-, -C(CH3)2~, -CH2CH(CH3)-, -CH = CH-,
-CE2CH(C3H7)-~ -CH2CH(C6H5)-, -CHtNH2) ~
CH2C NH CH2 or C NH CH2 CH2 , W2 is -COOH or -S03M,
O O
M is a mo~ovalent cation and v is an integer from 1 to 6,
and
(15) HOOC ~ tCH2)w-1-CH ~ SS03M
R15
in which ~ 5 is hydrogen, methyl or phenyl, M is a mono-
valent cation and w is 1 or 2.
The mercapto compou~ds and ~unte salts to be
used according to the i~ve~tion are compounds which are
known per se and w~ich are prepared by known methods.
(cf., ~or example, R. Kerber, Tetr.Le~ter~ 1966, page
3,007, B, Milligan and J. Swan, Rev. pure and appl~ chem.
12, 72 (1962) and H. Distler, Angew.Chem 79, 520 (1967)).
A pre~erred process ~or the preparation of the
sul~ur compounds described above 9 and especially of the
~-mercaptocarboxylic acids and derivatives thereof, com~
prises introducing the -SH or -SS03M group into an
unsaturated carboxylic acid or derivatives thereof
Suitable reagents are, for example, hydrogen sulfide,

- 14
thioacetic acid9 carbon disul~ide and derivatives thereof,
thiourea and inorganic thiosul~ates.
Suitable compounds for carrying out this process
are, for example, the following unsaturated acids and
their deri~atives: acrylic acid, methacrylic acid,
acrylonitrile, crotonic acid, 2- and 3-pentenic acid,
isopropylidenemalonic acid, itaconic acid, maleic anhyd-
ride 9 crotQnonitrile 9 vinylacetic acid, citraconic acid,
ethyl propiolate~ mesaconic acid, allylacetic acid, 3,3-
dimethylacrylic acid, tiglic acid, allylthioacetic acid,
trans aconitic acid, diethyl glutaconate, 2-hexenedioic
acid dinitrile~ allylmalonic acid 9 diethyl allylmalonate,
3-hexenedioic acid, 2 hexenoic acid, 3-cyclohexene-1-
carboxylic acid, 6-heptenoic acid, cinnamic acid, methyl
cinnamate, ethyl cinnamate, a-methylcinnamic acid, 4-
methylcin~amic acid, 2-, 3- or 4-methoxycinnamic acid, 4-
hydroxycinnamic acid, 4-chlorocinnamic acid, 4~sulfamoyl-
cinnamic acid, 3-hydroxy-4-metho~ycinnamic acid, ethyl 4-
sulfocinnamate, 2-carbox~cinnamic acid, 3,4-methylene-
dioxycinnamic acid, 2,3- or 3,4-dimethoxycinnamic acid,
3-(2~-furyl)-acrylic acid, 3-(2'-thienyl)-acrylic acid,
3 (~'-pyridyl)-acrylic acid, 3-(2g-pyridyl)-acrylic acid,
3-(4~-pyridyl)-acrylic acid, 5-norbornene-2-acrylic acid,
2-cyclopen~enyl-1-acetic acid, 5-norbornene-2-carboxylic
acid, bicyclo~2~202]oct-7-ene-2,3,5,7-tetracarboxylic acid
anhydride, methyl 2-nonenoate, eth~l phenylpropiolate,
diethyl diallylmalonate~ styrylacetic acid, 4-cyclooctene--
l-carboxylic acid, 4-cycloheptene-1-carboxylic acid and
4,4'-diaminostilbene-3,3'-dicarboxylic acid. Further-
more, the acid halides of the said acids can also be
employed. Furthermore, it is also possible to prepare
Bunte salts by sulfonation of the corresponding mer-
captans Of course, other alkylating agents, especi-
ally 3-membered to 6-membered oxygen-heterocyclic com-
pounds, for example epoxides, lactones or sultones, can
also be employed for the preparation of the sulfur com-
pounds to be used according to the invention.

8~)
-- 15 --
a~ ~ (Component a3
HOOC-CH2-SEI HOOC ~ 2_SH
~OOC -CH2 -CX2 - S~
HOOC-CH2~ -CH2-SH 3 S~2-CH2-CE~2-S~I
HOOC -CH-CH2 -SH
NH2 HS-CH2-CH--CH~H2-SH
OH OH
2 " 2
O ~N
H4-Nx co-cH2-cH2-sH HOOC~ N~H2-SH
2 ,C~~CH2 N~-CO-GH2_SH H
OH CH3
HOO~ CH2-~iH-CO-CH2-SX HOC)C-C-CH2-SH
o~NHCOCX2 ~ SH CH2
CûO~I OH
O N~
~HO-C2H4)2N-C~2 S~ HO ~ CH2-SH
H2N-C2H4-S~I
HOOC-C~H2--SH
~C2H4 - SX CH2 SH
KO 3 S~NH - CO -CH2 - SH
H2N-C~C2H -SH
0 4 HOOC-CHffH2-SH
CX2 ~COO~
H3
~ C2H4 SH ~ ~ CH2-SH
HO -CH~ ~CH -CH2 - SH 33
OH ( 3) 3N-cH2-cH2-sH
Br ~)

8C)~
-- 16 --
HOOC-CH-CEI2-CX2- SH . HOOC~ SH
NH2 .; ~H2 CH~
CH3 '
HOOC-C ~H2-S~ XOOC- (CH2) 2 -CH-SH
NH2 c~3
HOOC ~C2H4 - S02 -CH2 -CH2 ~ S~
.HOOC-CH2-CX-SX
H~03~- (CH2) 3-SH CH2 C~3
CH3-C-C~2-SH Ko3s~cH2-cH-sH
O CtI3
NaO3S-(CH2)2-S~ CH3 CH3
Na-OOC-C-CrcI2 -CH - SH
NaO3S (CH2) 3 SH CH3
~3
NaO3S - (CH2 ) 4-S~l HO~:)C -C- S~l
C~I3
NaO3S-CH- (CH 2 ) 2 ~SX ,c~3
CX3 HOOC~ C -SH
NaO3S-C~ - (CH2-CH-SH NH2 CH3
C6HS 3
CH3
NaO3S-C~-CH2~ S~ HOOC-CH2-C-SH
,~
C~3 ~3 ~ 3
Na3'- (C~2) 2-CH- S~ HOOC~ CH3
C~3 CH~C - SH
HOOC CH3
HOOC -CH -SH
CX3 C6H5
HOOC -C- SH
HOOC -CH2 CH-SH C6~5
c~3

8~0
-- ~7 --
SH
~C~2(::00H HOOC~-CH2~ SH
COOH
~OO~
6H5
SH
COOE CH2 CH-SH HOOC-CEI2-CH-SH
~COOH
S~ C~3 S02~2
SH
HOOC -CH2 -~H - SH
COOH ~0~
c~
~n ~H3
HOOC
HOOC -CH2 -CH- SH
SH ,~
~ S~
HO(:)C NH2
HOOC -C~12 -CH - SH
HOOC-C~ H~SH ~3
S03Na
HOOC-CX-SH
>-- CONX~ SH
~=~ \~CH2C6H5
~ SX
~/ HOOC -CX-C - SH
S03K ~6~5
HO~ SHH()OC -CH- (CH2 ) 2 -C~l-S~
>~/ SH COOH
HQOC~

-- 18 --
HOOC-C~2~ H N S~
ÇOOH [~
0
HOO(~ CH- SH
COOH
SH
KC~3~; N ,C~I ~3 ~ N~ N
H SH
OH
HC~OC ~H2 ~ ,~N
CH-SH 1~ ~
HOOCCH HO N SH
2 . N~2
~OOC ~
HOOC (CH2)4~ SH ' ~ ~
HO-CH2~CH2 N SH
~OOC (CH2) 4 ,CH SH M~N
~S-C~2-( H2 H~S~ SH
N~14-03$~ ~SH ~<~--NH
K03S~N~ SH 5t:)3R N SH
N S=C-NH2
HOOt:: J~N SH .s~ 6Hs
.~3, SH
HOOC HlY~
o~

2Z3~)at
-- 19 --
HOOC N
NH2 ~ SH
CH2COOH
N~ HOOC-CH2~r N
HS''~N OH N~h SH
H
SXX COOH
N SH SH
~2H4H ~ COOr
SH
~N C2H5~ OOH
SH ~ 2H5
C~2COOH SH
C2H5~C ~OOH
: HOOC~ N C4~I,9
N SH C5H~ COOH
H SH
~IOOC-CH-CH2 ~ N SH
NH~! N SX ~} '
H C2H5
H C
3 ~
HOOC S SH
.

30(~
-- 20 --
(ComponeIlt b)
NaO3S~ 2~X2-SS3M
K03S (Cx2) 3 SS03M
NaO35 (CH2) 4 SS03~
~aO3S -CH2 -CH2 -CH-SS03M
CH3
~aO3S (CH2) 7 SS03M
NaO3S-CX--CH2~, SS03M
C3~9 ~3
~aO3$ CH CH2 CH SS03~I
C6H~ ~I3
SS~3M
CH~,S03~a
2 3
503Na
NH
SS03M
NH2
0~
K03S~ SS03M
0~ .

~2~o
OH
03M
3Ss r
OH
OH
3 S S~l~,s S03M
: ~ .
: ~ ~ COCH2 SS03M
: HO ~
::
~ .. . OH _ ~
: HOOC-Ca-Cd2-SSO L~
~ 3
: NH2
:~ Na ~OC CH2 SS03M
HOOC-C~2-CH2-Ss03M
H2~-C~C~2-SS03~f
~2N C-CH2-CH2-s~o M
:~ 0 3
H2N-cH2-cH2-sso3M
~ OOH
.
,

o
-- 22 --
, ~ ~2CH~ S03M
CH N
3 ~ CH2C~12 - SS03M
~ C~2-C~2-SS03M
SO2 ~
C~2 -~H2 -sso3M
(CH2)4-SS03~
(C~2~ 4 SS03M
NH403S--1~3SO~ 2-C~2-SS03M
C:H20~
XO~C~2 -SS03M
H C
3~l Cl~
H00C (C~2) 3-SS03M
~: HOOC-CH2-CH-CH3
SS03~
}IOOC-CH2-CH-C6H5
SS03M
HOOC -CX2 -NH-C0 -CH2 - SS03M
,

~2
- ~3 -
HOO ~ ~ S SS03M
HOOC ~ CH2-SS03M
H2N-CH2-C~-CH2SS03M M = a monovalent cation,
OH prePerably the sodium,
potassium or ammonium
cation
The pr~erably aqueous developer solutions for
developing a photo~raphic material which has been exposed
image-wise, which are to be used accordIng to the inven-
tion~ can in other respects have the compositions known
per se.
For exampl~, they contain dihydroxybenzenes,
aminophenols, diaminobenzPnes, pyrazolidinones~ reduc-
tones or hydroxylamine derivati.ves as conventional com-
pounds which develop silver halideO
Conventional water-soluble silver halide solvents
are~ for example, thioethers or thioamides, salts of thio-
cyanic acid~ salts of sulfurous acid (sulfites) in high
concentration and, preferabl~, salts of thiosulfuric acid
(thiosul~ates)O ~he sulfites can, for example, as a
rule be employed in an amount o~ more than 20 g/l, and if
desired also in smaller amounts, for example 10 to 20 g/l,
and the thiocyanates and thiosulfates can be employed in
a concentration o~ 0.1 to 200 g/l, in the aqueous prepara~
tions.
The concentration of the thiosulfate is advan-
tageously 10 to 200 g/l when used in a monoba~h and 0.1
to 10 g/l ~or masking developers for silver dye-bleach
material. Suitable sulfur compounds are, in particular,
those of the formulae (9) to (15). The sulfur compounds
can also be used in developer preparations ~or reversal,

~5~
- 2~ _
chromogenic, X-ray or black-and-white ~ilm materials.
Components (a) and (b) are pre~erably added to the
aqueous developer preparation in amounts o~ 0.01 to 1 g/l
and of 0.1 to 10 g/l respectively.
Thus, suitable developer solutions contain, for
example, 0.1 to 20 g/l o~ the compound which develops
silver halide 9 0 . 1 to 200 g/l o~ the silver halide solvent
and 0.05 to 10 g/l of the combination o~ components (a)
and (b), th~ molar ratio o~ (a):(b) being 5:1 to 1:100
and preferably 1:1 to 1:20.
When preparing the aqueous developer preparations
of the present invention it proves advantageous to mix in
the combination o~ (a) and (b) some time before using the
developer solution. The quantity ratio of B~te
salts to mercapto compounds can be varied within the
indicated limit~.
The developer solutions can be prepared, for
example, from a single c,oncentrate or from separate con-
centrates of the compound which develops silver hal-
ide, the silver halide solvent and the combination of com-
ponents (a) and (b), and also, i~ desired, further compon-
ents, by diluting with water, which can be mixed with
organic solvents.
The concentrates can be in the ~orm of a liquid
or paste and i~ desired can also be in the solid form and,
per litre of concentrate~ can contain, for example, the
individual components in 2 to 25 times the amount in which
they are present in the ready-to-use developer solutions.
A very particularly valuable application of the
present process comprises developing silver dye bleach
material9 which has a layer build-up suitable for lowe~ing
the undesired secondary colour densities, with a developer
preparatlon o~ the indicated composition
Pre~erably, this relates to the process for the
production of masked, subtractive, p~sitive coloured
images by the silver dye-bleach process, by exposure,
silver developing, dye-bleaching, silver-bleaching and

o~ `
- 25 -
~ixing and with the use o~ a photographic material whichcontains one image w~se bleachable dye in each of at least
two layers, the absorption maximum o~ each d~e corres-
ponding to one of the three primary colours red, green and
blue and a silver halide emulsion layer sensitive in a
speci~ic spectral region being assigned to each dye, and
a silver halide ~mulsion layer which at least partially
consists o~ silver iodide being assigned, in this material,
to the dye which has the undesired secondary colour den-
sity which is to be compensated, there being at least a
second dye, which has a main colour density which corres-
ponds to a secondary colour density, of the first dye,
which is to be ~ompensated, and a silver halide emulsion
which is ~ree from iodide ions in a further layer and,
moreover, a ~urther layer, which is adjace~t to that con-
taining the second dye, containing colloidal nuclei which
are capable o~ depositing metallic sil~er ~rom soluble
silver complexes and a septum being located between the
layer containing the nuclei and the dye layer which has
the secondary colour density which is to be compensated,
and the silve~ deYeloping bath with which the material is
to be treated after exposure has taken place containing a
ligand, which is able to produce water-soluble and
dif~usible silver complexes, as well as a combination o~
the compounds of the formulae (l) or (2) and (3).
Particularly pre~erred comb~ations are those of compounds
of the formulae (13) and (15)1
The mixtu:res, to be used according to the inven-
ti.on, of mercapto compounds and Bunte salts are distin-
guished, in~er alia, by the fact that they prevent the
deposition o~ silver in developer solutions for an aston-
ishingly long time. In contrast to the anti-sediment
agents used hitherto, the mixtures of (a) and (b), which
are used according to the invention, are otherwise photo-
graphically virtually inactive and very stable under the
customary conditions, and this is advantageous in particu-
lar ~or a continuous procedure using the developers des-
,

- 26 -
cribed.
In the examples which follow parts and percent-
ages are by weight.
Example 1
A photographic material for the silver dye-bleach
process is prepared on a pigmented cellulose acetate base
using the cyan image dye of the formula
(101)
~3Co-NH OH O~C~3 ~ HN-OC~3
~ N=~I~N=N~q
HO3S~ SO3H H3C-1 HO3S SO3H
in the red-sensitised bottommost layer, the magenta dye
of the formula
(102)
H03S S03H
-N=N ~ N~l-OC ~ H-C-H~ ~ C0~
NH2 H3S . S03~ ~2N
in a green-sensitised layer above this and the yellow
dye of the formula
~103)
~03S H3C . CB3 S03H
N=N ~ ~-OC ~ 0-HN ~ N=N
S03H CH3 H3C H03S
in a blue-sensitive layer which is above the magenta layer.
- The photographic material used is buil~ up as

~2
- 27 -
follows ~cf. German O~fenlegungsschri~ten 2,036,918,
2,132,836 and 2,547,720)
Gelatin protective layer
Blue-sensitive, iodide-free AgBr emulsion
Yellow dye (103) + blue-sensitive, iodide-free AgBr
emulsion
~ellow ~llter: yellow Ag hydrosol (40 mg/m )
Green-sensitive AgBr/AgI emulsion
Magenta dye (102) + green~sensitive AgBr/AgI emulsion
Intermediate layer (gelatin)
Cyan dye (101) + red-sensitive AgBr/AgI emulsion
Red-sensitive AgBr/AgI Emulsion
Cellulose triacetate base, white opaque
Backing, gelatin
The layer build-up enables the blue secondary
colour densities of the cyan dye and magenta dye to be
corrected by additional bleaching of the yellow image dye
as a ~unction o~ the bleaching o~ the two other image
dyes (blue-sensitive la~er with yellow dye iodide-free;
other dye layers with iodide-containing emulsion).
The nuclei-containing layer is adjacent to the yellow
dye layer. It addition~lly contains a yellow light filter
dye and is separated from the magenta layer ~y a colourless
emulsion layer ~green-sensitive AgI-contalning emulsion
layer, which at the same time is the separating layer).
The iodide-containing emulsion layers contain
crystals with 2.6 mol % o~ silver iodide and 97.4 mol % o~
silver bromide. The image dyes are used in a concen-
tration such that their reflectance densities are each
2.0; the total silver content o~ the 22 ~ thick layers
is 2.0 g/m .
A coloured slide is copied on this material in an
enlarger. The exposed material is processed in accord-

~2
- 28 -
a~ce with the ~ollowing instructions (French Patent
Specification 2,247,755). The processing temperature
is 30C.
3 minutes
tetrasodium salt o~ ethylenediamine-
tetraacetic acid 2 g/l
85~ potassium hydroxide 30 g/l
boric acid 16 g/l
potassium metabisulfite 26 g/l
l-phenyl-3-pyrazolidinone 0.3~ g/l
hydroquinone 5 g/l
benztriazole 0 . 8 g/l
potassium bromide 2 g/l
anhydrous sodium thiosul~ate 0.8 g/l
compound of the formula (104) o. 5 g/l
compound o~ the formula (105) 0.85 gjl
(104) ~ CH~ 2-C.~ (component (a))
(105~ ~ CH-CH2-COOH (component (b ) )
SS03K
L~5 1 minute
5 minutes
sul~amic acid 100 g/l
sodium m-nitrobenzenesulfonate 10 g/l
l-thioglycerol 1 ml/l
potassium iodide 6 g/l
2~3,6 trimethylquinoxaline 2 g/l
1 minute
~5~ h 4 mlnutes
ammonium thiosulfate 250 g/l
potassium metabisullite 50 g/l
85% potassium hydroxide 20 g/l
6. _Washing 6 minutes

~ ~Z8~DO
-- 29 --
Total processing time 20 mi~utes
The re~lection print o~ the slide which is
obtained a~ter drying is distinguished by ~aithful re-
production of the tonalities and by unadulterated colour
reproductionO
As a result o~ the addition o~ the two compounds
(~ormula (104) and formula (105)), the developer is usable
for a relatively long time. Even a~ter processing
several colour enlargements 9 the solution remains clear,
i.e. free from the deposition of metallic silver~
I~ only the com~ound of the ~ormula (104) is added
to the developer, the solution does indeed remain clear
for a relatively long tîme, but the developer charac-
teristics are changed: in the developed colour printing
material, the yellow gradation in the shadows is too ~lat;
the grada-tion equilibrium is thus disturbed. Colour
prints processed with this developer have fewer saturated
yellow tones. Moreover, darker parts of the image
appear bluish~tinged.
If the developer contains only the compound of
the formula (105), the solution becomes decolorised a
short time after it is used; metallic sil~er separates
out.
In place of the combin~tion of the compounds o~
the formulae (104) and (105), it is also possible to
employ other combinations of mercaptans and Bunte salts
from the tables given above.
~ .
Material for the silver dye-bleach process is
processed in accordance with Example 1 but the compounds
of the formulae
(106) CH3 - CH - CH~ - COOH 0.5 g/l
SH
(107) CH3 - CH - CH2 - COOH l g/l
S - S03K

~2 8
- 30 -
are used in the silver developing bath.
The developing -tim~ is 2 minutes at a temperature
of 30~C. A~ter drying, re~lection prints of good
image quality are obtained. Even when the developer
is used repeatedly (total of 0,1 m2 of material per litre
of solution), no change in the image ~uality and no tur-
bidity in the solution are to be found.
~.~}
A black-and-white developer of the following com-
position is prepared:
potassium carbonate 30 g
sodium sulfite 100 g
potassium bromide 3 g
h~droquinone 40 g
ethylenediaminetetraacetic acid 1 5
(disodium salt) ' g
potassium hydroxide 17 g
water to make up to l litre
The solution is divided into two 500 ml portionsA and B.
O.~ g of the compound of the ~ormula (104) is
added to portion A.
0.5 g of 2-aminoethane-thiolsulfonic acid and
0.5 g o~ the compound of the ~ormula (104) are added to
portion B.
Black-and-white camera films are developed with
these solutions. Portion A remains clear for a certain
tlme but turbidity due to a silver sediment can then be
observed. The developer characteristics of this solu-
tion change in the manner indicated in Example l.
Portion B, on the other hand9 remains clear and
retains its good developer characteristics even a~ter pro
longed use~
A black-and-white developer of the ~ollowing com-
positio~
4-methylaminophenol sulfate 2 g

~5;28
_ 31 -
hydroquinone 5 g
sodium sulfite (anhy~rous) 100 g
borax 3 g
water to make up to 1 litre
is mixed with 005 g of the compound of the formula (104)
and 0.85 g of the compound of the formula (105).
Black-and-white camera films are each developed
~or 6 minutes at 20C with thi~ solution in a tank.
After a total of 10 ~6 exposure, size 135 ~ilms have been
developed 9 the solution starts to become exhausted and
must either be regenerated or replaced by fresh solution.
In contrast to a developer solution which has been pre-
pared without the addition of the compounds of the
formulae (104) and (105), there is still no trace of the
formation of silver sediment at this timeO