DE2161818A1 - Photographic material containing nitro compounds for use in silver dye bleaching processes - Google Patents

Description

CIBA-GEIGYAG, CH-4002 Dasol

Dec 13, 1371

(" Case TEL 5V? / E ) Attorney's file 21 713

Photographic material containing nitro compounds for the silver dye bleaching process (addendum to the patent ... (patent application 19 17 813.3) :)

Subject of the main patent

(Patent Application Nr-. 1917813.3) i _s t a photographic material for the silver dye bleach process, the bleaching in at least one layer of silver

209829/0884 bad original

~ 2 -

contains barable azo dye, characterized in that there is at least one at most in at least one layer weakly colored aromatic or heterocyclic nitro compound the formula

^J r

contains, in which Λ an aromatic or heterocyclic radical with at most 2 rings and 5 to 6 members per ring, B an at least eight-membered organic radical, D and E each an acidic, water-solubilizing group, m, η and ρ each denotes an integer with a value of at most 3 and q and r each denote an integer with a value of at least 1.

The present invention is a photographic, in at least one layer one through Silver bleachable azo dye-containing material for the silver dye bleaching process, and this material is thereby characterized in that there is at least one nitro compound of the formula in at least one layer

209829/0884

^BATH

(D

-H ₂ O (-

contains, where A contains 1 to 2 sulfonic acid groups, at most bieyclischen aromatic radical, R ,, RΛ Rp and Rp ¹ each a benzene radical, U, U ', V- and V ^! each a -CO-HN- or -SOp-HN- group and m, q, r and s each represent one of the numbers 1 and 2.

These nitro compounds thus correspond to one of the formulas, depending on whether m and q are 1 or 2

(1.1)

HJ'-R ₂ 'K-N0 ₂ ) _s

l <m <2; q = 1

(1.2)

Hj ₁ -E ₂ ) (-NO ₂ ) _B

m = 1; q = 2

(1.3)

(0 ₂ N-) _r (R ₂ -U-)

] n

) (-ITO ₀ I.

^ K-U'-R ₂ ') (-NO,

m = q = 2

BATH ORIGINAL

where A, R-, R, ¹ , Rp ¹ , U, U ^! , V, V ', r and s have the meaning given. The -CO-HN- and -SOp-HN- groups present in such a compound can, independently of one another, be bonded to the adjacent carbon atoms in any one of the two possible arrangements, for example in the arrangements -CO-HN-A-NH -OC-, -NH-OC-A-CO-HN-but also -CO-HN-A-CO-NH-. However, preference is given to the nitro compounds which have a certain or complete symmetry, for example those of the formulas (II), (1.2) and (1.3), in which [(0 _p N-WR _p -U) 3 equals [(-U ' -R _p ') (-NOp)]

CL L CZ. Cü CZ. £>

and q has the value 2, where A is connected to two - NH groups, two —CO groups or two —SOp groups can be bonded. As largely completely symmetrical in relation to A can be the compounds of the formula

!) - (O N-) (R -X-HiI-)

[E ₁ -Y-HH - ^ -.
(m-1) (ql) + l

be considered, in which A contains a 1 to 2 sulfonic acid groups, at most bicyclic aromatic radical, R and R are each a benzene radical, X and Y are each a -CO- or -SOg- group and m, q. And r each mean one of the numbers 1 and 2.

The following formulas (3) to (6) contain preferred embodiments, with symbols already defined always have the same, specified meaning.

20982Ü / 0884

BATH ORIGINAL

(3)

-Y-HN-

U-I) (2-I) -I-I

A ₁ -

(-IiH-XR ₀ ) HiO ₀ )

2 ^y r

(m-

A denotes one containing 1 to 2 sulfonic acid groups Benzene-j diphenyl, naphthalene or diphenyl radical;

η ι

'-HIT- k _n -NH-Y-

Ap denotes a benzene or diphenyl radical containing 1 to 2 sulfonic acid groups, Z and Z ¹ each represent a hydrogen atom or a methyl group and η is 1 or 2;

No. ¹

_-> - 50 ₂ -HN.

(o ₂ ok _r

No. ¹

No. ¹

HO _V S

SO ₃ H

MO ₂ SUN (NO ₀

. 209829/0884

In the individual benzene residues there are on the one hand the -NH and the -CO- groups, on the other hand also the -SOp- and OpN groups in the m or p position to one another.

The nitro compounds of formulas (1) to (6) can be prepared by customary methods known per se will. For example, A) a nitroaraino compound of the formula

(7.1) O ₂ NA- NH ₂

with an acid chloride of the formula

(7.2) Acylate Cl -.YR- NO ₀ (Y = SO ₂ or CO), the resulting dinitro compound- (7-3) O ₂ N - A - NH - Y - R ₁ to the diamine

(7.4) H ₂ N - A - NH - Y - R ₁ - ₂

and reduce this by diacylation on the two amino groups with an acid chloride of the formula

(7.5) (O ₂ N) ₁₁ (R ₂ -X-Cl)

into the compound of the formula

(7) E (O ₂ NJ ₁₁ (R ₂ -X-MH-) 3-A-NH-YR ₁ - [C-HN-XR ₂ ) (-N0 ₂ ) _r ]

convert.

209829/0884

B) Furthermore, by acylation with an acid chloride of the formula

(8.1) Cl-Y-A-Y-Cl

from a nitroamino compound of the formula

(8.2) O ₂ N -R ₁ -NH ₂ .

the dinitro compound

(8.3) O ₂ N - R ₁ - NII - Y - A - Y - HN "- R ₁ - · and then from the reduction product (8Λ) H ₀ N -R-, -NH-Y- A '-Y- HN -R ₁ - NH,

and an acid chloride of the formula (8.5) (0 ₂ N-) _r (R ₂ - X - Cl)
the compound of formula

(8) [(0 ₂ N-) _r (R ₂ -X-HN -)] [R ₁ -NH-Y -] - A - [- Y-HN-R ₁ ] [(-NH-XR ₂ ) (-:

can be obtained.

C) Those compounds of the formula (2) in which q is 2 are particularly readily accessible. You get them by making a diamine of the formula

(9.1) H ₂ NA-NH ₂

with a dinitrobenzoic acid chloride or preferably a mononitrobenzoic acid chloride of the formula

(9.2) ^t0 2 ^M " ^] m R ₁ - Y - ^C1

diacylated, the tetra- or dinitro compound (9-3) [OpN-L R ₁ -Y-HN-A-NH-YR [-NO ₀ ]

209829/0884

to the corresponding amine of the formula (9.4) CH ₂ NI _1n R ₁ -Y-NH-A-HN-YR ₁ [

reduced and this in a molecular ratio of 1: 2m with an acid chloride of the formula

(9-5) (0 ₂ N-) _r (R ₂ -X- Cl) condensed:
^ (9) C (OpN-) (R -X-HN-)] [R -Y-HN -] - A - [- NH-YR, 3 I (-HN-XR) (- NO)]

£ m x cm 111 J- Ju t— C * x Hl

In method A), for example, 1-methyl-2-amino-6-nitrobenzene-4-sulfonic acid can be used Use as starting material (7 · 1). In method B), e.g. benzene-3j5-dicarboxylic acid di-chloride-1-sulfonic acid is suitable as starting materials of the formula (8.1). The following compounds are examples of diamines of the formula (9 * 1) called:

3,3'-trolidine-6,6 ¹ -disulfonic acid, benzidine-2,2'-disulfonic acid, 4,4'-diamino-3,3'-dimethoxydiphenyl-β, β'-disulfonic acid, 4,4'-diaminostilbene -2,2'-disulfonic acid, ■ 2,6-diaminotoluene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 2,6-diaminonaphthalene-4-sulfonic acid, 1,6-diaminonaphthalene-4-sulfonic acid, 1 , 4-dianiinobenzene-2,5-disulfonic acid.

The following mononitro compounds, for example, come into consideration as nitro group-containing acid chlorides of the formula (7.2):

4- and 3-nitrobenzoic acid chloridej 4- and 3-nitrobenzenesulfonic acid chloride, 4-nitro ~ 2-chlorobenzoic acid chloride, ^ -nitro ^ -chlorobenzoic acid chloridej 4-nitro-3-chlorobenzoic acid chloridej 3-nitro-5-chlorobenzoic acid chloride, 4-nitro-2-methylbenzoic acid chloride., 5-nitro-2-methylbenzoic acid chloride j S-nitro - ^ - methylbenzoic acid chloride j 3-nitro - ^ - methylbenzoic acid chloride, 4-nitrotoluene-2-sulfonic acid chloride, 5-nitrotoluene-3-sulfonic acid chloride, 2-nitrotoluene - '! - sulfonic acid chloride, 4-nitro-2-methoxybenzoic acid chloride j 5-N2tro-2-methoxybenzoic acid chloride, 4-Ntro-3-methoxybenzoic acid chloride j 2-Nitro-1-methoxybenzo-4-sulfonic acid chloride j 5-chloro-3-nitro-4-methylbenzoic acid chloride, o-chlorine - ^ - nitrotoluene - ^ - sulfonic acid chloridej, 4-Nitro-2-ethylbenzoic acid chloride j 3-Nitro-4-isopropylbenzoic acid chloride.

These mononitro compounds can also be used as starting materials of formulas (7-5)., (8.5), (9-2) and (9-5) uses v / earth. Dinitro compounds also come here such as 35-D.! nitrobenzoic acid chloride or 2,6-dinitrotoluene-'l-sulfonic acid chloride into consideration.

For example, the following di- or tetranolro-compounds can be produced using the methods given above:

2 0 I ',; 2 9/0 a OA 'BAD ORIGINAL

Method a

O ₂ N CH

(11) <Z> - CO - IIN - A - mi - OC

O ₉ NT

^c SO H

Method B NO,

- -ην-oc

(12)

O ₂ N

CO-NH-OC-fyCO-HN-K > -ΝΗ-0

Method c

CO-HN-

SO ₃ H

(14)

O ₂ N

SO II

SO ₃ II

209029/0

-CO-HN-

SO ₇ Ji 3

T J

'° 2 ^N

O ₂ S-HN

SO ₅ H ^

O ₂ N

O ₂ S-HN-

SO ₃ H

3 ._

OC-HlT-

SO ₅ H

209829/0884

<_> -CO-HN- < > -C0-

-HN

-NH

<Ρ °

OC-HN

SO ₅ H

O ₂ N

O ₂ N

SO ₅ HY

OC-HN SO-II 5 _

OC-HN- <Z> 209829/0884

° ² L

<TI> -CO-HH

° 2 ^Ή

co

co-NH

I ρ

-NH

SO ₅ H

-NH

OC-HN

SO ₅ H

In the above formulas, the sulfonic acid groups are entered as HO., S groups. The products concerned ' can optionally receive salts in the form of sulfonic acids or be converted into such.

The nitro compounds of the formula (I) are completely colorless and generally per se or in the form of their alkali salts soluble in water or in a mixture of water and an organic solvent, preferably methanol. When incorporated into gelatine, they dry with it, even if they are present in the gelatine in dispersed form, crystal-clear on.

209829/0884 BATH ORIGINAL,

- lk -

In a multilayer material, the nitro compounds of the formula (I) are used depending on the desired effect added to all layers or only to the individual emulsion, dye, emulsion dye, intermediate or auxiliary layers. In the case of mixed grain emulsions, the nitro compounds of the dispersed phase and / or the binder layer, which serves as a matrix. Intermediate layers are primarily separating layers to understand and as auxiliary layers come sliding layers, protective layers, filter layers, antihalation layers, but also coatings, sub-layers and. Barytageη into consideration.

A particular advantage of the compounds of the formula (I) is that they are due to their diffusion resistance remain in the layers to which they are added and therefore neither migrate into the baths nor into the neighboring layers undesirably affect. Their diffusion resistance also prevents migration in the layer, so that only the Nitro compound at the place itself to act can come.

The use of the nitro compounds of the formula (I) in the intermediate layers when using bleach catalysts a function that improves image quality. It is known that the bleaching catalysts ground during the bleaching process by metallic silver to form hydro compounds

20.9829 / 0884 - _MNJ . _L.

OBlGlNAL

reduced, which then cause the dye to bleach with reoxidation. The reduced form, as far as it is The bleaching process does not work immediately, migrates to the neighboring layers and causes an undesirable and undesirable there harmful lead of the image dye. The nitro compounds in the intermediate layers prevent this harmful effect by preventing the migrating from the layer oxidize reduced catalyst.

The colorlessness of many nitro compounds of the formula (I) is particular when used in reflective materials important, where the eye for -even little felicity is particularly sensitive. For example, has an 8 * 10 "molar aqueous solution of the compound of the formula (23 / practically no more absorption in the visible area. The molar absorbance at 400 nm is only 206.5. In contrast to quinones and nitroso compounds, these nitro compounds are stable compounds that are formed when exposed to light suffer no change.

The nitro compounds do not react with developing substances such as under normal development conditions for example with hydroquinone. The diffusion-resistant and Soluble nitro compounds can be produced easily and cheaply. .

209829/0884

BATH ORIGINAL

The nitro compounds of the formula (I) offer a particular advantage as an additive to separating, filter or Antihalation layers, the colloidal silver or diffused Contain halogen silver emulsion.

The use of such layers in the silver color lead process material was previously opposed to the fact that this silver in the bleaching process the color lead catalyst in the reduced form transferred to the neighboring layers migrates and causes color bleaching in unexposed, i.e. silver-free areas. If you now set one of the nitro compounds of formula (I) the filter or antihalation layer en, then when the colloidal silver is lead or that when developing from the pre-exposed silver halide formed silver either the catalyst is not reduced or the activated catalyst generated immediately oxidizes again and can no un- in the nearby perch. produce desired dye bleach.

The Ni troverbin fertilize the formula (l) can without Disadvantage also being incorporated into the layers, especially the auxiliary layers, in excess.

By using the nitro compounds of the formula (I) in protective and top layers, the enrichment the reduced form of the color bleaching catalyst in the corresponding bath, in which otherwise the catalyst concentration difficult to keep constant.

2 0 9 8.: 3/0 8 8 4

BATH ORIGINAL

If the nitro compounds of the formula (I) are added to the dye-containing layers, the nitro compounds appear competes with the dye during the bleaching process, generally flattening the gradation is caused in the paint layer.

209829/0 3 84

Manufacturing specification Λ

AI 17.2 g benzidine-2,2'-disulfonic acid (23.1 g are heated to 70 ° C. with 100 ml v / ater and adjusted to pH 8.0 with sodium carbonate. A solution is added within J> 0 minutes of 46 g of p-nitrobenzoyl chloride in 200 ml of acetone, the pH being kept at 8 to 8.5 with sodium carbonate, the temperature is then increased to 9 ° C. so that the acetone evaporates, then 200 ml of water are added to, cooled to 10 ° C, filtered off and washed with 50 ml of -.. for water and 200 ml of ethanol Without to dry the product in 300 ^m l of boiling v / ater is dissolved in pH, treated with 5 g activated carbon and filtered off with suction the The filtrate is adjusted to pH 9 with sodium carbonate, mixed with 10 g of sodium chloride, cooled to 10 ° C; the precipitated crystals are filtered off with suction and washed with 50 ml of 5/6 sodium chloride solution and then with 100 ml of alcohol.

Yield: 28 g

A.2. 20 g iron powder, 20 ml hydrochloric acid conc. and 40 ml v / ater are heated on the steam bath for 1 hour. 80 ml of water and 23 g of product A.I. are then added. too, heated Hours of stirring at 90 °, sets up with lithium carbonate pH 9j sucks off hot and washes with 50 ml of water.

209829/0884

The piltrate is cooled to 10 ° C with concentrated Hydrochloric acid adjusted to pH 0.5, filtered off with suction, washed with 100 ml of water and the filter cake at 100 C im Vacuum dried. After recrystallization from 90% pyridine, 17.6 g of colorless crystals are obtained.

A.3. 50 g of product A.2. are suspended in 7OO ml of pyridine and 130 g of p-nitrobenzoyl chloride are added over 3 hours at boiling temperature. If amine can still be detected by a diazotization sample, the addition of p-nitrobenzoyl chloride is continued. It is suctioned off at 100 ° C. and washed with 500 ml of hot pyridine and then with 500 ml of methanol. After recrystallization from ⁰⁰ 3 rol dimethyl sulfoxide are obtained 80 g of bis- [p.-nitrobenzoyl-p-aminobenzoyl] 2,2'-benzidindisulfonsäure of formula (13) ·

A. h. If the p-nitrobenzoyl chloride in A. 3. is replaced by m-nitrobenzoyl chloride / then the product of the formula is obtained

A.5 If you replace in

3 * 5-dinitrobenzoyl chloride, then the product is obtained of formula (I5) - -

2098 2 G / 0834

^μ BAD ORIGINAL

Manufacturing specification B

BI 43 g benzidine ~ 2.2 ^! ~ Disulfonic acid are suspended in 3OO ml of water and brought into solution with sodium carbonate at pH 7.5. The mixture is heated to 80 ° C. and a solution of 58 g of m-nitrobenzenesulfonyl chloride in 20 ml of acetone is used at this temperature. within one hour, keeping the temperature at 80 ° C. and the pH at 7.5 to 8 by adding sodium carbonate. The acetone distills off. At the end of the reaction, crystals separate out. It is filtered off with suction while hot and washed with 100 ml of water and 50 ml of methanol and dried at 100 ° C. in vacuo. 56 g of this product are heated to boiling in 100 ml of water while stirring, and glacial acetic acid is slowly added at the boiling point until a clear solution is formed. It is cooled to 5 ° C., filtered off with suction and washed with 50 ml of water; dries at 100 ° C in a vacuum.

B.2. 20 g iron, 20 ml hydrochloric acid conc. and 20 ml v / ater are stirred and added to the steam bath for 1 hour slowly a solution of 23 g of product B.I. in 200 ml Glacial acetic acid and 20 ml of water are added. The mixture is heated for 2 hours

209829 / 08.8-4.

on the steam bath and sucking off hot, then you add the filtrate with 10 ml of hydrochloric acid and 2 l of water, cools to 20 ° C., filtered off with suction and washed with 200 ml of water. The filter cake is dissolved without drying in 100 ml. Ice acetic acid and 10 ml V / water at the boiling point. A possible Congo acid reaction is removed with a little potassium acetate, vacuumed off hot, then cooled The filtrate is reduced to 70 ° C., 10 ml of hydrochloric acid are added and 500 ml V / ater, sucks off, washed with 100 ml of water and dried at 60 ° C in a vacuum. You win that resulting product by dissolving in 50 ml of pyridine at 50 ° C, filtering and slowly in 250 ml to 5 ° C * Stir in cooled isopropanol, stir for 1/2 hour, suction off the precipitate, wash with 50 ml isopropanol and drying at 100 ° C in vacuo.

Yield ϊ- 17j5 6

3 * 26 g of product B.2. are suspended in 30 ml of pyridine and treated with 2 g of p-nitrobenzoyl chloride at the boiling point. When amine can no longer be detected by diazotization, the mixture is stirred into 200 ml of isopropanol cooled to 10 ° C., filtered off with suction and washed with 20 ml of methanol. The product of the formula (16) is boiled with 30 ml of methanol and 1 ml of 27% ammonia for 2 minutes, then evaporated to 20 ° C.

2 0982 9/088 4 'BAD ORIGINAL

cools, filtered off with suction, washed with 30 ml of methanol and at 100 ° C dried in vacuo: Formula (ΐβ).

B. ^. If one replaces in B.3. the p-nitrobenzoyl chloride through 3,5-dinitrobenzoyl chloride, then this is what you get Product of formula (17).

B.5 Replace the p-nitrobenzoyl chloride in B.3 with 'm-Nitrobenzenesulfonic acid chloride is then obtained in

analogously the product of the formula (18).

Manufacturing instruction C

Cl. Production of up to ~ [m, m '-diaminobenzoyl-benzidine-2,2'-disulfonic acid] analogous to A.l. and A.2.

C. 2. 20 g of product Cl. are suspended in 200 ml of pyridine and ² g of I>, 5-dinitrobenzoyl chloride are added at 105 C 3. 500 ml of isopropanol are then added, the mixture is filtered off with suction at 20 ° C., washed with isopropanol and dried at 100 ° C. in a vacuum. The compound of the formula (19) is obtained.

209829/0884

Manufacturing instruction JD

DI 20.2 g of 2,6-diaminotoluene-4-sulfonic acid are dissolved in 100 ml of pyridine at 100 ° C. and 30 g of p-nitrobenzyl chloride are slowly added. The reaction solution is then stirred into 200 ml of concentrated hydrochloric acid and 500 g of ice , the precipitate is filtered off with suction and washed with 1 liter of water. It is dried at 80 ° C. in a vacuum. The product is boiled with 300 ml of methanol while stirring for 10 minutes, suction filtered while hot, washed with 100 ml of methanol and dried at 80 ° C. in vacuo.

Yield: 29 g.

D.2. 72 g of product DI are dissolved in 800 ml of V / water with the addition of sodium carbonate at pH 8.5. This solution is slowly added to a boiling mixture of 70 g of iron, 70 ml of concentrated hydrochloric acid and 200 ml of water. The mixture is boiled for 5 minutes, adjusted to pH 9 * with sodium carbonate, filtered off with suction while hot and the residue is washed twice with 100 ml of hot water. The filtrate is adjusted to pH 2 with hydrochloric acid, cooled to 20 ° C., filtered off with suction and washed with 200 ml of v / ater.
Yield 59g.

209829/0 884

DJ 10 g product D.2. are dissolved in 50 ml of N-methylpyrrolidone at 100 ° C., and 150 ml of pyridine are added. At 100 ° C., a solution of 20 g of 3,5-binitrobenzoyl chloride in 100 ml of benzene is added dropwise. The reaction solution is stirred into 1 l of methanol , filtered off with suction, washed with 300 ml of methanol and dried at 80 ° C. in a vacuum. This product is dissolved in 50 ml of N-methyl-pyrolidone at 100 ° C., filtered off with suction while hot, and 15 ml of methanol are added to the filtrate. It is cooled to 5 ° C., filtered off with suction, washed with J> 0 ml of methanol and the product of the formula (20) is dried at 80 ° C. in a vacuum.

Yield: 11 g.
Creation rule E

Bl 18'g _4> 4'-diamino-3,3'-dimethyldiphenyl-2,2-di- ^r "· sulfonic acid are ER- with 100 ml of water at 80 ° C. Warms and adjusted with sodium carbonate to pH 8. Then a solution of hS g m-nitrobenzoyl chloride in 200 ml of acetone is added within 30 minutes, the temperature is increased to 90 ° C., maintained at this temperature for 20 minutes and the acetone is allowed to distill off, then 200 ml of water are added and the mixture is cooled 5 ° C, sucks off the precipitated crystals and washes with 30 ml

98 29/038 4 BATHROOM _{0R 1GINAL}

Water and 100 ml of methanol. The product is dissolved in 350 ml of water at 90 ° C. with 5% activated carbon offset and sucked off. The filtrate is adjusted to pH 9 with sodium carbonate, with 10 g of sodium chloride added, cooled to 10 ° C, the precipitated crystals v / earth suction filtered and with 50 ml 5% sodium chloride solution and 100 ml of methanol.

Yield: 25 g

E.2. 20 g of iron powder, 20 ml of concentrated hydrochloric acid and 100 ml of water are heated on the steam bath for one hour, then 00 ml of water and 20 g of product E1 are added, heated for 3 hours at 90 to 95 ° C. with stirring, and made up with sodium carbonate pH 9 / sucks off hot and washes with 50 ml v / ater. The piltrate is adjusted to pH 0.5 with concentrated hydrochloric acid, cooled to 5 ° C., the precipitated crystals are filtered off with suction, washed with 100 ml of v / ater and dried at 100 ° C. in vacuo. After recrystallization from 90% pyridine , 14.5 g of colorless crystals are obtained.

E.3- 50 g of product E.2. are in 700 ml of pyridine

100 ° C. and 30 g of m-nitrobenzoyl chloride were added over the course of 2 hours. If amine can still be detected by a diazotization sample, the 2 0 9 8 2 9/0884

BATH ORIGINAL

Addition of m-nitrobenzoyl chloride continued. After cooling to 20 ° C., the reaction mixture is introduced into a mixture of 150 g of ice and 700 ml of concentrated hydrochloric acid, filtered off with suction and washed with 4 l of water and dried in vacuo at 80 ° C. The product is recrystallized from dimethyl sulfoxide. Of formula (21), we obtain 52 g of bis- [m-nitrobenzoyl-m-aminobenzoyl-tolidine disulfonic acid ^t 2J2.

Manufacturing specification P

Fl production of m, m'-diaminobenzoy.l-benzidine
2,2'disulfonic acid analogous to A.Γ and A.2.

F.2. 20 g of product F.I. are suspended in 200 ml of pyridine and at 105 ° C 28 g of 3,5-dinitrotoluene-4- sulfonic acid chloride added. ·

If amine can still be detected, acid chloride is also added. When the amine can no longer be detected, the condensation product is precipitated with 500 ml of isopropanol, filtered off with suction and washed with 100 ml of isopropanol. The residue on the filter is heated to 9 ° C. with 500 ml of water, cooled, filtered off with suction, washed with 200 ml of water and the product of the formula (22) thus obtained is dried at 60 ° C. in a vacuum.
Yield : 17g

209829/08 84

example 1

9 * 9 ral of a bromoiodosilver emulsion / containing 8 % gelatin, are diluted with 9.9 ml of 6 # gelatin solution, with 3 ml of a solution of 2,4-dichlorotriazine-6-mphenylsulfonic acid sodium, 6 ml of water and 1, 2 ml of an aqueous solution of the dye. formula

OH

-CO-NH H-CO

OH ^J

IaO ₅ p

MaO "S SON 5

offset. This emulsion is divided into 3 parts; a part remains treated as O-sample (= A); the second part (= B) is mixed with 0.25 ml of a n / 50 aqueous solution of the ammonium salt of the compound formula (23), the third part (= C) with 0.25 ml of a n / 50 v / aqueous solution Solution of the ammonium salt of the compound formula (22) added. The 3 emulsions A, B and C are each placed on a glass plate in the format I3 cm. 18 era poured and dried at 38 ⁰ C for 2k hours. A strip from each plate is exposed under a silver wedge and developed and subjected to the silver dye bleaching process as follows:

209829/0884

Ö.minutes developer

a) Na sulfite anhydrous hydroquinone

Na metaborate (ty H ₀ O) borax (12 H ^ O] potassium bromide
Benzotriazole

b) V / a s s er

1-phenylpyrazolidone

a) + b) fill up

700 ml 50 G 6th G 15th S. 15th G 1 G ο, 1 g 100 ' ml 0, 25 g 1000 ml

Minutes of darning fixation bath

Sodium thiosulphate crystallizes Na sulphite anhydrous Na acetate (3 H ₀ O) glacial acetic acid
Water on

Water ty minutes

Minutes of parbone bleach

Sulfamic acid

Sodium hypophosphite crystallizes

Potassium iodide

Catalyst: 2,3-dimethylquinoxaline

Water on

G

15 g

25 g

13 ml

ml

60 g Ig 35 g 45 mg ml

209829/0884 ORIGINAL INSPECTED

Soak for 2 minutes, silver bleach bath for 2 minutes

Potassium ferricyanide Potassium bromide Na phosphate prim. (I. Na acetate (3

V / a sser on

75 g 15 g 10 g

5 g 1000 ml

Soak for 2 minutes, fix bath for 4 minutes

Approach is the same as that of the darning-fix bath. Soak for 8 minutes.

. If the color curves obtained are measured with a spectrophotometer, the table below shows the Color densities.

stages 1 Density of the steps in percent Substance of measured in the Max. 2 Formula (23) Substance of 3 Sample B - Formula (22) - 4th Sample A .74 io Sample C 5 22 ° / o 81 io 84 io 46 io 86 % 87 % 64 ^c / o 96 * 92 io loo % 96 * loo # 100 ok

20.9829 / 0884

It can be seen that the nitro compounds of the formula (23) and (22) bleaching the dye by activating * -.

As far as possible, prevent the catalytic converter. "'~

Similar results are obtained with the compounds of the formulas (II), (16) and - '(24).

Example 2 ■

> ■ '. ■ ·. ■■■■■■.

9.9 ml of a bromoiodosilver emulsion containing 8 % gelatin are diluted with 9 * 9 ml of oily gelatin solution, with 3 ml of 1 solution of 2, ^ - dichlorotriazine-6-mphenylsulphonic acid sodium, 9 ml v / water and 1.2 ml of a liquid solution of the dye of the formula

offset. This emulsion is divided into the three parts A, B, C. A remains as a blank sample, B is mixed with 0.25 ml of an n / 50 solution of the ammonium salt of the compound of formula (23) and C with 0.25 ml of an n / 50 solution of the ammonium salt of the compound of formula (22) are added. The three emulsions A, B and C are grounded each on a glass plate in the form of I3 cm. 18 cm cast and dried 2h hours at 38 ^0C. One strip each

20982 9/0884 T "

ORIGINAL INSPECTED

the plate is exposed under a silver wedge and as in Example 7 given, treated with the developer and stopper tape, soaked, dried and the silver density of the steps measured under a green filter. Then these wedges are added to the bleaching process, as indicated in example 1, subjected, and now the dye density of each Levels measured under a red filter.

If one now compares the dye densities of the three Wedges at the associated silver density 0.16, then get one the fourth:

Ag density Dye density Sample A Sample B Sample G 0.16 0.12 0.24 0.18

One recognizes again that the connections of the formulas (23) and (22) the bleaching of the dye by the Prevent activated catalyst as much as possible.

The compounds of the formulas (15) and (19) give analogous results.

20S829 / Ö884

Example 3

Eü are 2 glass plates, Λ and B, in the form 13 cm . 18 cm doused with the following emulsions:

A 3.3 ml bromoiodosilver emulsion containing 8 % gelatin 3.3 ml 6 ^ ige gelatin solution
2.3 ml of water

1.25 ml of 2% aqueous solution of N, N- (1,2-dihydroxyethylene) bis-acrylic acid amide ·

B Mixture as A, but with the addition of 0.25 ml of a n / 50 Solution of the ammonium salt of the compound of formula (.22).

After drying, panels A and B are provided with an overmolding of the following composition:

6.6 ml 6% gelatin solution
1.25 ml of 2% aqueous solution of O ₃ H ml of 1% aqueous solution of the dye of the formula

(52)

A step wedge is copied on each strip of panels A and B and developed as indicated in Example 1, treated with the stop fix bath, soaked and dried. These silver wedges are under a red filter with a Densitometer measured.

The same wedges are now given as in Example 1 treated with the dye bleach bath, the silver bleach bath and the fixing bath. The obtained color wedges are again

209829/0884 B _AD

measured with a densitometer under a green filter.

If one now compares the same silver densities corresponding dye densities of panels A and B, then the following table results:

Dense Ag wedge Dye wedge density on plate B on plates A 0.69 0.37 0.60 0.72 0.27 0.69 0.74 0.21 0.7 0.76 0.17 0.7 0.78 0.14 0.7 0.82 0.12 0.7

It can be seen that on plate B by the presence of the substance of formula (22) less dye is bleached 'than on plate A.

2 0 ^f ·· C 2 0/0:; 0 U

Example h

On each a glass plate 9 cm. 1.5 ml of silver bromide emulsion are added 12 cm, to which 1.5 ml of 6% solution are added Gelatin solution, 0.7 ml v / water and 0.9 ml of an IJoigen Solution of 1,3-dichloro-5-phenylamino-triazine-3'-sulfonic acids! Sodium (hereinafter referred to as hardener for short),

poured.

After drying, one glass plate is filled with 3.5 ml of a solution consisting of 50 ml of 10% gelatin, 9 ° ml water / water containing 0.7 g of the compound of formula (23) and 12.5 ml of hardener solution poured on (Plate A).

3. " 5 ml one solution of the same composition, but without the compound of the formula (23) j applied (panel B).

After drying, a mixture of 1.65 ml of oily gelatin, 1 ml of hardener and 0.29 ml is placed on each glass plate a l ^ ige aqueous solution of the dye of the formula

209829/0884

Cj
i N = N
Ν / ν CH-
■ Λ -NH-CO ιπ co- ι \ /
S. -NH I So ₃ K ι
OCH H CO ι

IUQ SOK

N = N ' ^y

EO, S

and poured 2 ^ 1 ml of water.

A strip of each of these plates Λ and B is exposed under a gray wedge for 3 seconds with 500 lux and treated according to the following recipe:

Minutes developer
a)

b)

water

Tetraacetic acid ethylenedxamine

Na sulfite anhydrous

Hydroquinone

Na metaborate (4 H ₃ O)

Borax (12 HgO)

Potassium bromide

Benzotriazole

water

1-phenyl-3-pyrazolidone a) -! - b) fill up to ml

2 g

50 g

6 g

15 ε

15 s

ι g

0.1 g 'ml

0.25 ε

ml

Minutes of darning fixation bath

Sodium thiosulphate crystallizes Na-. ^c 3ulfite v / ate free. Na acetate (3 H _g 0) glacial acetic acid
V / a £ 3ser on

200 6th 15th ε 25th S. 13th ml 1000 ml

Soak for minutes

Minutes of dye bleach

Soak for minutes
■ 4 minutes of fixer

Approach j is identical to the Stopfixierbad Soak for minutes.

Potassium iodide 20 g

Sodium hypophosphite crystallizes 0.2 g

concentrated sulfuric acid. 55 ml

Water 19 ^ 5 ml äth5 ^r lalkoholische solution containing 0.3 S 2,3- £ i ^inetn yl-6-ainino-quinoxaline in

Contains 50 ml of ethyl alcohol, 30 ml

Soak for minutes.

Minutes of silver bleach bath '. "■

Potassium ferricyanide '75 g

Potassium bromide 15 g

Na-phosphate prim, (1 HpO). 10 g

Na acetate - (3 HgO) '5g

Glacial acetic acid 10 ml

Water to 1000 ml

2 0 9 8 2 0 / Q b 8

The stripe B shows a yellow colored wedge, during the Strip A is globally colored yellow. Do you measure the Color density in abs.-max. of the dye of the two strips in the same place, namely where the strongest exposure has taken place, then one obtains the relative value of 1.6 for the strip A and of the Strip B is 0.26, i.e. that of the halogen silver layer diffusing reduced form of the catalyst reaches the dye layer and in strip B produces color bleaching there, while in strip A the reduction product due to the compound of the formula present there (23) is reoxidized and therefore in the dye layer can not or to a lesser extent come into effect.

If you replace the yellow dye in this experiment of formula (33) by the cyan dye of formula

SO-H

⁰ 0CH "HO ₇ S 3 3

NHi I

I ΛΤΤ TT Al f \

then one obtains for the strip A the value 1.29 and for strip B the value 0.6.

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Example 5

Two glass plates Ij5 cm. 18 cm, A and B be with a color gelatin solution of the following composition

poured:

3.3 ml gelatin 6 %

2.0 ml l _> 3-dichlorotriazine-5-aminobenzene-3'-sulfone

acidic 0.5 ml of a liquid solution of the dye of the formula

HO S

0H

SO "H

- <

SO ₅ H

^, 2 ml of water. The plate A is made with a coating

5.0 ml gelatine 10 % 1.0 ml liquid silver colloid solution 5> 0 ml v / water

2.0 ml 1,3-dichlorotriazine-5-aminobenzene-3 ^l sulfonic acid

provided, the plate B with such a

209829/0884

5.0 ml gelatine 10 Jg

1.0 ml liquid silver colloid solution 5.0 ml. V / ater

0.35 ml of a n / 50 solution of the aramonium salt

the compound of formula (23) 2.0 ml of l, 3-dichlorotriazine-5-aminobenzene-

3'-sulfonic acid l ^ ig--

Each of the plates A and B is divided so that 4 plates, A _3, Ap, and B ,, B "obtained.

In plates A and B, the metallic silver is oxidized with the following bleach bath:

150.0 ml hydrochloric acid 37 %

25.0 g copper sulfate "

30.0 g of potassium bromide with Yiasser

Add 1000 ml.

Soak for 2 minutes.

The panels Ap and B ₂ are subjected to the usual color bleaching process as follows:

You will be 1 minute in the dye bleach bath of the composition:

100.0 ml hydrochloric acid 37 %

150.0 grams of potassium bromide

8.0 g thiourea

1.0 ml of 2,5-dimethylpyrazine with water

1000 ml supplemented,

'bathed, watered for 2 minutes.

Then the plates A, A ·, B, B ₀ in a solution of

2 9/088 4

150.0 grams of sodium thiosulfate

15 * 0 g sodium sulfite

13., 5 ml acetic acid 100 %

15 * 0 g sodium metaborate

15j0 g of potassium aluminum sulfate with water

1000

ml supplements,

fixed and watered for 10 minutes.

The transparency of the remaining purple layer is measured on a spectrophotometer. The table shows the fourth obtained.

Λ
nm density H A ₂ ^B l ^B 2 630
600
575
550
500
450
400 0.00
0.16
0.84
0.83
0.50
0.18
0.21 0.00
0.04
0.30
0.30
0.18
0.07
0.10 0.00
0.15
0.80
0.80
0.54
0.18
0.24 0.00
0.17
0.80
0.79
0.49
0.18
0.24

2 0 9 8 2 0/0; 3 4

It can be seen that the added nitro compound the reduction of the catalyst on the colloidal silver prevents or possibly reduced catalyst again oxidizes so that it can no longer act on the purple layer underneath. ·

2 0 ^f J b 2 a / (, u 8

Claims (1)

Claims Photographic material containing an azo dye which can be bleached by silver in at least one layer Material for the silver dye bleaching process, characterized in that that there is at least one nitro compound of the formula - * ■ in at least one layer ) _r (R ₂ -U-) (m-lXq - l) + l contains, wherein A contains a 1 to 2 sulfonic acid groups, at most bicyclic aromatic radical, R ,, R, ¹ , R "and R ₂ ¹ each a benzene radical, U, U ', V and V', each a -CO-HN or -SO ₂ -HN group and m, q, r and s each mean one of the numbers 1 and 2. 209829/0884 2. -Photographic material according to claim (1), characterized in that it is in at least one layer at least one nitro compound of the formula (0 _o N-) _r (R ₂ -X-HH -) -A-HH-Y-R (m-I) (Q-I) -M contains, in which A is a 1 to 2 sulfonic acid group-containing, at most bicyclic aromatic radical, R, and R _? each represent a benzene radical, X and Y each represent a —CO— or —SOg group, and m, q and r each represent one of the numbers 1 and 2. 5 · Photographic material according to claim (2), characterized characterized in that there is at least one nitro compound of the formula in at least one layer (0 ₂ N-) _r (R ₂ -X-HN-) R ₁ -Y-HN- 1- A ₁ -NH-YR- (-NH-XR ₂ X-NO ₂ ). contains where R ₁ , R ₂ , X, Y, m, q and r have the meaning given and A _{1 is} a benzene, diphenyl, naphthalene or stilbene radical containing 1 to 2 sulfonic acid groups! 2 0 9 δ 2 9 / Ο U 8 4. Photographic material according to. Claim (3)., Thereby characterized in that there is at least one nitro compound of the formula in at least one layer X-HM _N ) KH-X- 2'r contains, in which Ap contains a 1 to 2 sulfonic acid groups containing benzene or diphenyl radical, X and Y each a -CO- or -SOp group, Z and Z ¹ each a hydrogen atom or a methyl group and r and η each an integer of mean at most 2. 5 · Photographic material according to claim 4, characterized characterized in that there is at least one nitro compound of the formula in at least one Schioht ΜΗ — Υ— <O contains, in which Ag, Y, Z, Z ¹ , η and r have the meaning given. 2 O 9 ü 2 9 / υ ·; 8th 6. Photographic material according to claim (5), characterized characterized in that there is at least one nitro compound of the formula in at least one layer HO "S contains, wherein Z 'and r have the meaning given and in the individual benzene residues on the one hand the -HN and the -CO groups and on the other hand the -SOg and the -OgN groups are in the m- or p-position to each other. 7 · Photographic material according to any one of the claims 1 to 6, characterized in that the nitro compound is in an intermediate layer. 8. Photographic material according to one of Claims 1 to 6, characterized in that the nitro compound is located in a filter layer containing silver colloid. 9 · Photographic material according to one of Claims 1 to 6, characterized in that the nitro compound in an antihalation layer containing silver colloid is located. 10. Photographic material according to one of claims 1 to 6, characterized in that the layer. Which contains the nitro compound, contains fogged silver halide. 11. Photographic material according to any one of claims 1 to 10, characterized in that it is at least in two Layers at least one nitro compound in each other P contains different concentrations. 12. A method for the preparation of a photographic material as recited in any one of claims 1-11 Composition, characterized in that in at least one layer a nitro compound according to one of the claims 1 to 6 is stored. Use of the nitro compounds of the composition specified in one of claims 1 to 6 as oxidizing agents for the reduced color bleach catalyst in photographic Silver dye bleach material contained in at least one Layer contains an azo dye that can be bleached by silver. 209829/0884