DE1900790A1 - Photographic material containing azo dyes - Google Patents

Description

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

-Case TEL 47 / E _ _ _

Dr. F. Zumsfein - Dr. E. Assrrtcmn

Dr. R. Koenigsberger - «^. , - * Dipl. Phys. R. Holzbauer

German _ΜΟηώβη

Photographic material containing azo dyes.

The invention relates to a photographic material, in particular for the silver dye bleaching process, characterized in that there is at least one dye of the formula in one layer

9098 3 7/1235

(D

A-N = N-B-NH-

contains, in which A is in the 1-position to the azo group, in 2-position to an amino group and in 8-position to an Naphthalene radical bound to a hydroxyl group and having at least one sulfonic acid or sulfonic acid amide group, B 1 to 2 sulfonic acid or sulfonic acid amide groups containing naphthalene radical, η a whole number with a value of at most 4 and D an n-valent acyl radical of an acylation component mean. -

Among the dyes of the formula (1), those of the formula prove to be the most common

as valuable, where G-., Gp, G, and G ₂ ^ each have a sulfonic acid or sulfonic acid amide group, E an amino group, ρ and q 1 or 2, η an integer of at most 4 and D an at least n-valent Mean acyl radical of an acylation component.

909837/1235

The photographic material preferably contains a dye of the formula

^(G 2 ⁾ (2-r) ( _P -l)

SO-H

n.

where G ,, G ^, ρ and q have the meaning given, r and n ^. an integer with a value of at most 2, R ₁ and R ₂ each represent a hydrogen atom, an alkyl, aryl or alkylaryl radical and a valent acyl radical of an acylation component. Dyes of the formula are particularly suitable

-NH-

^(G 2 ⁾ (2-r) (pl) N

\ R_ H

SO ₃ H

909837/1235

where G ,, Gp, η ,, r, ρ, q and D _{1 have} the meaning given and R, a hydrogen atom, an alkyl or phenyl radical .. means, as constituents of photographic material.

Dyes of the formula are then of particular interest

(SOY

H- (O-B)

SO ₃ H

where p, q, n. and R-. have the meaning given and Dp is a monovalent or divalent acyl radical that differs from an aliphatic, aromatic or heterocyclic carbon acid or a nitrogen heterocyclic compound is derived.

Special mention should be made of dyes of the formula 909 83 7/1235

(6)

where η, and D _{2 have} the meaning given and R _2,. denotes a hydrogen atom, a lower alkyl or a cyclohexyl group or a further substituted phenyl group at least in one position adjacent to the bond to the -NH- group.

Dyes of the formula

-NH-

909837/1235

190079Q

where D_ the group -CO-, a diacyl radical of thiophene-2,5-dicarboxylic acid, Terephthalic acid, isophthalic acid, pyridinedicarboxylic acid, diphenylsulfonic (l, l *) - 4,4'-dicarboxylic acid or which means cyanuric acid. "

The dyes of the formula (I) can be prepared in a known manner. The dyes of the formulas 1 to can be obtained, for example, by adding aminoazo dyes of the formula

A-N = N- B -NH,

with halides of an acylating component, wherein A and B have the meaning given.

Another option is that you can get diazonium salts of the formula

J == N ^ —B — NH-

t-J

in acidic medium with compounds of the formula (10) A-H

converts, in which A, B, D and η have the meaning given and X ~ is an anion, preferably a halogen anion.

If one proceeds according to the first method, it is expedient to couple a diazo compound from which the radical B is derived derives that contains an HpN group and not with itself

909837/1235

~ ^Ί ~ 190079Q

itself couples, or a diazo of the itself the radical B is derived, which has a group that can be converted into the HpN group, in an acidic medium with an aminohydroxynaphthalene of the formula (10) and, if appropriate, condensed after conversion of the group mentioned into the HpN group, the aminoazo dye with a halide of an n-valent acylation component in the molecular ratio n: 1.

If the second method is used, it condenses one expediently first the halide of the acylation component and the nitroamino compound, from which the remainder B derives, reduces to the amine, tetrazotizes and couples with a compound of formula (10).

Regardless of which of the two production methods the dyes of the formula (1) are produced by, these dyes are derived from three components; namely the coupling component resulting in the remainder A, the the diazo component giving the radical B and the acylating component giving the radical D.

The remainder A is derived e.g. from the following coupling components:

2-amino-8-hydroxy-naphthalene-6-sulfonic acid
2-amino-8-hydroxy-naphthalene-5-sulfonic acid
2-amino-8-hydroxynaphthalene-3,6-disulfonic acid 2-amino-8-hydroxynaphthalene-3,5-disulfonic acid 2-amino-8-hydroxynaphthalene-5,7-disulfonic acid 2-amino-8 -hydroxy-naphthalene-6,7-disulfonic acid

909837/1235

The amino groups of these sulfonic acids can be monosubstituted, for example, by the following radicals:

- <Z>

SO ₃ H

SO H

OCH

CH

-CH ₂ CH ₃

Cl

OCH

OCH

Cl

Cl

SO ₃ H

909837/1235

The following radicals are suitable for the formation of tertiary amines, i.e. 2-amino-8-hydroxynaphthalenesulfonic acids that are disubstituted on the N atom:

- (CH ₂ CH ₂ OH) ₂ - (CH ₂ CH ₂ CH ₂ CH ₃ ) ₂

The radical A can be used instead of the free sulfonic acid groups also contain sulfonamide residues. The sulfonamide residues correspond, for example, to the formulas

-SO ₂ -N

—SO ₂ —NH

-SO ₀ -NH 0 2 ν /

909837/1235

H \_

-SO ₂ -NH (CH ₂ )

₂ -N (CH ₂ CH ₂ CH ₂ CH)

CH ₀ CH ₀ OH

-SO ₂ -N-

CH "COOH I 5

-SO ₂ -N C-5

The azo component B is derived from nitro compounds, which after coupling with the coupling component, from which A is derived, reduced and then acylated, or reduced after acylation and then coupled will. The following are, for example, those containing nitro groups Diazo component called:

2-amino-6-nitro-naphthalene-4,8-disulfonic acid 1-Amino-6-nitro-naphthalene-4,8-disulfonic acid 2-Amino-7-nitro-naphthalene-1,5-disulfonic acid. α-Amino-ö-nitro-naphthalene-e-sulfonic acid

909837/1235

The remainder D of the acylation component conducts e.g. differ from the following acid halides:

Phosgene

Thiophosgene

Oxalyl chloride

Malonic acid dichloride

Succinic acid dichloride Glutaric acid dichloride Adipic acid dichloride Pimelic acid dichloride Succid dichloride Azelaic acid dichloride Sebacic acid dichloride Chlorosuccinic acid dichloride

2,3-dichlorosuccinic acid dichloride

Fumaric acid dichloride Terephthaloy1chiorid

oyl chloride

Thiophene-2,5-dicarboxylic acid dichloride * ■ Furan-2,5-dicarboxylic acid

dichloride

• Pyr.idin-2,5-dicarboxylic acid dichloride pyridine-2,6-dicarboxylic acid dichloride pyridine-3i 5-dicarboxylic acid dichloride, azobenzene dicarboxylic acid dichloride-3 * 3'-4.4 ^I 3.3 ^{I--Dimethylazobenzol} -dicarbonsäuredichlorid 4,4'-Dichlorazobenzol -3,3'-dicarboxylic _{acid dichloride azobenzene-4>} 4'-dicarboxylic acid dichloride

2,2'-dimethylazobenzene-5,5'-dicarboxylic acid dichloride 2,2 * -Dimethoxyazobenzene- 5 * 5'-dicarboxylic acid dichloride Pyrrole-2,5-azobenzene-5 »5'-dicarboxylic acid dichloride 2,2'-dichloroazobenzene-5,5'-dicarboxylic acid dichloride 2,2 * -Dimethylazobenzene-4,4'-dicarboxylic acid dichloride 3,3'-dichloroazobenzene-4,4'-dicarboxylic acid dichloride

4,4'-dichloroazobenzene-5,5'-dicarboxylic acid dichloride azobenzene-4,4'-disulfonic acid dichloride azobenzene-3,3'-disulfonic acid chloride diphenylsulfonic (1,1 ') - 4,4'-dicarboxylic acid dichloride benzene-1,3- disulfonic acid chloride 'Diphenylmethane-3i 3 ^! -dicarboxylic acid dichloride diphenylmethane-4,4 ^T -dicarboxylic acid dichloride diphenyl sulfide-4,4] -dicarboxylic acid dichloride diphenyl disulfide-2,2idicarboxylic acid dichloride. Diphenyl disulfide-4,4'-dicarboxylic acid dichloride cyanuric chloride, methoxycyanuric chloride, l-phenyl-3i 5-dichloro-s-triazine, l-methoxy-3,5-dichloro-s-triazine, compounds of the formula ^

01-0

σοσι

or

σ 1 - OC

NH-Υ-HN

ο-σι

909837/1235

wherein X ₁ and X ₂ = a hydrogen atom, an alkyl or

Alkoxy group and

Y mean the remainder of a bridge member such as phosgene or terephthaloyl chloride.

The necessary for the preparation of the dyes of the formula (I) Reactions can all be carried out in a conventional manner known per se. Mono, Prepare dis-, tris- and tetrazo dyes in this way.

Like the dyes themselves, the photographic materials, which in one layer at least should contain a dye of the formula (I), prepared in a conventional manner known per se and for production colored images can be used. The dyes of the formula (I) are usually purple in color in gelatin Tones, and they can conveniently be used in a multilayer material on a support in the green-sensitized Silver halide emulsion layer may be present, this material being a further layer greenish-blue red-sensitized emulsion layer and a yellow-colored, not particularly sensitized emulsion layer contains. The azo dyes of the formula (I) can be used in the photographic material, in particular those for the silver dye bleaching process, may be incorporated into any layer at any stage of manufacture, however the green sensitized layer is preferred.

909837/1236

190079Q

The present invention accordingly also relates to the use of the dyes of the formulas (1) to (7) as components of a photographic material, in particular as image dyes for the silver dye bleaching process.

Percentages in the following manufacturing instructions and the example are percentages by weight.

909837/1235

Manufacturing regulations

A. As indicated in the preceding description, the dyes of formula (1) can be prepared by two different methods. Using the example of dye A, the two methods are described in detail here:

g of 2-nitro-6-amino-naphthalene-4,8-disulfonic acid

1200 ml of water and

ml of a 30 # strength sodium hydroxide solution dissolved at 65 ° C. It is cooled to 0 ° C. and ml of 4N sodium nitrite solution are added

ml of hydrochloric acid. It is diazotized for 45 minutes and then destroys the excess sodium nitrite by adding sulfamic acid. You also solve g of 2-amino-8-hydroxy-naphthalene-6-sulfonic acid in ml of water and

ml of 30 # sodium hydroxide solution and make with acetic acid on Pu 5 · After getting the solution of the coupling component Has cooled to 0 ° C, this is poured into the diazonium salt solution and left for 24 hours stir. The mixture is then warmed to 60 ° C., g. Sodium chloride is added and, after cooling, filtered

to 30 ° G. The residue is slurried in 3000 ml of water and after having

g of sodium carbonate was set to p _H 9 to 10, is

Clarified by filtration at 60 ° C. The filtrate is with ml of 7N potassium acetate solution are added, the dye

909837/1235

19-0790

fails. It is filtered at 25 ° C. and the residue is washed with methanol. It is dried in a vacuum at 50 to 60 ° C and receives 104 g of a dark red powder that the compound of formula

(11)

SO ₃ H

N = N KJy)

SO H

represents. . ;;

g of the coupling product of the formula (11) are dissolved in ml of water at 55.degree. Then will g of sodium sulfide (60 #) in

Dissolved 1000 ml of water and allowed to drop in over the course of 2 hours.

Towards the end of the reaction, the mixture is heated to 60.degree. As soon as no Starting material can be more proven, one mixed with

ml of 7N potassium acetate solution and over the course of 1

Cool to room temperature for an hour. One filters, washed with methanol and dried in vacuo at 60 ° C; 38.7 g of azoamine of the formula (12) are obtained. More crystals can be obtained by concentrating the filtrate on a rotary evaporator.

909837/1235

SO, H (12)

300 ml 5 S. 1 G 50 ml

5.7 g of azoamine of the formula (12) are in

Water with the addition of ... .--. . '.. Sodium tetraborate dissolved at 60 ° C. Then be at room temperature
Terephthaloyl chloride dissolved in acetone poured. After 24 hours the addition of the same amount of sodium tetraborate and terephthaloyl chloride in acetone is repeated. As soon as no more diazotizable starting material can be detected in the thin-film material, the reaction mixture, which has been heated to 60 ° C., is added

70 ml of 7N potassium acetate solution and

ml of methanol and filtered after cooling to room temperature. It is washed with methanol and dried in a vacuum at 60 ° C. 4.7 g of the disazo dye are obtained A of the formula (13) which is not chromatographically uniform. The Dye chromatographed preparatively on aluminum oxide will.

909837/1235

Sp, H ^S0 3 ^H SO ₃ H

,. <Z> -oh Λλ — mh — co - ^^ - Go — iiH-YYS ho - <- ζ

^ 2 SO, HL Tl ^E o®

77 g of 2-nitro-6-aminonaphthalene-4,8-disulfonic acid

will be in
1300 ml of water with the addition of

50 g of sodium tetraborate dissolved at 60 ° C. and then again

. . cooled down. Thereupon 24 g of terephthaloyl chloride are dissolved in 5OO ml of acetone were added. One lets react until

no more diazotizable amine is present. For complete reaction of the amine: Another 2.4 g of terephthaloyl chloride are added. The reaction product is precipitated with 60 ml of a 7N potassium acetate solution and 50 ml of methanol, then filtered, washed with methanol and dried at 60.degree.
Yield ': 103 g of the compound of the formula'

(14) O ₂ ITUy --——

SO ₅ H SO ₅ H

909 8 37/1235

The 60 g of the compound of the formula (14) are dissolved in 150 ml of water and reduced with hydrogen on palladium / activated carbon as a catalyst. The reaction product is precipitated with ml of methanol, washed with ml of a 20 # strength sodium chloride solution and dried at 60 ° C. in vacuo. The yield is 41 g of the compound of the formula

(15) _H.

SO, H SO, H

Ll I ³

[J) HH — CO— <C—)> —CO — HH | ΛΛ

₂ Ν KXJ UJ-NH ₂

'SO ₃ H. SO ₃ H

g of the compound of the formula (15) are dissolved in ml of water, made weakly alkaline with sodium carbonate posed and

ml of a 4N sodium nitrite solution was added. This solution is allowed to form a mixture of within one hour
Ice cream,
Water,

a 1: 1 mixture of in-naphthalene-2-sulfonic acid and 2n sulfuric acid and

Drip 0.3 ml of 4N sodium nitrite solution. After finished The dropwise addition is stirred for a further hour at room temperature. The excess nitrite will withdrawn with sulfamic acid.

3.2 g of 2-amino-8-hydroxynaphthalene-6-sulfonic acid (titer 93.8 %) are in

ml of water dissolved in an alkaline solution and with 100% acetic acid neutralized. After adding a little ice, this solution is poured into the diazonium salt solution.

909837/1235

20th G 20th ml 16 ml

It is cooled to 0 to 5 ° C. with ice and allowed to couple with stirring for 12 hours. Then warmed up slowly to 40 ° C, the reaction product falls' each

g of potassium chloride and sodium chloride and siphoned off from the precipitated product at room temperature. The residue is slurried again in ml of water, adjusted to p "11 with sodium hydroxide,

heated to 60 C, mixed with

g of potassium chloride and siphoned off at room temperature. It is then dropped twice and then again dried at 50 ° C in vacuo. A dye which corresponds to the formula (13) is obtained.

2.9 g of an azoamine of the formula (16), which is analogous to the azoamine of the formula (12) is obtained,

SO ₃ H

(ie) W ^

will be in

909837/1235

25 ml of N-methylpyrolidone and

ml of pyridine heated to 70 ° C and filtered clear. The residue is J> times with

ml of N-methylpyrolidone rinsed. The filtrate will

heated to 90 ° C and with

g terephthaloyl chloride added. It is allowed to cool to room temperature and the dye is co-precipitated

20 ml of methanol and

ml of 20 # alcoholic potassium acetate solution.

It is filtered, the residue is suspended twice in methanol and filtered again. One dries in a vacuum at 60 ° C. and 1.6 g of the disazo dye are obtained B of the formula (17). Few secondary zones can be seen in thin-layer chromatography.

U (CH) ₂

SO H

NH,

• Η ΛΛ KHCC

-N = N kJU

SO H

SO H

JONH-

SO H

-N = N-

so,

NH.

909837/1235

5 * 9 S azoamine of formula (l6) are in 500 ml of water dissolved in the presence of 6 g of sodium tetraborate at 60 ° C. After this

3 g of monomethyl terephthalate monocarboxylic acid chloride are added to the mixture to cool to room temperature in

100 ml of dissolved acetone are added. The mixture is stirred at room temperature overnight and falls with 50 ml of methanol and

50 ml of 7N potassium acetate solution. The residue is in ml of water dissolved and heated to 60 to 70 ° C.

For the saponification of the carboxylic acid ester, 30 # sodium hydroxide solution is used to set p "11, stirs for 30 minutes at 60 ° C. and then falls with it 50 ml of methanol and

50 ml of 7N potassium acetate solution. After a customary work-up 1.6 g of a dark powder are obtained, which corresponds to the dye C! the formula

SO ₂ F (CH ₅ ) ₂ SO ₅ H,. <I> —ÖH ρΛ MC

⁽¹⁸⁾ C ^ -N = I ^ -VV

SO ₅ H

is equivalent to.

909837/1235

11.4 G 1500 ml 20th G 9 G 150 ml

the compound of formula (12) are dissolved in water with the addition of

Dissolved sodium bicarbonate. A solution of

p-nitrobenzoyl chloride in

Acetone fell. The mixture is stirred for 48 hours at room temperature. The precipitated ones are filtered off Crystals off, the piltrate is concentrated on a rotary evaporator, filtered again and dries. A total of 8.1 g of a compound of the formula are obtained

SO-H S0_H

Ji 1 ³ <TI> OH ΛΛ HHCC

(19) O> N = N IJJ

Π J

NH ₂ SO H

You are suspended

the nitro compound of the formula (19) in Water ,, heated to 50 ° C and added 2 of a 5 # strength sodium hydrogen sulfide solution. After a reaction time of 2 hours at 50 ° C., there was still no change in the thin-layer chromatogram determine. Another ml of a 5 # strength sodium hydrogen sulfide solution is added, the color suddenly lightening after 30 minutes. After another 30 minutes the starting material is no longer detectable in the thin-layer chromatogram. One cools to room temperature, filtered, washed with methanol and dried at 50 ° C in a vacuum. One solves again in ml of water and falls with 10 ml of potassium acetate solution.

909837/123 5

CO 700 G 200 ml ml

The reduction product corresponds to the formula

SOH

SOH

h ΑΛ nhc (

N = N UJ

Yield: 4.7 g.

3.3 S of the compound of the formula (20) are suspended in • 1100 ml of water and. ·

3.5 g of sodium tetraborate are added. Phosgene is then introduced, after reaching a ρ ^ - Value of 3 with alkaline and sodium carbonate again introduces phosgene at 40 ° C. After the phosgenation has ended, it is precipitated with methanol off, washed with methanol and dried. 2.9 g of compound D of the formula are obtained by further transformations can be cleaned.

(21)

SO H

SO ₃ H

<Z> —OE ΛΛ NHCO-

<CI> —N = N KJy}

-NH-

NH.

SO H

CO

Analogously as described in the preparation instructions A to D, the dyes E to N of Table I obtain.

909837/1235

2.5 g of the compound of formula (15) are dissolved in ml of water by addition of a little 2N sodium hydroxide solution by heating to 50 ° C (p _H 9) · Upon cooling to room temperature is added

Add 2.5 ml of 4N sodium nitrite solution and cool to Oo C. ¹ Then add

ml of a 1: 1 mixture of 1 n-naphthalene-2-sulfonic acid and 2 η-sulfuric acid and.

0.2 ml of 4N sodium nitrite solution mixed with g ice, and stir for 30 minutes at 0 ° C.

On the other hand will be
3 * 3 g coupling component of the formula

SO ₂ K "

(22) O-0

in.

ml- dimethylformamide dissolved at 80 ° C. After cooling down at 0 ° C the diazo component is turned over to the coupling component, and one sets to p "3- ^. The mixture is stirred overnight, heated to 50 ° C. and filtered and dries. .

2.3 g of a dark powder corresponding to dye 0 of the formula are obtained

909837/1235

SO ^ H

ΑΛ — νη — cc

SOJi

6.5 g of an azoamine of the formula (24), which is analogous to that
■ ■ azoamine of the formula (12) 'is obtained,

(24)

will be in '

600 ml of water and

g of sodium tetraborate slurried. One warms up 50 ° C and passes in phosgene for 12 hours, the p "value of the reaction mixture by adding

Xl

there would always be between 30% sodium hydroxide solution 6 and 9 is held. It is precipitated by adding a little 7N potassium metate solution, and the residue is boiled in

ml of methanol and filtered. After drying in vacuo, 1 g of the dye JP der is obtained
formula

909837/1235

. CH, SO,

SO "H

v> ^S0 3 ^H

^ ~ y-OE / γγ-mi — GO — m— λΑ <_>

(25) CI ^ -N = N IJJ. UJ N = N <p>

NH ^ L .. L "Η _Λ Ν

SO ₂ N-

SO ^ H SO ₅ H

909837/1235

TABELIB I

CO O CO

Clutch component e ² Diazo Il Acylation Absorption maximum H ₂ O: DMP = 1: 1 Color component component * λ in nm in 518 material Il gelatin and SO H SO ₃ H 533 540 8 ~ ^0Η σισο-Ο-σοσι and A. HH ₂ NH ₂ - K / sJ 566 508
and
531 SO ₃ H 507 517
and
539 and B. 517 530 ciccKZI ^ -cooch, and C. 550 i

Color Coupling component Diazo η Acylation Absorption maximum in material component component Anax in mn H ₀ O: DMF = 1: 1 SO H SO ₅ H
I. gelatin 519 \ _> - ° ^H / Yy-NO ₂ C1CQ- <C ^> - NH "'
CO. 526 and
540 D. NH ₂ ■ SO ₃ H C1CO- <I> -NH and
548 cico- <II> -coci 510
and B. 520
and 534 NH ₂ 540 C! F \ TT
Uw itII ■ "■
/ X r \ TT
\ y UXl ■ 524
and F. SO H ^ra 2 ni nr \ 'ΓΌΓΠ 534
and 546 vXwVj v ^ y -L »UV / X
S. 552

SZZi / Li 8 60 6

Color
material Coupling component Diazo
component 30 H. Acylation
component Absorption maximum
■ ^ max in nm in H _o 0: DMP = 1: 1 G NH ₂ , SO,
Nh ₂ -Aa
I. ClCO-U-COCl gelatin 518
and
.539 H SO ₅ H
NH ₂ Il
I.
i cico- <I> -so ₂
cico- <H> ■ 552
and
572 515 I. SO ₂ H
<I> OH
• ΛίΗ C_> •
(J ₁ Op- <3> -COCl 522
and
540 > . . .
555 564

CD O O

ζ.εβ606

Color
material Clutch component Diazo
component Acylation.
component Absorption maximum
■ Ληειχ in mn in
+ · * H ₂ O: DMP «1: 1 J SO ₅ H
<£> -0H
Q CH ₅
MTT., __-. / S SO ₃ H -
NH ₂ -UJ ²
SO ₃ H
η
M. ClCO-U-COCl gelatin 552 K CH ₃ C1CO- <I> --CO <31 560, 556 L. SO ^ I
Q-OH
NH C ^
Cl σισο-ΛΛ-οοοι 599 550 SO ₃ H
^ -%
NH C ^
Cl 569

CD CD CD »J CD CD

SZZU

Color
material ■ - coupling component component Acylation
component Absorption maximum
X
max in nm in H ₂ O: DMP = 1: 1 M, or »w / r« .iT \
öUplN l, v / ü „J ρ
C "~)> HQH.
NH ₂ SO ₃ H
SO ₃ H ClCO-IJ-COCl gelatin 507
and
531 N CH ₃
SO ₂ N <d>
NH ₂ W. ClCO - IJ-COCl 522
and
555 . 509
and
533 0 , Vl ti cico— <I> —coci 524
and
54O 510
and . ■
534 ■ <~> r-rOH
NH ₂ 518
-and
541

Color
material Coupling component Diazo
component AoyIation Com-
component Absorption maximum
max in nm in H ₂ O: DMP a 1: 1 gelatin SO "H
1 515 Jr y ^ \ —oh jYpH0 ₂ 520 and
538 Cl-CO-01 and
546

CD O O

example

On a subbed white-opaque acetate film the following layers are applied one after the other:

1. Red-sensitive silver bromide emulsion in gelatin, the the greenish blue dye of the formula

d> - CO-HiT OH

contains.

2. Colorless gelatin film with no silver halide.

3. Green-sensitive silver bromide emulsion in gelatin, the the purple dye A contains.

K. Yellow filter layer containing the dye of the formula

contains.

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5 «Blue-sensitive silver bromide emulsion in gelatin containing the yellow dye of the formula

contains.

The gelatin layers can also contain additives such as wetting agents, Contain hardeners and stabilizers for the silver halide. The rest of the work is done in such a way that the individual Layers per square meter of film 0.5 g of each Dye and the amount corresponding to 1 to 1.2 g of silver Silver broraid included.

This film is exposed under a colored slide with red, green and blue copying light. On that the copy is developed according to the following rule:

1. Develop for 6 minutes in a bath containing 50 g of anhydrous sodium sulfate, 0.2 g 1-phenyl-3-pyrazolidone, 6 g hydroquinone, 35 g Contains anhydrous sodium carbonate, 4 g of potassium bromide and 0.3 g of benzotriazoi

2. Soak for 5 minutes!

Fix 3 x 6 minutes in a solution of 200 g sodium thiosulphate Krist. and 20 g of potassium metabisul- fit in 1 liter of water;

909837/1235

4. Water for 5 minutes;

5 · 3 to 12 minutes color bleaching with a solution,
50 to 80 g of potassium bromide, 4θ per liter of water
contains up to 80 g thiourea, 35 to 80 g 30% sulfuric acid and, if desired, 0.001 g 2-aminooxyphenazine; . - _:. .

6. Water for 10 minutes;

7. Bleach residual silver for 5 minutes with a solution of 60 g of crystalline. Copper sulfate, 80 g of potassium bromide and 15 ml of 30% hydrochloric acid in the liter of water;

8. Water for 5 minutes; .

9. Fix for 5 minutes as indicated under 3 ·; 10. Water for 5 minutes.

A light-resistant, document-proof, positive reflective image is obtained. ■ ·, ■

Instead of the dye A, the purple dyes can also be used B to P incorporated into the green-sensitive layer with similarly good results.

909837/1235

Claims (9)

'> Claims 1. Photographic material, characterized in that that there is at least one dye of the formula in one layer A - N * N - B - NH contains, in which A is in the 1-position to the azo group, in 2-position to an amino group and in 8-position to a Naphthalene radical bound to a hydroxyl group and having at least one sulfonic acid or sulfonic acid amide group, B a naphthalene radical containing 1 to 2 sulfonic acids or sulfonic acid amide groups, η an integer of at most 4 and D an at least n-valent acyl radical one Mean aoylation component. 2. Photographic material according to claim 1, characterized characterized as having a dye of the formula 9 0 9 8 3 7/1236 contains, where G-., and each a sulfonic acid or Sulphonic acid amide group, E an amino group, ρ and q 1 or 2 _S η an integer not exceeding 4 and D an at least n-valent acyl radical of an acylation component mean. 3. Photographic material according to claim 2, characterized characterized as having a dye of the formula SO-H 909837/1235 contains, where G, and G ₂ each have a sulfonic acid or sulfonic acid amide group, r, ρ and q 1 or 2, R and Rp each a hydrogen atom, an alkyl, aryl or alkylaryl radical, n, an integer of at most 2 and D, an at least n, -valent acyl radical of an acylation component. 4. Photographic material according to claim 3 * thereby characterized as having a dye of the formula (SQ,) G. SO-H contains, where G, and one sulphonic acid or one sulphonic acid acid amide group, r, ρ and q are 1 or 2, R is a hydrogen atom, an alkyl or phenyl radical, n is an integer not exceeding 2 and D _{1 is} an at least n-valent acyl radical of an acylation component. 5. Photographic material according to claim 4, characterized characterized as having a dye of the formula 909837/1235 H-COJ3) (so “> 7 — rr — I 3 Cq-I) Oh ([^ ^m ~ SOJl contains, where ρ, q and η., 1 or 2, "IL, a hydrogen atom, an alkyl or phenyl radical and D ₂ an at least mono- or divalent acyl radical derived from an aliphatic, aromatic or heterocyclic carboxylic acid or nitrogen-heterocyclic radical , mean. 6. Photographic material according to claim 5, characterized in that it is a dye of the formula 909837/1235 • NH- contains, where η = 1 or 2, Dp is at least a mono- or divalent acyl radical derived from an aliphatic aromatic or heterocyclic carboxylic acid or nitrogen heterocyclic compound, and R ₂ , a hydrogen atom, a lower alkyl or cyclohexyl group or at least one a position adjacent to the bond to the -NH- group denote a further substituted phenyl group. 7. Photographic material according to claim 6, characterized in that it is a dye of the formula 909837/1235 contains, wherein D is the group -CO-, a diacyl radical of thiophene-2,5-dicarboxylic acid, terephthalic acid, isophthalic acid, pyridinedicarboxylic acid or diphenylsulfone-ίϊ, Ι- ¹ ) -4,4 * -dicarboxylic acid or a derivative of cyanuric chloride. 8. Photographic material for the silver dye bleaching process, characterized in that it is in a Layer at least one azo dye in one of the Contains claims 1 to 7 specified composition. 909837/1235