DE2406653A1 - PHOTOGRAPHIC RECORDING MATERIAL AND COMPOUNDS FOR MANUFACTURING THESE - Google Patents

Description

Photographic recording material and compounds for manufacture same.

The invention relates to a photographic recording material consisting of a layer support and at least one coated thereon light-sensitive silver halide emulsion and a cyan image dye forming compound in one Layer of the material as well as a blue-green oil-forming dye Compounds for the preparation of such a photographic Recording material.

For performing color diffusion transfer processes, it is known Photographic recording materials and recording units used, which consist of a support and at least one applied thereon with a silver halide emulsion layer an image dye forming compound in the emulsion layer or exist in an adjacent layer. The image dye-forming compounds are usually the same as Structure carrier component-color component, where the coloring component from a dye residue or a so-called dye precursor residue i.e. a residue from which a dye can be produced. The carrier component bound to the color component has the Function of bringing about a change in the diffusibility of at least the color component of the compound during alkaline development.

After the image-appropriate exposure, the recording materials become or recording units treated with an alkaline developing solution, thereby causing a change in diffusion behavior , iiat least the color component of the image dye forming agent Connection is established. The one forming an image dye Compound can be immobile or mobile in the developing solution. The alkaline developing liquid can, for example, when using an immobile liquid dye-producing compound a mobile dye can be set free image-wise or the compound can be image-wise soluble and thus made mobile

40 9 8 35/0947

will. If mobile fast dye-forming compounds are used, the developing solution can use these compounds imagewise make it insoluble and thus image-wise immobile.

Ils is in particular the carrier or control component which is responsible for what changes in the diffusion behavior of at least the coloring component of the compound takes place. For example, an increase in the solubility of compounds can be achieved by reducing their molecular weight, as is disclosed, for example, in US Pat. No. 3,698,897 and BE-PS 788,268 and "Product Licensing Index, Vol. 92, i. 'r. 9255, Dec. 1971.

Processes in which image uses dye-forming compounds which split off dye residues are known, for example, from US Pat. No. 3,227,552 and 3,443,940 and from CA Pat. Processes which use image dye forming compounds which are rendered imagewise immobile upon development are, for example, from US Pat. No. 2,756,142, 2,774,668 and 2,983,606 known.

For the production of blue-green dye images in the context of color photographic Diffusion transfer processes have so far been indoaniline, Anthraquinone, lis-azo or metallized phthalocyanine dyes used.

The object of the invention is to provide a photographic recording material with a new compound that produces a mauve image dye, which differs from comparable compounds distinguishes that. they the!. 'production of color photographic Images of particularly deep color tones as well as the production of particularly color-stable images enable. Furthermore, the new ones, one blue-green iildye-producing compounds characterized be that they have dyes with excellent fusibility and deliver liquidity.

The invention was based on the principle that certain blue-

409835/0947

Green azo dyes supplying compounds are excellent for implementation suitable for color diffusion transfer processes. These connections as a function of a typical development process under alkaline conditions, provide blue-green color dyes with a Mobility or diffusibility different from that of the compound from which they are obtained.

The depth of color used to produce color photographic images blue-green monoazo dyes are based on a p-nitro group and a second electron withdrawing group on a phenylazo radical, which is bound to the 4-position of a 1-naphthol nucleus which further has an electron donating group.

The invention thus provides a photographic recording material consisting of a support and at least a light-sensitive silver halide emulsion layer applied thereon and a cyan image dye forming compound in a layer of the material characterized in that it contains as a cyan image dye-forming compound a compound of one of the following formulas:

Y-Cv- (NR-J) 4

or

Y-X-J-NII

N-N

_{N N} -J ~ X-

NO.

^lNU 2

409S35 / 0947

- 4 where mean:

Y is a carrier residue resulting from an under alkaline condition oxidation taking place provides a compound with a mobility that of the compound of the formula given is different;

X is a bivalent link of the formula 2 2

-R -L -R -, in which mean: η ρ

R is an alkylene radical with 1 to 8 carbon atoms or optionally one substituted phenylene radical with 6 to 9 carbon atoms - where-

where applies that the two radicals R are the same or different Can have meaning;

L is an oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, Sulfamoyl, sulfinyl or sulfonyl group;

η = 0 or ;;

ρ = 1 if η = 1 and ρ = 1 mimi. or = 0, if η = 0,

where it holds that when ρ = 1, the sum of the carbon atoms of the two radicals R does not exceed 14;

R is a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms; J is a sulfonyl or carbonyl radical;
η and q each = 0 or 1;

Q represents a hydrogen atom, a hydroxy radical or a radical of one of the Formulas:

-NHCOR ³ or -NHSO ₂ R ³

409835/0947

2405653

in which R is an optionally substituted alkyl radical with 1 represents up to 6 carbon atoms, a benzyl radical or an optionally substituted plienyl radical having 6 to 9 carbon atoms;

G is a hydroxy radical, a salt thereof or a hydrolyzable one Remainder of one of the formulas

0 nights

-Ü-CR ⁴ or -GCOR ⁴

in which R is an alkyl radical having 1 to 18 carbon atoms or a represents optionally substituted phenyl radical with 6 to 18 carbon atoms;

D is a halogen atom or a cyano, nitro, trifluoromethyl or alkyl radical having 1 to 6 carbon atoms; an alkoxy radical with 1 to 6 carbon atoms; a carboxy radical; a Caruonsäureesterrest of the formula -CuOR, in which E ^{+ has} the meaning already given; a fluorosulfonyl radical; an optionally substituted —SO -, - phenyl radical having 6 to 9 carbon atoms; a sulforest; a sulfamoyl radical of the formula -SC ₉ NR R °, in which R is a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms and R is a hydrogen atom, an optionally substituted alkyl radical having 1 to 6 carbon atoms, a benzyl radical, an optionally substituted one Represents a phenyl radical with 6 to 9 carbon atoms, an alkylcarbonyl radical with 1 to 8 carbon atoms or a phenylcarbonyl radical with 6 to 9 carbon atoms, whereby the sum of the carbon atoms of the radicals R ⁵ and R does not exceed 14 ; a carbamoyl radical of the formula -CON (R ^) ₂ , in which the two radicals R ^{5 can have} one of the meanings already given and can be identical to or different from one another; an optionally substituted alkylsulfonyl radical having 1 to 8 carbon atoms; an optionally substituted phenylsulfonyl radical with 6 to 9 carbon atoms or a radical of one of the formulas:

409835/0947

-G-

Y — Ρ- X - (- NR-J-9 1 or

Y-X-J-,

provided that the substituent of the formula

on the naphthalene ring of the formula I by a radical of the for Ii given meaning is replaced or that the substituent of the formula Y-X-J-NIJ - on the naphthalene ring of the formula II by a radical of the meaning given for Q has been replaced, it being true that Y, X, J, R, q and m have the meaning already given to have;

h is a hydrogen or halogen atom or a nitro, cyano or tri fluorine thyl radical;

Ά a hydrogen atom; a carboxy radical; a carboxylic acid radical of the formula -COOR, in which R has the meaning already given; a sulfamoyl radical of the formula -SO ₇ NR ⁵ R ⁶ or a carbamoyl radical of the formula -CON (R ⁵ ), in which R and R have the meanings already given; an optionally substituted alkylsulfonyl radical having 1 to 8 carbon atoms; an optionally substituted phenyl sulfonyl radical having 6 to 9 carbon atoms; an optionally substituted alkyl radical having 1 to 6 carbon atoms; a benzyl radical or an optionally substituted phenyl radical;

with the proviso that the compound has no more than one Sulforest and no more than one carboxy radical.

The invention also relates to a cyan image dye generating compounds of the formulas given.

409835/0947

The mode of operation of the inventive, a cyan image dye Generating compounds results, for example, from the following reaction scheme:

Ballast group

NHSO

2 //

SO ₂ NH

SO ₂ CH ₃

oxidized

Developer association OH "'

Bailas

tgrugge

SO ₂ CH ₃

SO ₂ NH ₂

cationic

Pickling agents

Mordant-dye complex.

The compounds according to the invention thus have a carrier residue CY), which as a function of (direct or reverse) oxidation under alkaline conditions produces a substance that has a mobility which is different from that of the starting compound.

Depending on the carrier component used, the inventive

409835/0947

and dye-producing compounds belong to two basic types, namely:

(1.) Ls are immobile connections, of which at least a part is made mobile or diffusing as a function of development, or

(2.) ^They are mobile or diffusing compounds which are made immobile as a function of development.

Carrier residues of immobile picture dye-producing compounds, and although soldier in which the carrier residue under alkaline conditions causes a ballast group to split off from the dye group, are for example from CA-PS 602 607 and US-PS 3 227 55 2 · known. The preferred immobile compounds include those in which the carrier residue is a function of oxidation under alkaline conditions Conditions releases or splits off a dye that has a mobility that is different from the mobility of the parent compound is different. Suitable carriers or carrier residues for according to the invention Compounds in which the carrier residue undergoes an intramolecular ring closure with elimination of a dye remains, for example, from US-PS 3,443 Γ39, 3 443 Π40 and 3 443 Γ41 known.

Special immobile carriers or carrier scraps that can be used to generate Diffusing substances (with the opposite function of oxidation) are described, for example, in DT-OS 2 402 900. Particularly advantageous compounds which produce immobile image dyes and which are subject to a P.edox reaction and to alkali cleavage the carrier component with elimination of a dye are described in BE-PS 788 268, for example.

The phenolic and naphtholic ones with ballast groups

409835/0947

Carrier components of the last-mentioned application are particularly advantageous carrier components.

Further other suitable carrier components or carrier residues are known, for example, from US Pat. No. 3,628,952. Eventually be Carrier components or carrier residues that are suitable for the establishment of initially mobile connections, e.g. those in which the Carrier component has the action of a developing agent, described in U.S. Patents 2,543,691, 2,983,606 and 3,255,001. To the Carrier components or carrier residues of this last-mentioned type include the most varied of hydroquinone residues.

Examples of divalent alkylene radicals for which R ^ is, for example, -CH ₂ -, -C ₂ H ₄ -, -CH ₁₂ -, -Ch, -, -C.Hp- and the like, as well as branched-chain alkylene radicals, for example those of the formulas:

CH- CH, CIL CH-

I 3, j, _Λ , a

-CIi ₂ C-CII ₂ -, -CH ₂ -CH-CiI ₂ -, -CiI ₂ -CIi- and - (CIi ₂ ) g-Cll-,

Examples of optionally substituted phenylene radicals for which R are, for example, o-, m- and p-phenylene radicals, which can optionally be substituted by chlorine and / or Bromine atoms or methoxy, butoxy, cyano, nitro, liethyl, ethyl, Carboxy, sulfo and amino radicals and the like.

The oxygen- or sulfur-containing divalent solids represented by L are radicals of the following formula: Oxy - (- O -) -, Carbonyl - (- C0-), Carboxamido - (- COaIi-), Carbamoyl- ( -NHCO-), sulfonanido- (-SO ₂ NH-), sulfamoyl- (-NHSO ₂ -), sulfinyl - (- S0-) and sulfonyl - (- SO ₂ -).

As a result, the link represented by X could consist of, for example, a link from one of the following terms:

40983 $ / 0 <H7

-CH ₇ -O-CH ₉ -, -CH.-CO-

L · L · L · ^ r

-C ₅ H ₆ -MHCO-C ₄ H ₃ -, -C ₂ U

SO ₂ NH-,

OCK.

- !! ISO, -, -C ₂ H ₄ -SO-C ₃ H ₆ -,

COOIj

ν W

or

O ₇ H

If P has the meaning of an alkyl radical, this can, for example from a, '! ethyl, ethyl, isopropyl, pentyl or hexyl radical exist. The alkyl radical represented by P. can optionally be substituted, for example by one or more Cyano, hydroxy or ethoxy radicals. For example, Q can be a festival be one of the following formulas:

-NHCOCH ₃ , -NHCOC ₂ H ₅ , -MiCOC ₆ H ₁₃ , -NHCOC ₂ H ₄ CN, -NIiC

-2, ⁷ HCOCH ₂ C ₆ H ₅ , -KHCOC ₆ H ₄ CCOiI, -NHSO ₀ CH ₃ , -NHSO ₂ C ₆ H ₄ CN, -NHSO ₂ C ₆ H ₄ Cl -NHSO ₂ C ₂ H ₅ , - NHCOC ₃ H ₆ SO ₃ Ii or -NhSO ₂ C ₆ Ii ₄ OCH ₃ .

As already stated, G can be a hydroxy radical or a salt remainder thereof, i.e. for example an alkali metal salt residue, e.g.

-u well y

Li; -U i ·,

or a photographiscl; inert or inactive ammonium al zr es t,

409835/0947

e.g. the formula: -O

NH (CH ₃ ) ₂ ; -0 ^C 12 ^H 25

NH ₄ ; -0

NiI (CIi ₃ ) ₃ ; -0

-0

^θΘ

, i.e. a trialkyl or tetraalkyl

ammonium salt, sometimes also referred to as amine salt, which describe the photographic utility of the cyan image dye forming compounds as well as the physical and chemical processes that take place during the development of the dye image are not adversely affected.

If G has the meaning of a hydrolyzable acyloxy radical of the specified Formula, this hydrolyzable R.est can for example be a remainder of the following formulas:

0 0 0 0 j _v 0

11 "Il H // YV

-0-CC ₅ Ii ₁₁ , -0-C-OC ₂ H ₅ ; -OC-CH ₃ ; -OC-r y

Ii //

-Cl; -0-C- ^

0 y

" // 0-C-. Γ

-NO ₂ , -0-COC ₁₂ H ₂₅ ; -QCC ₁₂ II ₂₅ ;

If D has the meaning of a halogen atom, this can be for example. consist of a chlorine, bromine or fluorine atom. Typical alkyl and alkoxy radicals for which D can stand are, for example Methyl, isopropyl, ethyl, butyl, hexyl, ilethoxy, ethoxy, Isopropoxy, hexyloxy and butoxy radicals.

If D stands for a carboxylic acid ester residue, this can be for example

409835/0947

wise be a residue of the following formulas: -COOCK ,, -COOC ₂ Ii ₅ , -COOC ₆ Ii ₅ , -COO

, -COOC ₁₂ H ₂₅ , -COO- ^ ^ -Cl.

If D stands for a carboxy radical, it can also be in salt form, i.e. D can also stand for an alkali metal salt radical, for example or a photographically inactive ammonium salt residue, i.e. D can for example stand for solids of following formulas:

-COOH; -COO ^θ Li

-COO ° K

-COO ^Θ Na

-COO ^θ NH

D stands for a -SO ^ -Phenylrest, so this can for example have one of the following formulas:

Cl, -SO ₃

COOH,

If D stands for a sulpho radical, it can also be present in salt form, i.e. D can, for example, be an alkali metal sulpho salt radical be, or a photographically inactive ammonium salt residue, i.e. D can also be, for example, a remainder of the following formulas:

-SO ₃ II, -SO ₃ ** Li ^w ;

SO

If D stands for a sulfamoyl radical or a carbamoyl radical, so can for example, this can have one of the following formulas:

-SO ₂ NH ₂ ; -SO ₂ NHCH ₃ ; -SO ₂ NHC ₂ H ₅ ; -SO ₂ N (CH ₃ J ₂ ; -

CH ₃
-SO ₂ NC ₃ H ₇ ; -SO ₂ NH C y SO ₃ H; -SO ₂ NHC ₂ H ₄ CN; -SO ₂ NHCOC ₆ H ₅ ;

409835/0947

CIU

-SO ₂ NHCOCH ₃ ; -SO ₂ NHCOCH ₇ ; -VSO ₂ N-COC ₆ H ₄ CII ₃ ; -SO ₂ NHCOCH ₂ C ₆ H ₅ ;

-SO ₂ NHC ₂ II ₅ SO ₃ H; -SO ₂ NC ₃ II ₆ -COOH; also: -CONH ₂ ; -CON (C ₇ Hg) ₂ ; CH,

I ³

-CON-C ₂ II ₅ ; -CONH-CH ₃ ; -CONIIC ₅ H ₁₁ ; also: -SO ₂ CH ₃ ; -SO ₂ C ₂ Ii ₅ ;

H ₁₃ ; -SO ₂ C ₂ II ₄ CN; -SO ₂ C ₆ H ₅ ; -SO ₂ CII ₂ C ₆ H ₅ ;

ί / Λ

COOIi

OCIu; -SO- (CII ₀ ) -; -SO ₀ NH ₀ and -SO ₉ (Ch ₉ ), -SO-K ₇ ,

If Ii stands for a halogen atom, this can for example consist of a chlorine, bromine or fluorine atom.

In addition to a hydrogen atom, M can mean, for example have any of the following plagues:

-Carboxy; -COOC ₁₁ Ii ₂₃ ; -COOCH ,,; -COOC ₆ H ₅ ; -C

COO

NO ₉ ;

Cl; -COOC ₁₂ H ₂₅ ; -SO ₃ II; -SO ₃ "Li; -SO ₃ ~ Na;

also: -SO ₉ NII ₉ ; -SO ₉ NHCH ,; -SO ₉ NHC ₉ H ₁ -; -SO ₉ N (ClU) ₉ ;

CII

I-

; -SO ₂ KC ₃ II ₇ ; -SO ₂ NIi

SU ₃ Ii; -SO ₉ MIiC ₉ Ii ₄ SO ₂ NH ₉ ;

Ϊ25 -SO ₉ NHCOC ₆ H; -SO ₂ NHCOCH ₃ ; -SO ₂ NHCO (UH ₇ ; -SO ₂ N-COC ₆ H ₄ CIU; -

COCH ₉ C ₆ H ₅ ; -SO ₂ NHC ₉ H ₅ SO ₃ ; -SO ₉ NC ₃ H ₆ -COOH; also: -CONIi ₂ ;

409835 / 09U

-CON (C ₂ H ₅ ) ₂ ; -CON-C ₂ H ₅ ; COxMHCII ₃ ; -CONHC ₅ H ₅ ; also: -SO ₂ CH ₃ ;

• SO-C-iL ·; -SO ₉ (f ) SO ₉ NH ₉ ; -SO ₉ C, ^; -SO ₉ CH ₉ C, H _c ; -SO ₉ C ^ H,

LL 5 2 \ / LL Praise ' Z L O b Zo 3

* ' ^ COOH; -SO ₂ C ₉ H ₄ CN; -SO ₂ C ₃ Ii ₆ OH;

Particularly advantageous compounds of the formulas I and II are those in which:

Y is a carrier or a component carrier group, the or as a function of oxidation under alkaline conditions split off a dye or sets of freedom, the mobility or diffusivity is different from the starting compound uer;

P. "is an alkylene radical having 1 to 4 carbon atoms, one optionally by a carboxy, methyl, methoxy or chlorine radical substituted phonylene radical;

L is a sulfamoyl, sulfonamido, carbamoyl or carboxamido radical;

R is a hydrogen atom;

m = 0 or 1;

Q represents a hydrogen atom, a hydroxyl radical or a radical of the formulas - !, "iiCOR" ³ or -XHSO ₉ R " ⁵ , xv ^r orin R ^J represents an alkyl radical having 1 to 4 carbon atoms; or an alkyl radical having 1 to 4 carbon atoms, the is optionally substituted by a hydroxy, cyano, sulfa ^ oyl, carboxy or SuIfο-

409835/0947

rest; a benzyl radical or one which is optionally substituted by a carboxy, methyl, ethoxy, sulfamoyl or chlorine radical Phenyl radical;

D is a chlorine, fluorine or bromine atom or a cyano, trifluoromethyl, nitro or fluorosulfonyl radical or an alkylsulfonyl radical having 1 to 6 carbon atoms, which can optionally be substituted by a hydroxy, phenyl, cyano, sulfamoyl, carboxy -, fluorosulfonyl or sulforest; a phenylsulfonyl radical which can optionally be substituted by a hydroxy, sulfamoyl, fluorosulfonyl, carboxy or sulpho radical; a sulfamoyl radical of the formula -SO-NHR, in which R represents a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms, which can optionally be substituted by a hydroxy, cyano, sulfamoyl, carboxy or sulpho radical; a benzyl radical; a phenyl radical which can optionally be substituted by a hydroxy, sulfonyl, sulfamoyl, carboxy or sulpho radical; or a carbamoyl radical of the formula -CON (R ⁵ ) -, in which R represents a hydrogen atom or a methyl radical;

D is a radical of the formula Y- [x- (NR-J) q3 _m ~ or YXJ-, provided that the substituent Y - [. X- (NR-J) J _m on the naphthalene nucleus of the formula I is replaced by a radical of the formula M has been replaced, or that the radical YXJ-NH- on the naphthalene nucleus of the formula II has been replaced by a radical Q, with the proviso that Y, X, J, R, q and m have the meanings already given;

E is a hydrogen atom or a fluorine or chlorine atom, and

M is a hydrogen atom or a sulfamoyl radical of the formula -SO ₉ NHR,

ft

vforin R is hydrogen; an alkyl radical having 1 to 4 carbon atoms; an alkyl radical with 1 to 6 carbon atoms, which is substituted by a hydroxy, cyano, sulfamoyl, carboxy or Sulforest; a benzyl radical; or one which is optionally substituted by a hydroxy, sulfamoyl, carboxy or sulpho radical Phenyl radical.

409835/0947

As very particularly advantageous compounds of the formulas I and II those have been found in which the substituent Y-X-J-NH in formula II is in the 5-position of the naphthalene nucleus G and in which the substituent Y-IX- (NR-J) i in formula I the naphthalene nucleus is in the 5- or 6-position with respect to G and where also mean:

R is an alkylene radical having 1 to 4 carbon atoms or one Phenylene radical;

L is a sulfamoyl or sulfonamido radical; J is a sulfonyl radical;

Q is a hydrogen atom or a hydroxy, -NHSO-R- or -NHCOCH ₃ radical in the 5- or 8-position with respect to G;

G is a hydroxy group or a photographically inactive ammonium salt group thereof or a hydrolyzable acyloxy radical of one of the formulas:

-OCR or

-OCOR ⁴

wherein R is an alkyl group having 1 to 18 carbon atoms, a phenyl group or a chlorine atom or a nitro group is substituted phenyl;

D is a chlorine or bromine atom or a cyano, trifluoromethyl or nitro radical or an alkylsulfonyl radical having 1 to 6 carbon atoms or a benzylsulfonyl radical;

F, a hydrogen atom and M is a hydrogen atom.

Particularly advantageous compounds are those specified Formulas in which X is a phenylene radical of the following formulas:

409835/0947

and in which also mean:

G is a hydroxy radical or a hydrolyzable acyloxy radical and D is an alkylsulfonyl radical having 1 to 4 carbon atoms.

Compounds of the formulas I and are of very particular importance II, in which Y is a radical of the following formula:

III. Y ¹ τ— ball

NIISO ₂ -

wonn

Ball an organic ealast ^ group of such size and configuration represents, which the connection during the development process by means of an alkaline developing liquid does not diffuse and in what

Y ^{1 represents} the carbon atoms necessary to complete a benzene or naphthalene nucleus, including substituted benzene or naphthalene nuclei.

Y 'stands for the atoms that make up a naphthalene nucleus are required, the ballast group can be on one of the two rings. Particularly advantageous ballast group ball are those of the following formulas:

-CNH-BaIl or -SO ₀ NH-BaIl.

409835/0947

Examples of particularly advantageous carriers or carrier components Y are: ""

H 0 Il

CNH- (CH ₂ ) .O

NHSO ₂ -

OH ο

B I

-CNIICII ₂ CHO

NHSO

011

-CNH _{(CH2) 4} 0

C ₁₅ Ii ₃₁

NIISO ₂ -

OH

-SO ₂ NH (CH) .O

NHSO,

OH

^H 31 ^C 1S

NHSO ₀ -

409835/0947

OH

CONII

^C 14 ^H 29

NHSO.

OH

KHSO ₂ -OH

C ₇ II _n

ι ²

CONIiCH ₂ CO-

NHSO.

o ccii ₂ ) ₄ -o

* NHSO ₂ -

OH

CO (CH ₂ ) ₁₄ CH ₃ and

NHSO ₂ -OH

NHSO ₂ -

A09835 / 09A7

The nature of the ballast group (ball) in Formula III is not critical, i.e. the compounds of the formula III can have a wide variety of ballast groups, as long as these are only suitable for the Ensure non-diffusibility of the compounds. Typically, the Ba Hast groups consist of long-chain alkyl radicals that can be bound directly or indirectly to the molecule or from aromatic residues of the benzene and naphthalene series, which can be bound indirectly to the molecule or fused to the benzene nucleus. In general, they point Ballast groups have at least 8 carbon atoms, i.e. the Bailas tgruppe can consist, for example, of an optionally substituted alkyl radical with 8 to 22 carbon atoms or

or, for example, from an amide radical with 8 to 30 carbon atoms, / one Keto radical with 8 to 30 carbon atoms. Furthermore, the Ballast group, for example, can also be a polymer residue or consist of a polymer chain.

Such compounds have proven to be particularly advantageous, in which the ballast group is bound to the benzene nucleus via a carbamoyl residue (-NHCO-) or via a sulfamoyl residue (-SO-NH-), where the nitrogen atom is adjacent to the ballast group.

In addition to a ballast group, the benzene nucleus can be of the specified type Formula can be substituted by various other groups and / or atoms, e.g. by halogen atoms, alkyl, aryl, Alkoxy, aryloxy, nitro, amino, alkylamino, arylamino, amido, Cyano, alkyl mercapto, keto uride / or carboalkoxy groups and / or heterocyclic radicals.

According to a particularly advantageous embodiment of the invention, Y or Y ^{1 is} a radical which, as a function of oxidation under alkaline conditions, releases a dye which has a mobility or mobility that is different from the mobility or mobility of the compound producing an image dye.

Particularly advantageous new dyes which are derived from the carrier residue

409835/0947

Y or Y ¹ can be released as a function of the oxidation with alkaline clearances, can be represented by the following structural formulas:

IV.

D.

or

V.

wherein

Z is a residue of the formulas -SO ₉ IMi ₉ ; -30 _ο .Ί or IK- u displays,

where R ^{1 is} an alkyl radical having 1-4 carbon atoms, and in which further

X, II, J, q, m, Q, G, M, J and L · the meaning already given

have with the exception that the Y-substituent possibly standing for U is replaced by Z.

If Z represents a radical of the formula -CO ₀ Ii, the dyes shown can be released, for example, by reactions such as are known from US Pat. Nos. 3,443,940, 3,628,952 and 3,698,897.

If Z represents a radical of the formula y in which R ^{1 is} an alkyl

HN-

rest with 1 - 4 C-atoms, e.g. an I-iethylrest, then the represented Dyes released by reactions, as described in more detail, for example, in .BL-PS 78 8 268.

The compounds according to the invention are used advantageously in concentrations of e.g. 2.5 - 20 mg / dm ^ support surface.

Particularly advantageous dyes released are those of

409835/0947

Formulas IV and V in which Z is a radical of the formula -SO ₇ NH-. These dyes can be released by reactions such as are described for example in US-PS 326628, for example, of a carrier rest of Y ^1, as shown in Formula III.

An advantageous process for producing a photographic color transfer ^{image using compounds according to the invention, for example those in which Y 1 has} the meaning shown in formula III, consists of the following process steps:

1.) Treatment of the photosensitive recording material with an alkaline developing liquid in the presence of a silver halide developing agent to develop each of the exposed silver halide emulsion layers, wherein the developing agent is oxidized and the one is oxidized The developer compound in turn oxidizes the image-forming compound, e.g., a sulfonamido compound;

2.) Creation of an imagewise distribution of a diffusing, released dye as a function of imagewise exposure of each silver halide emulsion layer by breaking down each of the oxidized image-forming compounds, e.g. sulfonamido compounds, and

3.) Diffusion of at least part of the imagewise generated diffusing dye into an image-receiving layer.

The photosensitive recording material can be used to initiate the development process in a conventional manner with a alkaline developing liquid. A particularly advantageous method of using the developing liquid consists in the use of a splittable container that contains the developing liquid. The developer compound can be in advantageously be contained in the developing liquid.

409835/0947

On the other hand, however, the developing agent may be present in the recording material are accommodated, in many cases only an alkaline solution to activate the incorporated developer compound needs to be used.

The photographic recording material can advantageously be used according to the invention consist of a so-called photographic recording unit which is constructed so that it through Passing through the gap formed by two pressing members can be developed. Such a recording unit can be composed of:

1.) a light or photosensitive recording material, as already described;

2.) an image receiving layer and

3.) at least one splittable container with alkaline developing liquid, which is so arranged and arranged that when it is split it will contain its contents in the recording unit able to distribute;

with the proviso that the recording unit further comprises a silver halogen developer compound contains.

The image receiving layer of such a recording unit can be arranged on a separate layer support which is connected to the light-sensitive part of the recording unit in such a way that that it can be applied thereon after exposure of the photosensitive member. Such image receiving layers or image receiving layers elements are known, for example, from US Pat. No. 3,362,819. If the developing liquid is supplied via a splittable container, this is expediently related to the photosensitive recording part and the image receiving part arranged so that when pressure is applied, e.g.

409835/0947

two pressure-exerting members, such as those in so-called self-development cameras are present, the contents of the container between the image receiving part and the outermost layer of the photosensitive Recording part is distributed. After the development has been carried out, the image receiving part of the photosensitive Record part are separated.

However, the image receiving layer of the recording unit may also be integrated with the light-sensitive recording part and e.g. between the .i layer support of the recording part and the be arranged at the lowest light-sensitive silver halide emulsion layer. This means that a recording unit according to the invention with a so-called integrated image receiving layer, for example, can have a structure such as that from the BE-PS 757 960 is known. In such an embodiment of a recording unit the substrate of the photosensitive recording part is transparent and has an image receiving layer, a practically opaque or light-impermeable, light-reflecting layer, e.g. a titanium dioxide layer, and the light-sensitive or coated with photosensitive layers. After exposure of the photosensitive or light-sensitive part of the recording unit, a splittable container of alkaline developing liquid and an opaque or opaque cover sheet are placed on the exposed photosensitive Part applied. The splittable container is split open by the action of the pressure-exerting members of a self-development camera and distributes its contents over the photosensitive recording part of the recording unit when it comes out of the Camera is withdrawn. The developing liquid then develops the exposed silver halide emulsion layers to produce image dyes as a function of development which are then used in the image-receiving layer diffuse to produce a positive, right-sided image that passes through the transparent support can be viewed on the opaque reflective background.

A recording unit according to the invention with an integrated

409835/0947

_ 25 -

The image receiving layer can also have the structure known from BE-PS 757 959, for example. In this The trap is the support of the photosensitive recording part transparent and with the image receiving layer, a practically opaque or light-impermeable, light-reflecting one Layer and one or more light-sensitive silver halide emulsion layers coated. In this case, a splittable container is used with an alkaline developing liquid and an opacifying agent in contact with the top layer of the recording unit and a transparent cover sheet brought. The recording unit can then be in a camera with exposure through the transparent cover sheet, followed by two pressures on the unit exercising members is guided,; ^ enn the unit removed from the camera. Thereby the splittable container split up and distributes its content along with opacifying agents or opacifying agents over the negative part of the recording unit and makes them light-insensitive. The developing liquid develops the silver halide layer or layers to produce image dyes which are incorporated into the image receiving layer diffuse and zxvar producing a positive laterally correct Image that passes through the transparent substrate on the opaque or opaque reflective background layer can be considered, other so-called integrated Recording units, for their production the invention image-forming compounds can be used are, for example, from U.S. Patents 3,415,644, 3,415,645, 3,415,646, 3,647,437 and 3,635,707 are known.

Recording units according to the invention can be used for production positive monochrome as well as multicolored images can be used. In the case of a three-color system, each silver halide emulsion layer exists the recording unit is in contact with an image-boosting compound which is a predominant or predominant one has spectral absorption within the range of the visible spectrum, in contrast to the silver halide emulsion class

409835/0947

is sensitive. This means that the blue-sensitive silver halide emulsion layer either contains or has a yellow image dye forming compound Veroverbindung containing rail is in contact that also the green-sensitive silver halide emulsion layer contains or with a magenta image dye-forming compound Layer with such a compound in contact, and that finally the red-sensitive silver halide emulsion layer a cyan image dye-forming compound contains or is in a layer with such a compound Contact is available. It is understood that the cyan image dye forming compound is a cyan image dye forming compound of the present invention.

When G is hydrolyzable acyloxy, the absorption spectrum becomes of the azo dye shifted to the region of shorter wavelengths. Such, in the patent literature as "shifted dyes" Dyes that have become known absorb light outside the range, in contrast to the Si / berhalide emulsion layers assigned to these dyes are sensitive. The usability of so-called. "Shifted" azo dyes is inherently from the U.S. Patent 3,307,947 is known. The dyes according to the invention with absorption spectra shifted to shorter wavelengths can be incorporated into silver halide emulsion layers without any significant reduction in the sensitivity of the layers. Of the Acyloxy radical is hydrolyzed by the alkaline developing liquid, releasing the blue-green dye.

The yellow and magenta image dye forming compounds may consist of conventionally known compounds, for example those as described in BE-PS 788 268. Other suitable magenta image dye forming agents Compounds are described, for example, in U.S. Patent Application Serial Number 331,729.

409835/0947

The concentration of the compounds used according to the invention which can be split up by alkali metal oxidation in the compounds according to the invention Recording materials and recording units can be very different, depending on the compound used in the individual case and the desired result. The image dye-forming compounds can be layered in the form of dispersions into a natural or synthetic hydrophilic film-forming Polymers may be included, the binder made of one of the usual naturally occurring binders or a synthetic one Binder, i.e. a synthetic polymer, e.g. gelatin or polyvinyl alcohol, which can be used for aqueous alkaline developing fluids is permeable. The relationship from the image dye-forming compound to the polymer is preferably from 0.25 to 4.0.

The compounds according to the invention are typically prepared using a common color coupler solvent, e.g., a high-boiling water-immiscible organic solvent in the. incorporated coating materials used to produce the recording materials and recording units, the usual known methods being used.

Depending on the meaning of Y or Y 'in the given formulas, a large number of different silver hebgeniderite can be used connections can be used. If the carrier component corresponds to the formula III, for example, the recording materials can be developed and recording units for each silver halide developing agent can be used as long as this only leads to a so-called upper cross oxidation with one image dye generating connection is enabled.

As already stated, the developing agent can be used not only in the alkaline developing solution but also in the recording material or the recording unit itself, in which case this by the alkaline developing liquid is activated.

409835/0947

Examples of developer compounds which can be used in the present invention are:

Hydroquinone; Aminophenols, for example N-methylaminophenol; 1-phenyl-3-pyrazolidone; 1-phenyl-4,4-dimethyl-3-pyrazolidone; 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; Ν, Ν-diethyl-p-phenylenediamine; 3-methyl-N, N-diethyl-p-phenylenediamine and 3-methoxy-N, N-diethyl-p-phenylenediamine. Black-and-white developer compounds are advantageously used, since these have a reduced tendency to discolour the image-receiving layers. If a silver halide developing agent is used, it will be oxidized during development and reduce silver halide to metallic silver. The oxidized developing agent then in turn oxidizes the image dye releasing compound. The reaction product of this cross-over oxidation then undergoes alkaline hydrolysis, releasing a diffusing anionic dye imagewise, which diffuses into the image-receiving layer and here produces a positive dye image. The diffusing dye is transferred in the alkaline developing liquid either because of its intrinsic diffusibility or by one or more solubilizing radicals, for example radicals of the formulas -COOH, -SO ₃ H, -SO ₂ NR ⁵ R ⁶ or -OH, where R ⁵ and R ^{6 have} the meaning already given, at least one of these radicals being a hydrogen atom.

The generation of diffusible image dyes from the image dyes releasing compounds is a function of the development of the silver halide emulsion layers with a developing agent producing negative or direct-positive silver images in the emulsion layers. Are used to manufacture the recording materials direct positive silver halide emulsions or solarizing emulsions used in the non-exposed Districts are developable, are layers in the image receiving received positive pictures. After exposure of one made using direct positive silver halide emulsions

409835/0947

Recording material or a corresponding recording unit, the alkaline developing liquid permeates the various layers to initiate the development of the exposed light-sensitive silver halide emulsion layers. The silver halide developing agent present in the recording material or in the recording unit then develops each of the silver halide emulsion layers in the unexposed areas (since the silver halide emulsion layer consists of direct positive emulsion layers), the developing agent being oxidized in an imagewise fashion corresponding to the unexposed areas of the direct positive silver halide emulsion layers. The oxidized silver halide developing agent then in turn oxidizes the dye-releasing compounds, whereupon the oxidized form of these compounds undergoes a base-catalyzed reaction, whereby, according to an advantageous embodiment of the invention, preformed dyes are released from these compounds as a function of the image-specific exposure of each silver halide emulsion layer. At least some of the imagewise released diffusing dyes then diffuse into the image-receiving layer to form a positive image of the original. After the recording material or the recording unit has been brought into contact with the alkaline developing liquid, a pH-reducing layer in the recording material or the recording unit, for example in the image receiving part, can reduce the pH of the recording material or the recording unit, and for example with stabilization of the image generated in the image receiving layer. The use of a layer which reduces the pH value has proven to be advantageous. However, the use of such a layer is not absolutely necessary.

Advantageously, so-called internal image silicon / overhalide emulsions can be used for the production of photographic recording materials according to the invention or so-called inner grain emulsions can be used. These emulsions are direct positive silver halide emulsions, which latent images for the most part inside

409835/0947

of the silver halide grains to the difference of such Silver halide grains, the majority of which form latent images on the surface of the grains. Such interior or internal grain emulsions are known, for example, from US Pat. No. 2,592,250. Others suitable for making photographic Emulsions suitable for recording materials and recording units according to the invention are, for example U.S. Patent No. 3,761,276. Internal image or internal grain silver halide emulsions are those that are characterized by an increased maximum density, which is reached when this Emulsions are developed in a so-called internal grain developer, in contrast to development in a so-called surface developer. Particularly suitable internal image or internal grain emulsions are those which are characterized by the following properties, determined by customary known photographic methods:

If a test sample of the silver halide emulsion is applied to a transparent layer support, the recording material obtained is exposed to a light intensity scale for a certain period of time between 0.01 and 1 second and the exposed material is used for three minutes at 20 ° C. in a developer A, as stated later composition, ie, a so-called. Innenkornentwiekler developed, these emulsions have a maximum density that is times as large at least 5 as the maximum density that is erreicnt when an exposed in a corresponding manner, the silver halide emulsion for 4 minutes at 20 ⁰ C in a developer B of the composition given below, ie a so-called surface type developer. Preferably, the maximum density when using developer A is at least 0.5 density units greater than the maximum density when using developer B.

Developer A

Hydroquinone 15g

Monomethyl p-aminophenol sulfate 15 g

Sodium sulfite (dehydrated) 50 g

409835/0947

Potassium bromide 10 g

Sodium hydroxide 25 g

Sodium thiosulphate 20 g

Made up to 1 liter with water

Developer B

p-hydroxyphenylglycine x 10 g

Sodium carbonate 100 g

Made up to 1 liter with water

Become such internal image or internal grain silver halide emulsion layers developed in the presence of a fogging agent or a nucleating agent. direct positive images are obtained. Such emulsions have proven particularly advantageous for the production of photographic recording materials and recording units proven according to the invention. Suitable fogging agents are, for example, hydrazines, such as those described in, for example U.S. Patents 2,588,982 and 2,563,785, and hydrazides and hydrazones such as that disclosed in U.S. Patent 3,227,552 Type, furthermore quaternary hydrazone salts, e.g. of the type known from US-PS 3,615,615 or BE-PS 749,703, furthermore the Polymethine dyes containing hydrazone radicals according to US Pat. No. 3,718,470 or mixtures thereof. The amount of used Fogging agents can vary widely depending on the results desired. In general, it has been found to be useful about 0.4 to about 8 g of fogging agent per mole of Ag in the light-sensitive layer of the light-sensitive material or about 0.1 to about 2 g per liter of developer, provided that the fogging agent is incorporated in the developing liquid is going to use. The fogging agents known from US Pat. Nos. 3,615,615 and 3,718,470 are preferably used in concentrates from 0.5 to 10 mg per mole of silver of a photosensitive layer is used.

409835/0947

In those which can be used for the production of photographic recording materials and recording units according to the invention solarizing direct positive silver halide emulsions are known silver halide emulsions which either chemically or by irradiation to a point approximately equal to the maximum density of the inverse curve, (See Mees, "The Theory of the Photographic Process", publisher Macmillan Company, New York, New York, 1942, pages 261 to 29 7) have been veiled. Typical processes for making solarizing Emulsions are known from GB-PS 443, for example. In these processes, emulsions are used as long as Exposure to X-ray radiation until an emulsion layer formed from these emulsions develops without any previous exposure is blackened to the apex of the gradation curve. Other methods are for example from GB-PS 462 730 known. In these processes, common silver halide emulsions are grown or used from chemicals, e.g. silver nitrate, or organic sulfur compounds or dyes, into solarizing, direct-positive emulsions. From US-PS 2 005 837 it is the further known, for example, to achieve solarization silver nitrate and other compounds in connection with the Use exposure to heat. Other suitable solarized emulsions are known, for example, from U.S. Patent 2,541,472. These emulsions are particularly for exposure to longer wavelength light and for development to generate the von Mees described Herschel effect, caused by the addition of benzothiazoles and other compounds to the emulsions, which have been obscured either chemically or by white light. The veiled ones are also particularly suitable direct positive emulsions such as those described in U.S. Patents 3,367,778, 3,501,305, 3,501,306, and 3,501,307 as well as combinations thereof.

409835/0947

Further recording materials and processes for their production or carrying out the image dyes according to the invention producing Compounds that can be used are disclosed, for example, in U.S. Patents 3,227,550; 3,227,551; 3,227,552 and 3,364,022 are known.

In the case of photographic recording materials according to the invention which contain compounds according to the invention of the formulas given in which Y or Y 'is a silver halide developer radical, for example according to US Pat a solution of the dye developing agent and uniformly distributing it in the emulsion layer (s). In the development of exposed silver halide, the oxidation product of the dye developer is immobilized or precipitated in situ with the developed silver, under generation of an imagewise distribution of unoxidized dye developer compound _t dissolved in the developing liquid. Obviously, this immobilization is due, at least in part, to a change in the solubility characteristics of the dye developing agent due to oxidation. At least a portion of the imagewise distributed unoxidized dye developer bond is then transferred to an applied image receiving layer to form a transfer image.

Negative silver halide emulsions suitable for the production of photographic recording materials and recording units can, for example, from silver chloride, silver bromide, silver chloride bromide, silver bromide iodide or silo chloride bromide iodide emulsions or mixtures thereof. The emulsions can be coarse-grained or fine-grained emulsions act, which can be prepared by customary known methods. This means that the emulsions for example, so-called single enema emulsions, as described e.g. by Trivelli and Smith in the magazine "The Photographic Journal ", Volume LXXIX, May 1939, pages 330 to 338, or so-called double enema emulsions, for example

409835/0947

wise Lippmann emulsions, ammoniacal before emulsions, in the presence emulsions ripened by thiocyanates or thioethers, such as those disclosed, for example, in US Pat. Nos. 2,222,264, 3,320,069 and 3,271 to be discribed. Finally, surface-sensitive or surface-image emulsions can be used or internal image emulsions, as known, for example, from U.S. Patents 2,592,250, 3,206,313, 3,367,778 and 3,447,927. In the case of emulsions, there are also so-called regular emulsions, e.g. that of Klein and Moisar in the journal J. Phot. May be. , Vol. 12, No. 5, 1964, pages 242-251.

The image dye-forming compounds of the invention can also be used, for example, in the context of image reversal processes, such as those from GB-PS 904 364, page 19, lines 1 to 41, are known. In the case of such a process, the image dyes of the present invention are used generating compounds in combination with physical development nuclei used in a seed layer adjacent to a photosensitive silver halide emulsion layer. The for Carrying out the method contains a suitable recording unit further a silver halide solvent, preferably in a separable container with the alkaline developing liquid.

The various silver halide emulsion layers of a color photographic Recording material or a color photographic Recording units according to the invention may be arranged in the usual known order, i.e. the blue-sensitive silver halide emulsion layer may be the layer which is closest to the light source used for exposure, whereupon öta ^ xxKXxSatfxskXMKgxxsxMSÄ £ e: taEÄXkx! diXQfiisxx * xM die green-sensitive and the red-sensitive silver halide emulsion layers follow. If necessary, a layer containing a yellow dye or a so-called Carey Lea silver layer can be interposed the blue-sensitive and green-sensitive silver halide emulsion layers be arranged to absorb blue radiation which passes through the blue-sensitive layer, or

409835/0947

to filter out. Optionally, however, the selectively sensitized silver halide emulsion layers can also be in a different one Order on the support, i.e. the blue-sensitive layer can be, for example, the first layer on which light strikes during exposure, followed by the red-sensitive layer and the green-sensitive layer.

That present in recording units according to the invention Fissile containers can, for example, have a structure such as that disclosed in U.S. Patents 2,543,181, 2,643,886, 2,653,732, 2,723,051, 3,056,490,2; 3,056,491; and 3,152,515. In general, such splittable containers consist of sheet-shaped, for Liquid and air impermeable materials that are folded and welded so that they form a space in which the Development fluid was housed.

In the case of color photographic recording units according to In the invention, any silver halide emulsion layer having an image dye-forming compound or having a the layer associated with the silver halide emulsion layer one image dye forming compound from another Silver halide emulsion layer and optionally its associated layer with an image dye-forming layer Connection must be separated by separating layers, e.g. separating layers made of gelatine, calcium alglnate or substances like them for example in U.S. Patent 3,384,483 or made of polymeric materials such as polyvinylamides such as those described in U.S. Patent No. 3,384,483 3,421,892 are known, or compounds such as those described, for example, in FR-PS 2 028 236 or US-PS 2 99 2 104, 3 043 69 2, 3 044 873, 3 061 428, 3 069 263, 3 069 264, 3 121 011 or 3,427,158.

- 36 -

409835/0947

The individual silver halide emulsion layers advantageously exist Photographic materials and recording units according to the invention composed of emulsion layers, for example gelatin emulsion layers about 0.6 to 6 microns thick.

The photographically effective compounds of the present invention such as the yellow dye forming compounds can, if they are not accommodated in the silver halide emulsion layers themselves, e.g. in permeable to aqueous alkaline solutions polymeric binders, e.g. gelatin, and in a special layer, e.g. a layer thickness of 1 to 7 microns. Contain the recording materials or recording units for alkaline solutions permeable, intermediate layers made up of polymers, e.g. gelatin intermediate layers, so these are preferably 1 to 5 microns thick. The specified layer thicknesses can, depending on the type of material to be produced Recording material or the recording unit to be produced are fallen below or exceeded.

The usual known ones can be used to produce the image receiving layer Compounds can be used as long as they only have the desired function, i.e., those that diffused into the image-receiving layer To pickle dyes or to fix them in some other way. In the individual case for the production of the image receiving layer The substances used depend of course on the type of dye or dyes to be stained. When pickling For acidic dyes, the image-receiving layer can contain a basic polymeric mordant or be composed of such. Such polymeric mordants can consist, for example, of aminoguanidine derivatives of vinyl methyl ketones, as they are, for example are known from US Pat. No. 2,882,16. Other suitable basiche polymeric mordants are for example from US-PS 3625694u. 3 709 690 known.

Particularly advantageous mordants are cationic mordants, e.g. polymeric compounds with quaternary nitrogen atoms and at least two aromatic nuclei per quaternary nitrogen atom

409835/0947

in polymerization, i.e. with at least two aromatic nuclei, for each positively charged nitrogen atom, with the proviso that such polymeric compounds should be free or practically free of carboxy radicals. Examples of mordants of this type are such with repeating units of the following formula and repeating units of at least one other ethylenically unsaturated Monomers:

CH

11

R '- C -

10

where mean:

7 8
R and R each represent a hydrogen atom or a short-chain alkyl radical having 1 to 6 carbon atoms;

R is a hydrogen atom, a short-chain alkyl radical or a Radical with at least one aromatic nucleus, for example a phenyl, naphthyl or tolyl radical;

Q is an alkylene radical with 1 to 6 carbon atoms, an arylene radical, an aralkylene radical or an arylenealkylene radical, also reads one of the following formulas:

Il

1 ? ' 1 ? M 1

-C-OR-, -OC-Pv or -C-NH-R ¹

1 2
wherein R is an alkylene radical;

R together with Q is a radical of the formula

-C -C

NO

12th

409835/0947

Ii. , K. and κ a short-chain alkyl or aryl radical or IX " and R, together with the nitrogen atom on which they are located, and together with Q the atoms and bonds that form a heterocyclic ring containing a quaternary nitrogen atom are required and

\ a monovalent negative salt-forming radical or a corresponding atom in ionic relation to the positive salt-forming radical,

with the proviso that the polymer is free or practically of carboxy groups should be free and where the positive salt-forming reads of the polymer have at least two aryl radicals per quaternary nitrogen atom target. In a particularly advantageous manner, Q is an optionally substituted phenylene radical and P ″, R and R are the same or various alkyl radicals, with the proviso that the sum of the carbon atoms does not exceed 12 due to alkyl radicals. Such particularly advantageous polymeric cationic mordants are for example in U.S. Patent 3,709,690.

Other suitable mordants for the preparation of image-receiving layers are, for example, poly-4-vinylpyridines and also 2-vinylpyridines of the type known from US Pat. No. 2,484,443 and, for example, cetyltriethylammonium bromide. Particularly effective pickling agents for Frzeuguiij of iilder.ipfangsschichten are further for example in U.S. Patents 3,271,143 and 3,271,147.

particularly advantageous results can be obtained when the image-receiving layer is per-

409835/0947

is meabel and transparent and has a thickness of about 0.00635 to 0.010 mm. However, this thickness range can also be exceeded or fallen below. Optionally, the image receiving layer furthermore ultraviolet radiation absorbing ver. contain bonds to the stained dye images before Protect from fading from exposure to ultraviolet light. Finally, the image receiving layer can also be optical Contain brighteners, e.g. based on stilbene, coumarin, triazine or oxazole and / or dye stabilizers, e.g. chromanols and / or alkyl phenols.

t-

By using a pH-reducing substance or a pH-reducing layer in the image receiving part of a recording unit according to the invention, the stability of the transferred image can be improved. It has proven to be expedient to use substances that reduce the pH value which reduce the pH value of the image layer from about 13 or 14 to at least 11, preferably to at least 5-8 within a short period of time after exposure to the Lead developing liquid. As the pH lowering substances example \ v ^r else polymeric acids can be used as they are described for example in U.S. Patent No. 3,362,819 or solid acids or metallic salts such as zinc acetate, zinc sulfate, or magnesium acetate, as described for example in US -PS 2 584 030 are known. Such pH reducing agents lower the pH of a recording unit after development and stop development and reduce further dye transfer while stabilizing the transferred image.

Advantageously, a photographic recording material or a photographic recording unit according to the invention further a so-called inert delay or Control layer, e.g. over the pH-reducing layer, which has the task of reducing the pH-value as To control or control the function of the speed with which the alkali diffuses through the inert control layer.

Examples of such .Control or delay layers are Layers of gelatin, polyvinyl alcohol or other substances, v.'ie they are described, for example, in Uo-PS 3 455 686. Such a control or timer layer can also be compensatory act on the various reaction rates within a wide temperature range. Σ.Β. can a Premature decrease in pH value can be prevented if the exposure the alkaline developing solution is carried out at a temperature above room temperature, for example at 35 to 37.8 ° C. the The control or delay layer can advantageously have a layer thickness of 0.0025 to 0.015 mm. Particularly advantageous Results are obtained when such control or timing layers are built up from a hydrolyzable polymer or a mixture of such polymers which are slowly hydrolyzed by the developing liquid. Examples for such hydrolyzable polymers are polyvinyl acetate, polyamides and cellulose esters.

For the development of photographic recording materials and recording units according to the invention may be conventionally known ones aqueous solutions of alkaline substances, e.g. sodium hydroxide, sodium carbonate or amines, e.g. diethylamine, are preferred with a pH above 11, can be used. These developing liquids preferably contain a developing compound. These solutions advantageously contain or Liquids also contain a viscosity increasing compound such as a high molecular weight polymer such as a water soluble one Ether which is inert to alkaline solutions, e.g. hydroxyethyl cellulose or alkali metal salts of carboxymethyl cellulose, e.g., sodium carboxymethyl cellulose. The concentration of the viscosity-increasing compound is preferably at about 1 to about 5 percent by weight based on the weight of the developing liquid, and preferably that much of the viscosity enhancing agent Compound used that the developing liquid is a Has viscosity from about 100 cps to about 200,000 cps.

As already explained, the developing liquid can also

409835/0947

ters contain an opacifying agent or an opacifying agent, e.g. TiO «or soot. or pH indicator dyes.

Although the alkaline developing liquid is preferably placed in a splittable container, so can other methods of introducing the developing liquid into a photographic recording unit according to the invention have been used will. For example, the developing liquid by means of communicating limbs, similarly hypodermic Introduce syringes, which can be arranged in the camera or a camera cartridge, into the recording unit.

The present in some recording units according to the invention, for alkaline solutions permeable, practically opaque or opaque, light-reflecting layer can consist of any Binder and an opacifying agent dispersed therein. Whites have proven to be particularly advantageous light-reflecting layers have been shown to provide an aesthetically pleasing background, on which a transferred dye image can be viewed and because such layers further have the optical properties necessary for reflection of incident radiation are desired. Suitable opacifiers or opacifying agents are for example titanium dioxide, barium sulfate, zinc oxide, larium stearate, Silver flakes, silicates, aluminum oxide, zirconium oxide, zirconium acetylacetate, sodium zirconium sulfate, kaolin, mica or Mixtures of these in various concentrations, depending on the degree of opacity desired. never opacifiers or opaque-making compounds can thereby be dispersed in a wide variety of customary known binders, e.g. in gelatin permeable to alkaline solutions or Polyvinyl alcohol. Optionally, optical brighteners can also be incorporated into the light-reflecting layer, z.H. on syllables ~, Coumarin, triazine or gxazole base. Should the licitundurclassigkeit or the opacity capacity of the light-reflecting layer is particularly high, so for the production of the light-

409835/0947

reflective layers used dark-colored opacifiers e.g. soot, nigrosine dyes and the like, such compounds or substances also being accommodated in a separate layer adjacent to the light-reflecting layer can be.

For the production of the photographic recording materials or recording units according to the invention can be the usual ones known supports can be used, such as those used for the production of photographic recording materials and recording units are common. The layer supports typically consist of flexible films made of cellulose nitrate, cellulose acetates, polyvinyl acetals, Polystyrene, polyethylene terephthalate, polycarbonates or poly-a-plefins, e.g. polyethylene and polypropylene or foils from similar or corresponding resinous substances. The layer support advantageously has a thickness of approximately 0.050 to 0.15 mm.

Silver halide emulsions suitable for the production of photographic recording materials and recording units according to the invention are for example in the journal "Product Licensing Index", Volume 92, December 1971, publication 9232, Described in more detail on page 107 in Paragraph I under "Emulsion types". The emulsions can be chemically and spectrally sensitized, as for example from page 107, paragraph III, "Chemical Sensitization" and pages 108 to 1CC, Section XV "Spectral Sensitization" is known. Finally, the emulsions can be protected from the formation of a haze in a conventional manner and stabilized against loss of sensitivity during storage, e.g. by using compounds, as for example on page 107 in paragraph V uiter of the headline "Antifoggants and Stabilizers" will be described. Finally, the emulsions can also be development-modifying Contain compounds, hardening agents and / or layering agents, as they are on pages 107 to 108, paragraph IV under the fiberscurift "development modifiers", paragraph VII un-

409835/0947

ter the heading "hardener" and paragraph XII under the Heading "Coating Aids". are described in more detail. Furthermore, the emulsion layers and other layers can be used of the recording materials and recording units plasticizers or plasticizers and such binders and / or filter dyes as they are on page 108 in paragraph XI under the heading "Plasticizers and softeners" as well as in paragraph VIII under the heading "Binding agents" and on Page 109 in paragraph XVI under the heading "absorption and filter dyes" are described in more detail. Finally they can Silver halide emulsion layers the other layers of photographic materials and recording units according to the invention contain additives which are incorporated by methods such as those on page 109 in paragraph VII under the heading "Methods of addition" are described in more detail. Finally, the emulsion layers and other layers can be used after the conventional known coating processes can be applied to the substrate, e.g. by methods such as those on page 109 in Paragraph XVIII under the heading "Coating Process" is described in more detail.

It should be noted that nac>: image transmission has taken place in the recording section a recording unit of dye and developed Silver remains in image-wise splitting. From the recording part With the non-diffusing compound, a color image can be produced by removing the silver and Silver halide can be removed by conventionally known methods, e.g. by means of a bleaching bath and the use of a fixing bath, a bleach-fixing bath or the like.

If so desired, you can also use the image-wise distribution present dye or the dyes present in imagewise distribution from the recording part or recording material diffuse into a bleach or fixer or a bleach-fixer instead of the dye (s) into one Diffuse image receiving layer. If a negative ar-

409835/0947

beiter.de Silver halide emulsion for the production of a photographic When recording material is used, a positive Dye image, e.g. a color slide or a motion picture in this one Way to be generated. Become direct positive silver halide emulsions used to produce such recording materials, negative dye images can thus be produced in this way.

Shall the generated image dyes in the image-forming unit remain, "shifted" compounds can advantageously be used as image dye-forming compounds (G is a hydrolyzable acyloxy group) and the compounds are advantageously contained in the superhalide emulsion layers.

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

The structure of the compounds prepared was determined by infrared spectra and nuclear magnetic resonance spectrum and in some Cases also confirmed by tlementary analysis.

In the case of the radical C ₁ -H ₁ --t. it is a t-pentyl radical.
I. Preparation of Compounds According to the Invention
Example 1 - creation of connection 1:

CONiI- (CIl ₂ ) ₄ -G

3 ¹ 11

A mixture of 3.05 g (0.0065 moles) of S-II-hydroxy-8- (2-methylsulfonyl-4-nitrophenylazo) -2-naphthalenesulfonyl chloride and 3.2 g
(0.00C5 moles) 4-Amino-N- [4- (2, 4-di-t. -Pentylphenoxy) -butyl] -1-hydroxy-2-naphthamide in 75 ml of tetrahydrofuran was treated under nitrogen at room temperature with 4, 5 ml pyridine for 90 minutes

409835/0947

stirs. The solid precipitate which separated out on dilution with 500 ml of hexane was then filtered off and dried. The yield of reaction product was 4.8 g, corresponding to 80 % of theory. The reaction product was then purified by dissolving it in tetrahydrofuran and precipitating it by adding hexane. The still slightly contaminated solid reaction product was then purified by chromatography using silica gel, the reaction product being eluted using tetrahydrofuran. The eluates were concentrated and the reaction product was precipitated using hexane. The yield of reaction product was 2.2 g, corresponding to 37 % of theory. The melting point of the compound was 170 to 173 ^° C.

The necessary intermediate connections were made in the following way:

a.) The 5-hydroxy-8- (2-methylsulfony1-4-nitrophenylazo) -2-naphthalenesulfonyl chloride was prepared from the sodium salt of the acid with chlorosulfonic acid, as follows: 3.55 g (0.00757 moles) of sodium 5-hydroxy-8- (2-methylsulfony1-4-nitrophenylazo) -2-naphthalenesulfonate in 35 ml of chlorosulfonic acid was ^{heated to 60 °} C. for 1 hour. The solution was then cooled and poured onto ice. The deposited precipitate was filtered off and dried in a vacuum desiccator. The yield of reaction product was 2.3 g, corresponding to 80 % of theory. The reaction product contained a small amount of the starting compound.

b.) Sodium S-hydroxy-S- (2-methylsulfonyl-4-nitrophenylazo) -2-naphthalenesulfonate was produced by the diazotization and coupling reaction described below:

To a solution of 55.8 g (0.25 mol) of i-amino-6-naphthalenesulfonic acid in 100 ml of water with 10 g (0.25 diols) of sodium hydroxide was added 17.3 g (0.25 mol) of sodium nitrate in 50 ml V / assor raised. At a temperature of 0 to 5 ° C, a dilute sulfuric acid solution, prepared by adding 50 g of ice to 125 ml of concentrated

409835/0947

2406553

centered sulfuric acid, added dropwise. After one hour, the solution was placed in a 3 liter flask and slowly heated to reflux temperature. At about 70 to DO ⁰ C gas evolved. The solution was refluxed for 1 1/2 hours and then cooled. The ρ-Fi value of the solution was adjusted using a 50 ⁹ ₀ Natriumhydroxyulösung strength at 7, followed by further 425 g of a 50 öigen sodium hydroxide solution were added (solution A). 17.3 g (0.25 moles) Katriumnitrit were added in portions to 150 ml of concentrated sulfuric acid at 0 ⁰ C. The mixture was left at 70 ⁰ C eraärmen. It was then cooled to 1O ⁰ C, followed by 54 g (0.25 moles) of 2-Ainino-5-nitrophenylmethylsulfon added. The resulting mixture was stirred for 90 minutes after which it was poured onto 25 g of ice. The resulting mixture was filtered and the filtrate was saved (solution B).

Solution B was then added to solution Λ ^{at a temperature below 30 ° C.} When the addition was complete, the pH was adjusted to approximately 5 and the mixture was stirred for half an hour. The deposited precipitate was filtered off and then slurried in water. After the solid precipitate had been filtered off and dried, the yield of reaction product was 85 g, corresponding to 72 % of theory.

Example 2 - Establishing the connection 2:

QrH

CONIJ- (CII ₂ ) ₄ -ü— '

OH

409835/0947

To a mixture of 4.2 g (0.009 moles) of 5-hydroxy-8- (2-methylsulforiyl-4-nitrophenylazo) -1-naphthalenesulphonyl chloride and 4.4 g (0.001? ^ Iols) of 4-amino-N - {β- (2,4-di-t-pentylplienoxy) -butyl] -1-hydroxy-2-naphthamide in 100 ml of tetrahydrofuran under nitrogen were given 4.5 ml of pyridine. The solution was stirred at room temperature for two hours and then diluted with 800 ml of hexane. The deposited precipitate was filtered off and dried. Ls were 4, C & crude reaction j; roduct obtained corresponding to 58 % of theory. The solid reaction product was chromatographed in a silica column using tetrahydrofuran as a ripening device. By concentrating the eluates, 3.2 g of a weakly impure solid compound was obtained. After suspending the solid Hasse twice in 200 ml of chloroform and diluting it with 400 ml of hexane, a pure reaction product was obtained. The yield was 2.4 g, corresponding to 29 % of theory. The melting point of the compound was 15 to 196 ° C (dec.)

The output connections required to establish the connection were made as follows:

a.) 5-Hydroxy-8- (2-methylsulfonyl-4-nitrophenylazo) -1-naphthalenesulfonyl chloride was made from the corresponding sodium sulfonate manufactured. 23.9 grams (0.05 moles) of sodium 5-hydroxy-8- (2-methylsulfonyl-4-nitrophenylazo) -1-naphthalenesulfonate in 150 ml of chlorosulfonic acid were heated to 65 ° C. for one hour. The mixture was then left to cool and poured onto lis. The reaction mass obtained was then filtered, the mixture being added by adding kept below 5 ° C by ice until filtration was complete. The filtered solid mass was then placed in a vacuum exiccator dried. The yield of the reaction product was 13.4. g corresponding to 78 I of theory. The solid reaction product was dissolved in 150 ml of tetrahydrofuran, whereupon the solution passed through Addition of GOO ml of chloroform was diluted. The precipitated solid Hasse was filtered off and discarded. The filtrates were Chromatographed by means of a silica column, chloroform was used as an eluent. The chloroform eluates were

A09835 / Ö9A7

then evaporated to dryness. 5.4 g of pure product corresponding to 23 % of theory were obtained.

b.) The Xatriun-5-hydroxy-3- (2-methylsulfonyl-4-nitrophenylazo) i-naphthalenesulfonate was prepared according to the method described in Example 1, in which instead of solution A a solution of 1-naphthol-5-sulfonic acid used in dilute sodium hydroxide. J) The yield was 1GO %.

Example 3 - 1 division of connection 3:

CONH- (CiI ₂ ) ₄ -Ü -V _

This connection was prepared in the same way as described in Example 1. After recrystallization from vinyl acetate, 46 % of the compound with a melting point of 10 2 · 164 ° C. (dec.) Were obtained.

Preparation of the starting compounds.

a.) Production of 5-hydroxy-8- (2-chloro-4,6-dinitrophenylazo) -2-naphthalenesulfonyl chloride:

2> 5 β (0.02 hole) sodium 5-hydroxy-8- (2-chloro-4, 6-dinitrophenylazo) -2-naphthalenesulfonate were added in portions to 20 ml of chlorosulfonic acid. Then 20 ml of thionyl chloride were added, whereupon the mixture was ^{heated to 60 °} C. for 30 minutes. The solution was then cooled and poured into fresh water and filtered.

409835/0947

trotted. The still moist solid mass was dissolved in 800 ml CiICl and dried using magnesium sulfate. The resulting mixture was then filtered to remove the magnesium sulfate and the filtrates were evaporated to dryness. The solid mass obtained was slurried in hexane, filtered off and dried. The yield of reaction product was 6.7 g, corresponding to 71 % of theory. No impurities were found in the reaction product on thin-layer chromatography.

b.) Preparation of sodium 5-hydroxy-8- (2-chloro-4,6-dinitrophenylazo) -2-naphthalenesulfonate:

55.8 g (0.25 moles) of 1-amino-6-naphthalenesulfonic acid was dissolved in 100 ml of water containing 10 g (0.25 moles) of sodium hydroxide. To the resulting solution, 17.3 g (0.25 mol) of sodium nitrite in 50 ml of water was added. This solution was added dropwise at 0 to 5 ° C to a dilute sulfuric acid solution prepared by adding 50 g of ice to 125 ml of concentrated sulfuric acid. After one hour the solution was placed in a 3 1 flask and heated slowly with evolution of gas at 70 to 9O ⁰ C to reflux temperature. The solution was heated to reflux for 11/2 hours and then allowed to cool (solution A).

To 125 ml of a mixture of two parts of propionic acid and 5 parts of acetic acid containing 25 drops of Triton X-IO, 66 g of solid 82% 2-chloro-4,6-dinitroaniline in the form of a fine powder are added. The mixture was stirred for 11/2 hours at room temperature and then for a further hour at 40 ° C. The mixture was then ^{cooled to 0} ° C., whereupon you 3ß & §? a solution was slowly added, which had been prepared by adding 17.3 g (0.25 mol) of sodium nitrite to a concentrated sulfuric acid at 10 ^° C., heating to 70 ^° C. to dissolve the sodium nitrite and cooling to 20 ^° C. When the addition was complete, 125 ml of the propionic acid-acetic acid

+ / non-ionic isooctylphenyl polyethoxyethanol dispersion

^mlttel 409835/0947

Mixture in 50 g of ice added. The solution obtained was then stirred for a further two hours at 10 to 15 ^° C., urea being added to trap or bind excess nitrite. After stirring for an additional 30 minutes, the mixture was filtered to remove starting compounds and the filtrates were used as solution B. Solution B was added dropwise to solution Λ at a temperature of -10 to -5 ° C. The mixture was stirred for 30 minutes, after which the deposited precipitate was filtered off and dried. The yield of reaction product was 148 g, corresponding to 125 % of theory. The reaction product contained salts which could be easily removed.

Example 4 - Preparation of Compound 4

OIL

The compound was prepared from the corresponding sulfonyl chloride according to the procedure given in Example 1. The yield of reaction product was 6 %. The melting point of the compound was 241 to 242 ° C (dec).

The 4-acetamido-5-hydroxy-8- (2-methyl-sulfonyl-4-nitrophenylazo) -1-naphthalenesulfonyl chloride required to prepare the compound was prepared by the method described in Example 3 from the sulfonic acid given below. The yield was 50 %. The 4-acetawido-5-hydroxy-G- (2-methylsulfonyl-4-nitrophenyl-

409835/0947

¹ 1 -

azo) -1-naphthalenesulfonic acid was prepared according to the method described in Le Example 1 using a solution of 4-acetamido-5-hydroxy-1-naphthalenesulfonic acid in dilute sodium hydroxide solution instead of the solution Λ. The yield was 75 %.

Example 5 - Preparation of Compound 5

COKH- (CH ₂ ) ₄ -0-V

This compound was prepared according to the procedure described in Example 1. The yield of the compound was 23 % . The melting point of the compound was 153 to 156 ^° C. (dec).

The 5-hydroxy-8- (4-nitro-2-trifluoromethylphenylazo) -2-naphthalenesulfonyl chloride required for the preparation of the compound was prepared according to the method described in Example 1. The yield was 70 %.

Sodium 5-hydroxy-8- (4-nitro-2-trifluoromethylphenylazo) -2-naphthalenesulfonate was prepared in a manner similar to that described in Example 1. The yield was 107 l, namely due to the presence of salts. T he / P.eacti on product was used without further purification for the production of the acid chloride,

409835/0947

Example 6 - Preparation of Compound 6

SO ₂ CII-

CII ₃ COIiN

x ^ -CONH- (CH ₂ ) ₄ -0 OH

The compound was prepared according to the procedure given in Example 1. The yield of the compound was 19 %. Of the
Melting point of the compound was 268 to 27O ⁰ C (dec).

The 4-acetamido-5-hydroxy-8- (2-methylsulfonyl-4-nitrophenylazo) -2-naphthalenesulfonyl chloride required to prepare the compound was prepared according to the method described in Example 3. The yield was 6½ "". The -i-Acetainido-S-hydroxy-S- (2-methylsulfonyl-4-nitrophenylazo) -2-naphthalenesulfonic acid was prepared in the same way as described in Example 1, using an alkaline solution of 4-acetamido- 5-hydroxy-2-naphthalenesulfonic acid instead of solution A. The yield was 100 %.

Example 7 - Preparation of compound 7:

SO ₂ CH ₃

C ₃ H ₇ CONI

CONH- (CII ₂ ) ₄ -0

OH C

40983S / 0947

The compound was prepared according to the procedure described in Example 1. The yield was 16 %. The melting point of the compound was 248 to 24P ⁰ C (dec.) · UEAs 4-butyramido-5-hydroxy-8- (2-methylsul £ onyl-4 ~ nitrophenylazo) -2-naphthai insulfonylchlorid was described in Example 3 after the Process made. The yield was 86 ^? o. The 4-butyramido-5-hydroxy-8- (2-methylsulfonyl-4-nitrophenylazo) -2-naphthalenesulfonic acid required for the preparation of the compound was prepared according to the method described in Example 6.

Example 8 - Preparation of Compound 8

c ₅ ii _ir t

To a mixture of 3.2 g (0.006 moles) of 4-acetamido-5-bydroxy-8- (2-iaethylsulfonyl-4-nitrophenylazo) -2-naphthalenesulfonyl chloride and 3.9 g (0.006 moles) of 4- (m-aniinobenzenesulfonaraido) -M- 4- (2,4-di-t.-pentylphenoxy) butyl -1-hydroxy-2-naphthamide in 75 ml of tetrahydrofuran 3.0 ml of pyridine were added. The resulting mixture was stirred for one hour at room temperature under nitrogen, whereupon it was filtered. The filtrates were diluted to 500 ml by adding hexane. The precipitate formed was filtered off and dried. The reaction pro du! ·: T was taking

409835/0947

Chromatographed using silica gel and ethyl acetate. The yield of reaction product was 1. C g, corresponding to 15 % of theory, with a non-pronounced melting point.

Example 9 - Preparation of Compound D:

HO—

CONII- (CH ₂ ) ₄ -0- ^

This compound was de n procedures described in Example 8 in a 16 intrinsically yield with a non-salient
Melting point established.

Example 10 - Preparation of compound 10:

cn] ₂ -Nir

^C 2 ^H 5

CONH- (CH ₂ ) ₄ -0-T__

409835/0947

This compound was prepared according to the procedure described in Example 8 with the exception that it was chromatographed in the presence of DiisoT} ropyläthylamin. The 1-I yield of the compound was 17 %. The melting point of the compound was over 150 ^° C.

Example 11 - Preparation of compound 11:

CH ₃ CONH

c ii _ir t

CONH- (CIl ₂ ) ₄ -0 - \ _

on

This compound A was prepared according to the process described in Example 1 in a yield of 50%. The limit of the compound was 19 5 to 19 7 ⁰ C (dec).

The 4-acetamido-8- (2-chloro ~ 4,6-dinitrophenylazo) -5-hydroxy-2-naphthalenesulfonyl chloride required to prepare the compound was, as described in Example 3, prepared in 85% yield. 4-Acetamido-8- (2-chloro-4,6-dinitrophenylazo) -5-hydroxy-2-naphthalenesulfonic acid was prepared according to the procedure given in Example 3 in a yield of 53 liters.

II. Use of the Compounds of the Invention in Example 12 - Photographic Examination

The express dye-forming agents prepared in the manner described Compounds were tested for their reactivity and the diffusibility of the dyes released from them in a Image receiving layer checked.

409835/0947

Each of the compounds was made in an equal amount by weight iJiäthyllauramid dissolved, whereupon the solutions in gelatin fine were dispersed. The resulting dispersions then became a monodisperse negative working gelatin-silver bromide emulsion a grain size of about 0.8 inu added, whereupon the modified emulsions on polyester substrate in such a way

2 - 5

that on a support area of dm about 1.1 χ 10 ^: Iole of the compound to be tested, C, 2 mg of silver and 32 mg of gelatin were allotted. A gelatin top layer with 8.6 mg gelatin per dm, hardened with formaldehyde, was applied to each of the emulsion layers.

A. Image resolution

Sections of the produced recording materials were then made exposed through step wedges and then in the presence of a viscous developing liquid with a? using an irritant produced image receiving element brought into contact. From the recording materials, the image receiving elements and the Developing fluid, sandwiches were created by the were guided by two superposed pressure-exerting rollers gap formed.

The express receiving elements used consisted of a layer carrier, the one with a mixture of gelatin (21 mg / dm) and a mordant, namely a copolymer of styrene and K-benzyl-N, N-dimethyl-N- (3-maleimidopropyl) ammonium chloride (21 rng / dm ^) had been coated.

The developing liquid contained 20 g sodium hydroxide per liter of solution, 0.75 g of ^ hydroxymethyl-'t-ynethyl-i-phenyl-S-pyrazolidone, 10 g potassium bromide and 25 g hydroxyethyl cellulose. After a period of contact of 60 seconds, the image receiving elements were separated from the recording materials and washed in water, to bring the pH to around 7. In all cases,

409835/0947

the excellent one. Density achieved in the exposed areas. There was practically no transfer of dyes in the unexposed areas. The determined i) - and I). -Values

in ο. λ in L η

of the transfer images obtained are in the following one later Table compiled under the heading "Image resolution".

ß. Spectrophotometry

The spectra of the released dyes were after they were obtained from the mordant had been absorbed on a transparent substrate, on spectrophotoinetrjscheir. IVcge determined. In the the following table are the maximum wavelength (λ max) and the Bandwidth in mil at half the density at χ max of the curve one specified for each dye. This "lial.be bandwidth" illustrates together with λ max the hue, with the luminosity or the strength and purity of the hue are greater, the smaller the half range.

C. Dye transfer into the image receiving element

Another portion of each AufZeichnungsr ^ aterials; uit one Kildfarbstoff generating compound has been fogged by exposure to light and developed by means that the portion in the form of a sandwich with a di Idemp catch element and a viscous liquid developing agent by the performing of two pressure rollers formed gap was driven. The thickness of the developer layer of the laminates produced was about 0.075 to 0.10 mm.

The image receiving elements used had the following structure:

The support consisted of cellulose acetate. A layer of 21 mg pickling agent and 11 mg gelatin each per dm was applied to this. On this layer there was a layer of 215 mg TiO ₇ and 21 mg gelatin, each per dm ". A layer of 27 mg carbon black and 17 mg gelatin per dm" was applied to this.

409835/0947

The developing liquid contained 2 μg per liter of solution iNatriuiiihydroxyd, 0.75 g 4-LiUroxy-methyl-4-methyl-1-phenyl-3-pyrazolidone, 10 g of potassium bromide and 25 g of hydroxyethyl cellulose. After applying the developing fluid to the veiled In the emulsion layer, the dyes were set free and diffused through, containing the base and titanium dioxide Layers in the mordant layer. The mordant of the mordant layer consisted of the above-mentioned copolymer.

The density of the dye images produced in the adhesive layer was read off through the layer support by means of a reflection densitometer after 30, 60 and 120 seconds at 24 ^° C. The increase in density, which results from the values determined in the table, is an allowance for the speed of the release of the dyes and, moreover, a hatred for the diffusibility of the dyes.

409835/0947

Connect max half

dung (nm) bandwidth of width

Example (nm)

6 39 119 634 113 645 115 645 133 637 132 615 130 622 132 669 114 653 110 640 122 660 120

Table I. Dm ax Dmin icnaften 30th Sec. 60 sec. 120 sec. Photographic Own " 2.70 0.72 0 , 33 0.34 2.04 Image resolution 1.80 0.70 0 , 35 ' 1.04 1, 92 ] Coating
strengthening
ke lioIe χ
ΙΟ " ⁴ per
on ¹ 2.60 0.44 Density of the transfer image 0 , 64 1, 48 2.30 11 3.20 1.46 Coating
strength
Mole x., 10 " ⁶
per dm * ¹ 0 , 77 1.29 1, 78 11 1.20 0.20 1 1 0 , 24 0.35 0.5S 11 1, 52 0.50 11 0 , 36 0.71 1.10 11 2, 10 0.71 11 0 , 32 0.76 1.43 11 3.00 0.52 11 0 , 51 1.11 1.08 6th 1.45 0.50 6th C. , 42 0, SD 1, 50 6th 2.70 0.63 6th 0 , 81 1.63 2, 35 6th 2.84 0.56 6th 0 , 20 0.46 0.85 6th 6th 6th 6th 11 6th 6th

cn cn cn

Example T3

A mixture of 3 grams of NaHCO ₃ , 4.2 to 3 grams (8.10 millimoles) of Compound A, and 3.97 grams (8.10 millimoles) of 1-hydroxy-4-amino-N-J4- (2,4-di -t-pentylphenoxy) -butylj -2-naphthamide (referred to in the following reaction scheme as H ₂ NX) in 30 g of dry dimethyl sulfoxide was ^{stirred at 80 to 100 0} C for 60 minutes, whereupon the reaction mixture was cooled and poured onto ice water, which was so much dilute hydrochloric acid contained that the excess NaHCO3 was neutralized. The precipitated compound B was filtered off, washed with water and air-dried. The yield of crude dye cake was 102%.

The compound B was isolated in a comparatively clean form, but was in one with equal parts by weight of silica gel and Cellulose-filled dry column by an ascending development with a mixture of ethyl acetate (9 parts by volume) and methanol (1 part by volume) chromatographed.

The manufacturing process can be described by the following reaction equation reproduce:

step 1

ClO

SO ₂ F

409835/0947

Level 2

level 3

OK

- 61 -

^H Ä ° 4 ^K 2

> ■

1: 5 acid U-IO ⁰ C

I SO, F

A.

Λ. +

DMSO

NaIiCO

I N = N-T 7 NO

V = - / ^L

so

SO ₂ CIi ₃

B.

SO ₉ NH-X

The compound obtained was tested as described in Example 12. The dye released had a λ max value of 640 nm and a Dniax of 2.35 at 60 seconds and 2.5 at 120 Seconds.

A compound with a cyano residue behaved accordingly instead of the methylsulfonyl radical on the nitrophenyl ring.

409835/0947

Example 14

A solution of 4.14 g (5.00 millinioles) of coupler A in 20 ml of pyridine and 150 ml of an acid mixture consisting of one part by volume of propionic acid and 5 parts by volume of acetic acid was cooled ^{to 5 ° C.} Further, a solution of 1.2 g 2-Amino-5-nitrobenzenesulfonic acid, sodium salt (5.00 millimoles) and 0.036 g of sodium nitrite (5.00 Milliniole) cooled in 50 ml of water at 0 ⁰ C and then added dropwise to a solution of 1 ml of 37% hydrochloric acid in 20 ml of water at ⁰ ° C. was added. The diazotization proceeded very quickly. The resulting suspension of the diazonium salt was slowly added to the coupler solution at 5 ° C. The coupling was rapid (ie it was presumably complete after 30 minutes at 5 ° C.). However, the mixture was stirred at 5 ° C. for two hours, after which the dye produced was precipitated by adding ice water. The orange-red compound B, which was filtered off, was washed with 5 l of cold water and dried in vacuo. It was then chromatographed by means of a column filled dry with equal parts by weight of silica gel and cellulose by ascending development with a solution of 8 parts by volume of chloroform and 2 parts by volume of methanol.

In the following the production process is shown in the scheme.

step 1

COCl

CCII ₂ CH ₃

OH

SO ₂ Cl Pyridini H _O ~ NX

0 =

Ψ r-π- SO-NH-X

^ ²

A.

409835/0947

Level 2

CH ₃ CO ₂ H
CH ₃ CH ₂ CO ₂ H

OH

NH N = N-f

C = O

SO ₃ H

SO ₂ NH-X

B.

Compound B was tested as described in Example 12. They had a λ max value to v _r on 660 nm. After 30 seconds the poetry was 1.33, after 60 seconds it was 0.66 and after 120 seconds it was 1.08.

Example 15

It is an image dye-forming compound as follows

Structure made:

HO

A solution of the compound in diethyl lauramide was applied to a polyester support in the form of a dispersion in gelatin. The layer contained 7.1 mg of the compound, 14 mg of solvent and 21 mg of gelatin, in each case per dm ^{2 of the} support surface. A gelatin-silver bromide jadide emulsion layer containing 11 mg of silver and 22 mg of gelatin, each per dm ² , was applied to the layer. The resulting recording material was then exposed and thereafter immersed in a developing liquid of the following composition for 30 seconds. Sections ν

409835/0947

of the recording material for different lengths of time with an image receiving element made of a paper backing with a stain layer of poly-4-vinylpyridine and polyvinyl alcohol applied to it brought in contact.

The developing liquid used contained more aqueous per liter Solution 50 g potassium hydroxide, 40 g potassium bromide, 20 g N-benzyl-a-picolinium bromide, 20 g benzotriazole and 50 g sodium sulfate. After separating the image receiving element from the recording material after 30, 60 and 120 seconds, reflection densities of 1.20, 1.55 and 1.80 were found in the image-receiving layer, respectively determined.

Example 16 - Preparation of Compounds 15-21

Compound 12 of Example 13 was treated with acetyl chloride in dry acetone using one equivalent of pyridine as Esterified hydrogen chloride acceptor. The one made in this way Compound 15 corresponded to compound 12 of the example 13, with the exception, however, that the hydroxy radical in the para position on the naphthalene nucleus with respect to the azo group is replaced by a radical of Formula -OCOCH3 had been replaced.

Compound 16 was prepared in a similar manner, however propionyl chloride was used for esterification.

The compounds were tested as described in Example 12. The following results were obtained:

Connection 15: Xmax of the transmitted image 640 n », densities: 1.36 (after 30 seconds), 2.11 (after 60 seconds), 2.7 (after 120 seconds);

Connection 16: Xmax of transmitted image 640 na, densities; 1.20 (after 30 seconds), 1.95 (after 60 seconds) and 2.4 (after 120 seconds).

- 64 a -

409835/0947

In a similar manner, further compounds 17-21 were prepared by having the hydroxy radical in the para position on Naphthalene nucleus with respect to the azo group of compound 12 through the residues indicated in the following table have been replaced. These connections gave the following results:

Compound replaced hydroxide no. Rest

max D density of the transmitted

17th

18th

20 -OC-C ₁₁ H ₉ , 11 2ο

(mn)

Max

Dye image after

30 sec. 60 sec. 120 sec.

643 2.8 0.77 1.46 2.3

Cl 640 2.0 0 _s 70 1.26 2.0

NO ₂ 640 2.9 1.41 2.4 2.9

640 1.18 0.50 0.77 1.18

21

ti

-OC

640

0.26 0.47 0.79

- 65 -

409835/0947

Example 17

-et »

Ls uurden further dyes corresponding to the dyes that from the described supports (Y) by alkaline development Were set in freedom, prepared and in 3ü ml of a 0.5 N sodium hydroxyl solution with a content of 30 g per liter of hydroxyethyl cellulose solved.

Each of the readings obtained was zv: is before η a cellulose acetate coverlet and brought a Lildempfar.gselement in such a way, that the alkaline dye solution was 0.1 Hin thick.

The image receiving elements used corresponded in their structure the egg Iclerap catch element described in example 12, showed jedocti additionally a celatin layer made of 43 mg gelatin per dm over the carbon black gelatin layer.

The spectra of the dyes after adsorption on the Mordant layer, as described in Example 12, determined.

The following table II shows the structure of those tested Dyes and the results obtained with them.

Table II Oil

409835/0947

Dye no. DE ■ μ] Q ¹ λ max

1 -H-H 5-SO ₂ NH ₂ -H 610

2 -SO ₂ CH ₃ -H 5-SO ₂ NH ₂ -H 654

3 -SO ₂ CH ₃ -H 6-SO ₂ NH ₂ -H 639

4 -SO ₂ CH ₃ -H 7-SO ₂ NH ₂ -H 630

5 " ^SO 2 ^CH 3" ^H 8-SO ₂ NH ₂ -II,. 616

6 -SO ₂ CH ₃ -H 5-J ₁ ⁺ -H 630

7 -SO ₂ CH ₃ -H 6-J ₁ ⁺ -H 640

8 -H-H 6-SO ₂ NH ₂ -H 612 O 9 -Cl -H 6-SO ₂ NH ₂ "* -H 625 J £ 10 -BR -H 6-SO ₂ NH ₂ -H 634

J £ 11 -CN -H 6-SO ₂ NH ₂ -H 636

^ 12 -CF- -H ■ 6-SO ₉ NH ₇ -H 637, $

ο ^ 2 2 ^ t *

(θ 13 -NO ₂ -H 6-SO ₂ NH ₂ -K 638 <* ι

^ 14 ~ ^0CH 3 " ^H 6-SO ₂ NH ₂ -H 625

-CH ₃ -H 6-SO ₂ NH ₂ -K 606

-SO ₃ Na -H 6-SO ₂ NH ₂ -H 617

-SO ₂ NHC ₂ H ₅ -H 6-SO ₂ NH ₂ -H 633

-NO ₂ -SO ₂ NH ₂ 6-SO ₂ NH ₂ -H 632

-, Cl * ^N0 2 ^ 6-SO ₂ NH ₂ '-H 645

-Cl -Cl 6-SO ₂ NH ₂ -II 630 _M

J ₁ - SO ₂ NH-C ₆ H ₄ Cm) -SO ₂ NH ₂ cn

Dye no. D. E. 21 -CN -NO ₂ 22nd -SO ₂ NH (CH ₂ ) ₂ C00H -H 23 -Cl -NO ₂ 24 -Cl -H 25th -CN -H 26th -NO ₂ -H 27 -SO ₂ CH ₃ -H 28 -SO ₉ CH- -H 29
30th -NO ₇
-Cl -Cl
-H 31 -H -H 32 -CN -H 33 -SO ₂ CH ₃ -H 34 -SO ₂ CH ₃ ■ -H 35 -SO ₂ NHC ₂ H ₅ -H 36 -SO ₂ CH ₃ -H ■

λ max

6-SO ₂ NH ₂ 6-SO ₉ NH ₉

5-SO ₂ NH ₂ 5-SO ₂ NH ₂ 5-SO ₂ NH ₂ 5-SO ₂ NH ₂

6-SO ₂ NH ₂ 5-SO ₂ NH ₂

5-SO ₂ NH ₂ ⁺

6-y

5-SO ₂ H

-H 621 -H 639 -H 653 -H 633 -H 633 -H 630 8-NHCOCH ₃ 645 8-NHCOCH ₃ 615 8-NHCOCH ₃ 6 60 8-NHCOCH ₃ 610 8-NHCOCH- 603 8-NHCOCH ₃ 625 " 8-NHCOCH ₃ 650 js 8-NHCOCH ₃ 669 *? 8-NHCOCH ₃ 625 -H 633

Ibid

dye

37
38
39
40
41
42
43
44
45
46
47
48

M ¹

O ¹

Xm ax

-SO ₂ CH ₃
-SO ₂ C ₂ H ₅

-so.

-SO-CH-C _n H ₁ .
2 6 5

Cl
-CF ₃
• Br
■ CN

■ SO C _ft H _c
365

-Cl
-COOH

-Ce

-H

-H

-H

-H

-H

-H

-H

-H

-H

-NO-

-H

-H = - ^J 2 ⁺ 640 -H 5-J ⁺ ₂ 640 -H 640 -H 640 -H 5-J ⁺ ₂ 645 -H 660 -H 652 -H 5-J ₂ 657 -H 638 -H 5-J ⁺ ₂ 657 -H 5-J ⁺ ₂ 645 -H SJ ⁺ _

J ₉ = NHSO ₉ - (C _n H.), -SO ₉ NH ₇ 2 ^v 6 4'm 2 2

409835/0947

Example 18

A multilayer, multicolor photographic recording material with an integrated image receiving layer was produced by applying the layers specified below to a transparent cellulose acetate substrate in the following order: (The concentrations given below relate to a substrate area of 0.0: 29 ti ² )

1.) an image receiving layer made of 200 mg of a copolymer from styrene and N-benzyl-N'jN-dimethyl-K- (3-inaleimidopropyl) -aminonium chloride and 100 rag gelatin;

2.) a reflective layer made of 2000 mg titanium dioxide and 200 mg Gelatin;

3.) an opaque layer of 250 ng ounces and 312 ounces of gelatin;

4.) a layer with a blue ^ green image dye producing Compound according to Example 13 (65 mg) and 100 mg gelatin;

5.) a layer of a red-sensitive gelatine-silver chloride-broride inner grain emulsion with 100 ng gelatine and 125 mg silver as well as 25 mg 2,5-di-sec-dodecylhydroquinone and 1 g per mol of silver formyl-4-methylphenylhydrazine as a nucleating agent ;

o.) an intermediate gelatin layer of 100 ml of gelatin and 50 mg 2, 5- 'i - s cc. - do ciecy! hydroquinone;

7.) a layer containing 150 mg of a magenta image dye generating compound of the following formula:

409835/0947

CONH (CK ₂ )

^C 5 "11

^C 5 ^H 11

NHSO

NHCOCHCH
Ο

? ^CH

N = N

and 175 mg gelatin;

SO ₂ NH ₂

8.) a layer of a green-sensitive gelatin silver chloride bromide inner grain or internal image emulsion schiclit with 125 mg gelatine and 150 mg silver and 50 mg 2,5-di-sec.-dodecy / hydroquinone and 1 g per mole of silver formyl-4-methylphenyluydrazine as a seed ner;

9.) an intermediate gelatin layer made from 100 mg gelatin and 50 mg 2,5-di-s ec.-dodecy! hydroquinone;

10.) a layer with a yellow image dye forming Ver bond of 100 mg of this compound of the following formula:

40983S / 0947

and 150 mg gelatin;

11.) a layer of a blue-sensitive gelatin silver chlorobromide inner grain emulsion with 100 mg gelatin and 150 mg silver, 50 mg 2,5-di-sec-dodecylhydroquinone and 1 g per mole of silver formyl-4-methylphenyl-hydrazine as nucleating agents;

12.) a top layer of 82.5 mg gelatin.

The silver halide emulsions used to prepare the recording material consisted of direct positive emulsions of high internal sensitivity and low surface sensitivity of the type known from US Pat. No. 2,592,250.

The photographic recording material produced in the manner described was exposed to a multicolored test object with graduated density levels.

A splittable container became a developing liquid of the composition given below between the recording material described and an opaque cellulose acetate cover sheet spread by the sandwich formed from recording material, cover sheet and splittable container by the two superimposed pressure rollers gap formed was guided.

The developing liquid used had the following composition:

Sodium hydroxide 40 g

^ Hydroxymethyl-i-methyl-i-phenyl-3-pyrazolidone 4 g

5-methylbenzyltriazole 0.1 g

Potassium iodide 0.01 g

Hydroxyethyl cellulose 25 g

Make up to 1000 ml with distilled water.

409835/0947

After a contact time of 4 minutes, the recording material became separated from the opaque cover sheet, rinsed for 1 minute with an acid solution, fixed for 4 minutes, washed and dried. The following sensory functions were obtained:

Maximum calibration

Minimum density

Red 1.24

Red
0.36

Crün

0.4;

Blue

0.42

The compound used to make the purple colored dye for the preparation of the recording material was how is made as follows:

250 mg of distilled os Ν, Ν-l-ethyl formamide was placed in a dry flask with 22.2 g (0.05%) of α- [4-hydroxy-3-(2-metho.xy-5-sulfainylphenylazo) -1-naphthoxy] propionic acid , 32.5 g (0.05-ole) 1-hydroxy-4-m-aminobenzenesulfamyl-N-rä- (2,4-di-t-amylphonoxy) butyl] -2-naphthamide and 12.3 g (0.05 Ίοίε) N - '\ thoxycarbonyl-2-ethoxy-1,2-dihydroxycliinoline given. The reaction mixture was protected from ingress of atmospheric moisture and stirred for 4 hours at room temperature. The reaction mixture was then cooled in an ice bath, whereupon a solution of 25 g (0.3 mole) sodium bicarbonate in 500: ul V. water was added in portions, whereby an oily mass separated out. A further 500 ml / water were then added to complete the precipitation. The supernatant liquid was then decanted from the deposited oily lasse, whereupon the oily mass was washed repeatedly with water: tired until the aqueous phase was almost colorless ml of water was stirred, resulting in a crystalline mass which was ground further using a mortar under Kasser. The resulting slurry was filtered off, whereupon the precipitate was washed again with water and dried. The yield of reaction product was 52 ι · According to L'7 'a

40983S / 0947

the iiieorie. The melting point of the icing product was lei
120; jis 16U ⁰ L. im :; The reaction product was then purified so that it lasted for 1 1/2 hours; in 3UO ml of acetic acid
Lt, y oratar verniert '..was. Yeah, Jas went firm! Ieaktioiisprodukt ia Lcsuug and was again ;; filled in, the resulting slurry was filtered, whereupon the solid residue with
2oü iVil cold Lssigsilure and 5üO r.il hate washed v; urde. The yield of pure magenta Lildfarbstoff providing compound was Jei 33 g corresponding to 71 I of theory. The melting point of the compound was 16G to 17 1 ° C. üaber Xüiax value (Diip.otiiylaCetainid with existing Triy thylan.in) was 52C to 545 nn-,

The materials used to produce the described recording material yellow dye-forming compound manufactured as follows:

To a solution of 7.3 g (0.15 mls) of 1-i-HydroAy-4-amino-N-LA- (2,4-di-t.-aluylphenoxy) butyl-2-naphthanide in 60 nil dry
Pyridine, cooled to Z ° C in an egg tray, was added with stirring in a nitrogen atmosphere, 4 g (0.16 moles) of 1-phenyl-3-methylcarbainyl-4- (p-chlorosulfonylphenylazo) -5-pyrazolone . The 'iisstellung was then stirred for two more hours at room temperature and then poured into 1 liter of lisbasser with a; Content of 75 ml of hydrochloric acid given. The deposited precipitate was filtered off, dried and crystallized. hs were 10.4 g
of the yellow lilac dye-forming compound.

409835/0947

Example 19

According to the US patent application Serial Number 326 62 8 The method given became another kild dye-forming method Compound, i.e. Compound No. 22 of the following structural formula:

OH

SO ₀ CH-

SO ₀ -NCH ₀ CH ₀ -N-CH, 2 ι 2 2 ι 3

Using the prepared compound, a photographic Recording material produced by applying the layers indicated below to a layer support (the concentration data given below relate in each case to a layer support area of

0.0529 m "):

1.) A layer of 125 mg gelatin and 40 mg of the> compound of given structure, dissolved in 20 mg of diethyl lauramide, and 10 mg of 5- (2-cyanoethylthio) -1-phenyltetrazole, dissolved in 30 mg Tricresyl phosphate;

2.) a negative silver bromide iodide emulsion layer with 100 mg silver and 100 mg gelatin as well

+ / German patent application P 24 02 900.3

409835/0947

3.) a gelatin layer made of 50 mg gelatin.

A section of the recording material produced was made exposed to a step wedge according to the image and then in a developer solution of ii; following specified composition Developed with a pH of 9.0 for 15 minutes at 20 ° C.

Water, about 50 ° C 500 ml

p-methylaminophenol sulfate 2.5 g

Sodium sulfite, dehydrated 30.0 g

Hydroquinone 2.5 g

Sodium borate 10.0 g

Potassium bromide 0.5 g ₄ iit Kasser made up to 1 liter

The recording material was then washed for 5 minutes, dried and exposed to light and then the section was exposed in contact with a Di Idemp catch element uit an image receiving layer Brought with a mordant in the presence of a viscous developing liquid between the recording material and image receiving material has been introduced. The viscous developing liquid had the following composition:

Potassium hydroxide 60 g

Ilydroxyethyl cellulose 30 g

^ Hydroxymethyl- ^ methyl-i-phenyl-S-pyrazolidone 3 g

Sodium thiosulphate 3 g

Potassium bromide 10 g Make up to 1 liter with water

After a contact time of 10 minutes, recording material became and image receiving element separated from each other. The image-receiving element was washed and dried. In the image receiving layer a negative image of excellent quality was obtained. The recording material was washed, bleached, washed, fixed, washed and dried. In the recording material was a positive, good quality blue-green dye image emerged.

409836/0947

Example 20

r, s were further compounds which produce low levels of chemical substances ταχΐ ilen from the following 'lamella III and IV apparent structures presented and according to the procedure described in Example 12. tested, Any results never obtained are also included in the following Tables III and IV compiled.

409835/0947

5-1

rf

σι ο

υ ο

• Η -M

; 'η tr,

t'l

tn

409835/0947

Connection no.

25th

ΟΡΟ CO OO b>

26th

Continuation from Table III

OH

NIiSO ₂ -m

CONHCH ₀ CI] -O 2 1

Γ ^: -τ

NHS0 ₂ -m density of the transferred dye image

Sec. ■ 60 sec. 120 sec.

1.09

1.14

1.99

1.71

2.2D

2.07

N>

CD

cn cn co

Table IV

ο co α »cc» cn

Connection no .

27

28

SO ₂ NH

NH I

so. I '

NO.

-CH ₃

O ₂ II

ι - t

Density of the transferred dye image after 60 sec. 120 sec.

1.57

0.73

1.36

0.93

O CO CO

cn

Claims (1)

PATENT CLAIMS 1. Photographic recording material consisting of a Support and at least one light-sensitive silver halide emulsion layer and one applied thereto a cyan image dye-forming compound in a layer of the material characterized in that it is a cyan image dye forming compound contains a compound of one of the following formulas: or II. Y-X-J-NH N = N N = N where mean: Y is a carrier residue which, as a result of an oxidation taking place under alkaline conditions, forms a compound with provides a mobility different from the compound of the formula given; 409835/0947 a bivalent link of the formula 2 2 -R -L _n -R -, in which mean: 2
R is an alkylene radical with 1 to 8 carbon atoms or an optionally substituted phenylene radical having 6 to 9 carbon atoms - with the proviso that the two radicals R can have the same or different meanings; L is an oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl group; η = 0 or 1; ρ = 1 if η = 1 and ρ = 1 mmi. or = 0, if η = 0, where it holds that if ρ - 1, the sum of the co- lensto: lies; 2 carbon atoms of the two radicals R not exceeding 14 R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; J is a sulfonyl or carbonyl radical; η and q each = 0 or "!; Q represents a hydrogen atom, a hydroxy radical or a Remainder of one of the formulas: -NHCuR ³ or -NHSO ₂ R ³ 409835/0947 in which R is an optionally substituted alkyl radical with 1 to 6 carbon atoms, a benzyl radical or an optionally substituted phenyl radical with Represents 6 to 9 carbon atoms; a hydroxy radical, a salt thereof or a hydrolyzable radical of one of the formulas "4" A -OCR * or ^r -0-COR ⁴ in which R is an alkyl radical having 1 to 18 carbon atoms or represents an optionally substituted phenyl radical having 6 to 18 carbon atoms; D is a halogen atom or a cyano, nitro, trifluoromethyl or alkyl radical having 1 to 6 carbon atoms; an alkoxy radical with 1 to 6 carbon atoms; a carboxy radical; a carboxylic acid ester radical of the formula -COOR, in which R has the meaning already given; a fluorosulfonyl radical; an optionally substituted —SO— phenyl radical with 6 to 9 carbon atoms; a sulforest; a sulfamoyl radical of the formula -SO-NR ⁵ R ⁶ , in which R ^{5 is} a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms and R is a hydrogen atom, an optionally substituted alkyl radical having 1 to 6 carbon atoms, a benzyl radical, a optionally substituted phenyl radical with 6 to 9 carbon atoms, an alkylcarbonyl radical with 1 to 8 carbon atoms or a phenylcarbonyl radical with 6 to 9 carbon atoms, where it applies that the sum of the carbon atoms of the radicals R and R does not exceed 14 lies; a carbamoyl radical of the formula -CON (R) ₂ »in which the two radicals R can have one of the meanings already given and can be identical to or different from one another; an optionally substituted alkylsulfonyl radical having 1 to 8 carbon atoms; an optionally substituted phenylsulfonyl radical with 6 to 9 carbon atoms or a radical of one of the formulas: 409835/0947 - Jr - Yf- X-fr-NR-J 7 _m or YXJ-,
provided that the substituent of the formula on the naphthalene ring of the formula I is replaced by a radical of the meaning given for M or that the substituent of the formula Y-X-J-NH - on the naphthalene ring of the formula II by a radical of those specified for Q. Meaning is replaced, with the proviso that Y, X ^ R, q and m have the meaning already given; E is a hydrogen or halogen atom or a nitro, cyano or trifluoromethyl radical; M is a hydrogen atom; a carboxy radical; a carboxylic acid ester radical of the formula -COOR, in which R has the meaning already given; a sulpho radical, a sulfamoyl radical of the formula -SO-NR R or a carbamoyl radical of the formula -CON (R) ₂ in which R and R have the meanings already given; an optionally substituted alkylsulfonyl radical having 1 to 8 carbon atoms; an optionally substituted phenylsulfonyl radical having 6 to 9 carbon atoms; an optionally substituted alkyl radical having 1 to 6 carbon atoms; a benzyl radical or an optionally substituted phenyl radical; with the proviso that the compound has no more than one Sulforest and no more than one carboxy radical. 409835/0947 2. Photographic recording material according to claim 1, characterized characterized in that it contains a compound of one of the formulas given, in which η and ρ are each = O. 3. Photographic recording material according to claim 1, characterized characterized in that it contains a compound of one of the formulas given in which m = 0. 4. Photographic recording material according to claim 1, characterized characterized in that it contains a compound of one of the formulas given in which G is a hydroxy radical. 5. Photographic recording material according to claim 1, characterized characterized in that it contains a compound of one of the formulas given, in which represent: E is a hydrogen or halogen atom or a nitro radical and M is a hydrogen atom or a sulfamoyl radical of the specified Formula. 6. Photographic recording material according to claim 1, characterized characterized in that it contains a compound of one of the formulas given in which Y is a radical as a consequence an oxidation taking place under alkaline conditions sets free a dye whose mobility depends on the Mobility of the dye releasing compound is different. 7. Photographic recording material according to one of the claims 1 to 6, characterized in that it contains a compound of one of the formulas given, in which G has the meaning given and which mean: 35/0947 2
R is an alkylene radical with 1 to 4 carbon atoms or one Phenylene radical, which may be replaced by a carboxy, Chlorine, methyl or methoxy radicals can be substituted; L is a sulfamoyl, sulfonamido, carbamoyl or carboxamido radical; R is a hydrogen atom; q - 1; m = 0 or 1; Q is a hydrogen atom; a hydroxy radical or a radical of one of the formulas -NHCOR ³ or -NHSO ₂ R ³ , in which R ^{3 represents} an alkyl radical having 1 to 4 carbon atoms, which is optionally substituted by a hydroxy, cyano, sulfamoyl, carboxy or sulpho radical may be substituted; a benzyl radical or a phenyl radical which can optionally be substituted by a carboxy, chlorine, methyl, methoxy or sulfamoyl radical; D is a chlorine, bromine or fluorine atom or a cyano, trifluoromethyl, nitro, fluorosulfonyl or alkylsulfonyl radical with 1 to 6 carbon atoms, which is optionally replaced by a hydroxy, phenyl, cyano, sulfamoyl, carboxy , Fluorosulfonyl or Sulforest can be substituted; a phenylsulfonyl radical which can optionally be substituted by a hydroxy, sulfamoyl, fluorosulfonyl, carboxy or sulpho radical; a sulfamoyl radical of the formula -SO ₂ NHR, in which R represents a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms, which can optionally be substituted by a hydroxy, cyano, sulfamoyl, carboxy or sulpho radical; a benzyl radical; a phenyl radical, which optionally by 409835/0947 a hydroxy, sulfonyl, sulfamoyl, carboxy or sulfo radical can be substituted; or a carbamoyl radical of the formula -CON (R ⁵ ) ₂ in <* er R ^{5 is} a hydrogen atom or a methyl radical; or a substituent. of the formulas: Y - ^ - X - (- NR-J 7 _m or YXJ, provided that the substituent Y - ^ - X - ^ - NR-J _m ^{on the} naphthalene nucleus of the formula I is replaced by a radical M or that the Substituent YXJ-NH- on the naphthalene nucleus of the formula II is replaced by a radical Q, where Y, X, J, R, q and m have the meanings already given; E is a hydrogen or halogen atom, in particular a fluorine or chlorine atom or a nitro radical and M is a hydrogen atom or a sulfamoyl radical of the formula -SO ₂ NH ₂ ; an alkyl radical with 1 to 4 carbon atoms; an alkyl radical with 1 to 6 carbon atoms substituted by a hydroxy, cyano, sulfamoyl, carboxy or sulpho radical; a benzyl radical or a phenyl radical which can be substituted by a hydroxy, sulfamoyl, carboxy or sulpho radical. 8. Photographic recording material according to claim 7, characterized characterized in that it contains a compound of the specified structure in which η and ρ are each * 0. 9. Photographic recording material according to claim 7, characterized characterized in that it contains a compound of the specified structure in which m = 0. 10. Photographic recording material according to claim 7, characterized characterized in that it contains a compound of the structure indicated in which G is a hydroxy radical. 11. Phot ο graph is before s recording material according to claims 1 to ι. 10, characterized in that there is a connection between the 409835/0947 Contains given formulas, with the rule that the substituent YXJ-NH- of the formula II is in the 5-position of the naphthalene nucleus with respect to G and the substituent Y- £ - X - (- NR- of the formula I is in the 5- or 6-position of the naphthalene nucleus with respect to G; and where furthermore: 2
R is an alkylene radical with 1 to 4 carbon atoms or a phenylene rest; L is a sulfamoyl or sulfonamido radical; J is a sulfonyl radical; Q is a hydrogen atom or a hydroxy radical or a radical of the formula -NHSO ₉ R ³ or -NHCOCH. in the S- or 8-position with respect to G, where it applies that R has the meaning already given; G is a hydroxy radical or a photographically inactive one Ammoniumsalζ thereof or a hydrolyzable acyloxy radical of one of the formulas 0 0 -OCR ⁴ or -OCOR ⁴ in which R ^{4 is} an alkyl radical with 1 to 18 carbon atoms or a phenyl radical which can optionally be substituted by a nitro radical or a chlorine atom; D is a chlorine or bromine atom or a cyano, trifluoromethyl, nitro or alkylsulfonyl radical with 1 to 6 carbon atoms or a benzylsulfonyl radical; E is a hydrogen atom »and M is a hydrogen atom. 409835/0947 12. Photographic recording material according to one of the claims 1 to 11, characterized in that it contains a compound of one of the formulas given in which represents place: X is a phenylene radical of one of the formulas: or G is a hydroxy radical or a hydrolyzable acyloxy radical and D is an alkylsulfonyl radical with 1 to 4 carbon atoms. 13. Photographic recording material according to claims 1 to 12, characterized in that it is a blue-green Express dye-generating compound contains any of the following formulas: NIISO N = N or 409835/0947 OH - yß - II. Γ, ball NHSO ₂ -XJ-NH wherein X, R, J, ι, q, Q, E, G, M and D have the meaning given have and D can be a substituent of one of the formulas: OH ball -X-t-NR-J OH Y ¹ NHSO ₂ -XJ- or provided that the substituent OH ball X-f-NR-J 409835/0947 on the naphthalene nucleus of the formula I is replaced by a radical M, or that the substituent ball NHSO, -X-J-NH- replaced by a radical Q on the naphthalene nucleus of the formula II is, and in which also mean: Ball an organic ballast group of such size and configuration that the connection during the Makes development in an alkaline developing solution non-diffusing and Y ¹ the atoms required to complete a benzene or naphthalene nucleus. 14. Photographic recording material according to claim 13, characterized characterized in that it contains a compound of one of the formulas given, in which: X is a radical of the formula -R ² -L _n -R ² pin which represent: 2
R is an alkyl radical with 1 to 4 carbon atoms or a phenylene radical which can optionally be substituted by a carboxy, chlorine, methyl or methoxy radical, L is a sulfamoyl, sulfonamido, carbamoyl or Carboxamido radical and where η and ρ have the meaning given to have; 409835/0947 Y ¹ the atoms required to complete a benzene or naphthalene nucleus. 14. Photographis this recording material according to claim 13, characterized characterized in that it contains a compound of one of the formulas given, in which: X represents a radical of the formula -R ² -L _n -R ² in the: 2
R is an alkyl radical with 1 to 4 carbon atoms or a phenylene radical which is optionally substituted by a carboxy, chlorine, methyl or methoxy radical can be, L is a sulfamoyl, sulfonamido, carbamoyl or Carboxamido radical and in which η and ρ have the meanings given; R is a hydrogen atom; q - 1; m »0 or 1; Q is a hydrogen atom; a hydroxy group or a group one of the formulas -NHCOR ³ or -NHSO ₂ R ³ , in which R ^{3 represents} an alkyl radical having 1 to 4 carbon atoms, which can optionally be substituted by a hydroxy, cyano, sulfamoyl, carboxy or sulpho radical; a benzyl radical or a phenyl radical which can optionally be substituted by a carboxy, chlorine, methyl, methoxy or sulfamoyl radical; 409835/0947 D is a chlorine, bromine or fluorine atom or a cyano, trifluoromethyl, nitro, fluorosulfonyl or alkylsulfonyl radical with 1 to 6 carbon atoms, which optionally substituted by a hydroxy, phenyl, cyano, sulfamoyl, carboxy, fluorosulfonyl or Sulforest can be; a Phenylsulfonylrest, which optionally can be substituted by a hydroxyl, sulfamoyl, fluorosulfonyl, carboxy or sulfo radical; a sulfamoyl radical of the formula -SO-NHR, in which R is a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms, which is optionally replaced by a hydroxy, cyano, sulfamoyl, May be substituted by carboxy or sulpho; a benzyl radical, a phenyl radical or the optionally can be substituted by a hydroxy, sulfonyl, sulfamoyl, carboxy or sulfo radical; or a carbamoyl radical of the formula -CON (R) - in R is hydrogen or methyl; or one Substituents of the formulas: or ball NH-SO ₂ -XJ- ₅ provided that the substituent 409835/0947 - YC- ball NH-SO ₂ - f- Χ-f-NR-J-) - is replaced by M on the naphthalene nucleus of the formula I or that the substituent OH ball NH-SO-X-J-NH- on the naphthalene nucleus of the formula II is replaced by Q, where it applies that Y ¹ , Ball, R, J, q and m have the meaning given; E is a hydrogen or halogen atom, in particular a fluorine or chlorine atom or a nitro radical and M is a hydrogen atom or a sulfamoyl radical of Formula -SO ₉ NH-, an alkyl radical with 1 to 4 carbon atoms; an alkyl radical having 1 to 6 carbon atoms substituted by a hydroxy, cyano, sulfamoyl, carboxy or sulpho radical; a benzyl radical or a phenyl radical which can be substituted by a hydroxy, sulfamoyl, carboxy or sulpho radical. 409835/0947 15. Photographic recording material according to claims 13 and 14, characterized in that it contains a compound of the specified structure in which η and ρ each = 0 are. 16. Photographic recording material according to claims 13 to 15, characterized in that it is a compound of the specified structure, in which m = 0. 17. Photographic recording material according to claims 13 to 16, characterized in that it is a compound of the specified structure contains, in which G is a hydroxy radical is. 18. Photographic recording material according to claims 13 to 17, characterized in that it contains a compound of the structure indicated in which E and M, respectively represent a hydrogen atom. 19. Photographic recording material according to claims 13 to 18, characterized in that it is a compound of the specified structure, in which the substituent of the formula: )H ball NH-SO ₂ -XJ-NH- is in the 5-position of the naphthalene nucleus with respect to G and where also mean: 409836/0947 Y ¹ the atoms required to complete one naphthalene nucleus; 2
R is an alkylene radical with 1 to 4 carbon atoms or one Phenyl radical; L is a sulfamoyl or sulfonamido radical; J is a sulfonyl radical; Q is a hydrogen atom or a hydroxy radical or radical of the formulas -NHSO ₂ I 8-position with respect to G; Remainder of the formulas -NHSO ₂ CH ₃ or -NHCOCH ₃ in 5- or G is a hydroxy radical or a photographically inactive one Ammonium salt thereof or a hydrolyzable acyloxy radical one of the formulas: 0 -OCR ⁴ or -OCOR ⁴ in which R represents an alkyl radical having 1 to 18 carbon atoms or a phenyl radical which is optionally substituted by a chlorine atom or a nitro radical; D is a chlorine or bromine atom or a cyano, trifluoromethyl, nitro or alkylsulfonyl radical with 1 to 6 carbon atoms or a benzylsulfonyl radical and E and M each represent a hydrogen atom. 20. Photographic recording material according to claims 13 to 19, characterized in that it contains a compound of the structure indicated in which X is a phenylene radical
of the following formulas is: 409835/0947 or and where also mean: G is a hydroxy group or a hydrolyzable acyloxy group and D is an alkylsulfonyl radical with 1 to 4 carbon atoms. 21. Photographic recording material according to claims 13 to 20, characterized in that it is a compound of the specified Contains structure in which the ballast group corresponds to one of the following formulas: -CNH-Ball ¹ or -SO ₇ NH-Ball ' where Ball 'represents the rest of the ballast group. 22. Photographic recording material according to claims 13
to 21, characterized in that there is a connection of the
contains the specified structure in which the ballast group of the
corresponds to the following formula: ? 5 ^H 11-t. - CONH - e CH "Hr 0 {' ^ C ₅ H ₁₁ _ _t ^ 23. Photographic recording material according to claim 22, characterized characterized in that it contains a compound of the specified structure in which the ballast group is in the 2-position with respect to the hydroxy group. 409835/0947 24. Photographic recording material according to claims 1 to 23, characterized in that the compound forming a cyan image dye is contained in one layer, that is adjacent to the silver halide emulsion layer. 25. Photographic recording material according to claim 1 with a substrate with: a) a red-sensitive silver halide emulsion layer, containing a cyan image dye-forming compound or having a layer containing such a compound is in contact, b) a green-sensitive silver halide emulsion layer, which contains a magenta image dye-forming compound or has a layer thereof Connection is in contact, and c) a blue sensitive silver halide emulsion layer containing a yellow image dye forming compound contains or is in contact with a layer with such a compound, characterized in that it is a compound according to claims as a cyan image dye-forming compound 1 to 23 contains. 26. Photographic recording material according to claims 1 and 25, characterized in that the silver halide emulsion layer or layers of direct-positive silver halide emulsion layers exist. 27. Photographic recording material according to claims 1 to 26, characterized in that there is an image-receiving layer and at least one container which can be split open by the application of pressure with alkaline developing liquid and with the image receiving layer and the cleavable container 409835/0947 a recording unit constitutes which by passing can be developed through the gap formed by two pressing members. 28. Photographic in the form of a recording unit according to claim 27 present recording material, characterized in that the image receiving layer is between the support and the lowermost light-sensitive silver halide emulsion layer is arranged. 29. Photographic in the form of a recording unit according to claim 27 present, recording material, characterized in that the image receiving layer on a special Layer support is arranged and that the image-receiving element formed from this layer support and the image-receiving layer can be applied to the silver halide emulsion layer or layers after exposure. 30. Photographic, in the form of a recording unit according to Recording material according to claim 27, characterized in that the splittable container is arranged in this way is that when pressure is applied, its content is between the image-receiving layer and that of the layer support of the light-sensitive Layer or layers furthest layer pours. 31. Photographic recording material in the form of a recording unit according to Claim 27, characterized in that that the image receiving layer contains a polymeric cationic mordant. 32. Photographic, in the form of a recording unit according to Recording material according to claim 27, characterized in that the image-receiving layer contains a mordant Copolymer of units (a) represented by the following formula 409835/0947 -C (Q) in which: 8th
R and R individually each represent a hydrogen atom or a short-chain alkyl radical and R additionally a radical with at least one aromatic nucleus; a divalent alkylene, arylene, aralkylene or arylenealkylene radical or a radical of the formulas ¹¹ 12 -OC-R ^Δ or -C-NH-R, in which 12 8 R is an alkylene radical, or together with R a remainder of the formula: -C ^X N - R ¹² ■ \ 12th
in which R has the meaning given; 409835/0947 R% R ^1O and R ¹¹ - yi - short-chain alkyl or aryl radicals and R and R also with the nitrogen atom. that they are bound and together with Q the atoms and bonds that have to be completed elimination of a quaternary nitrogen-containing heterocyclic ring required are and X is a monovalent anion, and (b) at least contains another ethylenically unsaturated monomer, with the proviso that the polymer has no carboxyl groups and the positive salt-forming cation of the formula given contains at least two aryl radicals per quaternary nitrogen atom. A cyan image dye forming compound characterized by one of the following formulas: I. or -N = N- NO, II. ball NHSO ₂ -XJ-NH where mean: N = N V W ■ NO, 409835/09 2 ? a bivalent link of the formula -R-L -R -, η ρ in which: 2
R is an alkylene radical with 1 to 8 carbon atoms or an optionally substituted phenylene radical with 6 to 9 carbon atoms - it being the case that both R radicals can have the same or different meanings; L is an oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl group; η = O or 1; ρ = 1 if η = 1 and ρ = 1 or = 0 if η = 0; where it holds that when ρ = 1, the sum of the Carbon: 14 lies; 2 carbon atoms of the two radicals R does not have R is a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms; J is a sulfonyl or carbonyl radical; m and q each = 0 or i; Q represents a hydrogen atom, a hydroxy radical or a Remainder of one of the formulas: -NHCOR ³ or -NHSO ₂ R ³ in which R is an optionally substituted alkyl radical with 1 to 6 carbon atoms, a benzyl radical or an optionally substituted phenyl radical with Represents 6 to 9 carbon atoms; 409835/0947 G is a hydroxy radical, a salt thereof or a hydrolyzable radical of one of the formulas O O -OCR ⁴ or -OCOR ⁴ in which R is an alkyl radical with 1 to 18 carbon atoms or represents an optionally substituted phenyl radical having 6 to 18 carbon atoms; D is a halogen atom or a cyano, nitro, trifluoromethyl or alkyl radical having 1 to 6 carbon atoms; an alkoxy radical with 1 to 6 carbon atoms; a carboxy radical; a carboxylic acid ester radical of the formula -COOR, in which R has the meaning already given; a fluorosulfonyl radical; an optionally substituted -SOg-phenyl radical with 6 to 9 carbon atoms; a sulforest; a sulfamoyl radical of the formula -SO ₉ NR R, in which R is a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms and R is a hydrogen atom, an optionally substituted alkyl radical having 1 to 6 carbon atoms, a benzyl radical, an optionally substituted one Phenyl radical with 6 'to 9 carbon atoms, an alkylcarbonyl radical with 1 to 8 carbon atoms or a phenylcarbonyl radical with 6 to Represents 9 carbon atoms, where it applies that the sum the carbon atoms of the radicals R ⁵ and R ⁶ does not exceed 14; a carbamoyl radical of the formula -CON (R) - ,, in which the two radicals R can have one of the meanings already given and can be identical to or different from one another; an optionally substituted alkylsulfonyl radical having 1 to 8 carbon atoms; an optionally substituted phenylsulfonyl radical with 6 to 9 carbon atoms or a radical of one of the formulas: 409835/0947 )H ball X-f-NR-J or OH NHSO ₂ -XJ- provided that the substituent ball NHSO., - / - X-f-NR-J on the naphthalene nucleus of the formula I is replaced by a radical M, or that the substituent ball NHSO ₂ -XJ-NH- is replaced on the naphthalene nucleus of the formula II by a radical Q, 409835/0947 E is a hydrogen or halogen atom or a nitro, Cyano or trifluoromethyl radical; M is a hydrogen atom; a carboxy radical; a Carboxylic acid ester radical of the formula -COOR, in which R has the meaning already given; a Sulforest, a Sulfamoylrest of the formula -SO ₀ NR R or 5 5 a carbamoyl radical of the formula -CON (R) _? in which R and R have the meanings already given; an optionally substituted alkylsulfonyl radical having 1 to 8 carbon atoms; an optionally substituted phenylsulfonyl radical having 6 to 9 carbon atoms; an optionally substituted alkyl radical having 1 to 6 carbon atoms; a benzyl radical or an optionally substituted phenyl radical; and in which also mean: Ball is an organic ballast of such a size and configuration that the connection during development does not diffuse in alkaline developing solution and Y ¹ the atoms required to complete a benzene or naphthalene nucleus with the rule that the compound is no more than one Sulforest and has no more than one carboxy residue. 34. Image dye-producing compound according to claim 33, characterized in that it has one of the formulas given corresponds to, where mean: 409835/0947 R is an alkylene radical with 1 to 4 carbon atoms or one Phenylene radical which can optionally be substituted by a carboxy, chlorine, methyl or methoxy radical; L is a sulfamoyl, sulfonamido, carbamoyl or Carboxamido radical; R is a hydrogen atom; q - 1; m = 0 or 1; Q is a hydrogen atom; a hydroxy radical or a radical of one of the formulas -NHCOR ³ or -NHSO ₂ R ³ , in which R ^{3 represents} an alkyl radical having 1 to 4 carbon atoms, which is optionally replaced by a hydroxy, cyano, sulfamoyl, carboxy, or Sulforest can be substituted; a phenyl radical which can optionally be substituted by a carboxy, chlorine, methyl, methoxy or sulfamoyl radical; D is a chlorine, bromine or fluorine atom or a cyano, trifluoromethyl, nitro, fluorosulfonyl or alkylsulfonyl radical with 1 to 6 carbon atoms, which is optionally replaced by a hydroxy, phenyl, cyano, sulfamoyl, carboxy , Fluorosulfonyl or Sulforest can be substituted; a phenylsulfonyl radical which can optionally be substituted by a hydroxy, sulfamoyl, fluorosulfonyl, carboxy or sulpho radical; a sulfamoyl radical of the formula -SO ₂ NHR ⁶ , in which R is a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms, which may be substituted by a hydroxy, cyano, sulfamoyl, carboxy or sulpho radical 409835/0947 can represents; a benzyl radical; a phenyl radical, which may be substituted by a hydroxy, sulfonyl, sulfamoyl, carboxy or sulfo radical can; or a carbamoyl radical of the formula -CON (R) - 5
in which R is a hydrogen atom or a methyl radical; or a substituent of the formulas Ball· ^ - X-f-NR-J ball JH-SO ₂ -XJ or Provided that the substituent OH Υ «Η ball X-f-NR-J-} on the naphthalene nucleus of the formula I is replaced by M, or that the substituent 409835/0947 OH ■ • ν «—T — ball NH-SO ₂ -XJ-NH ara naphthalene nucleus of the formula II is replaced by Q, where it applies that Y ¹ , Ball, R, J, q and m have the meaning given; E is a hydrogen or halogen atom, in particular a fluorine or chlorine atom or a nitro radical and M is a hydrogen atom or a sulfamoyl radical of Formula -SO ₂ NH ₂ , an alkyl radical with 1 to 4 carbon atoms; an alkyl radical having 1 to 6 carbon atoms substituted by a hydroxy, cyano, sulfamoyl, carboxy or sulpho radical; a benzyl radical or a phenyl radical, which you can be substituted by a hydroxy, sulfamoyl, carboxy or sulpho radical. 35. image dye-forming compound according to claim / 33 and 34, characterized in that it corresponds to one of the formulas given in which η and ρ «are 0. 36. Image dye-producing compound according to claims 33 to 35, characterized in that it corresponds to one of the specified formulas in which m »0. 37. Image dye-producing compound according to claims 33 to 36, characterized in that it is one of the specified Corresponds to formulas in which G is a hydroxy radical. 409835/0947 38. Image dye-forming compound according to claims 33 to 37, characterized in that it corresponds to one of the formulas given in which M is a hydrogen atom. 39. Image dye-forming compound according to claims 33 to 38, characterized in that it is one of the specified Corresponds to formulas in which: NH-SO ₂ -XJ-NH- is in the 5-position of the naphthalene nucleus with respect to G and where also mean: Y ¹ the atoms necessary to complete a naphthalene nucleus; 2
R is an alkylene radical with 1 to 4 carbon atoms or a phenyl rest; L is a sulfamoyl or sulfonamido radical; J is a sulfonyl radical; Q is a hydrogen atom or a hydroxy radical or radical of the formulas -NHSO ₂ CH ₃ or -NHCOCH ₃ in the 5- or 8-position with respect to G; A0983S / 0947 G is a hydroxy radical or a photographically inactive ammonium salt thereof or a hydrolyzable acyloxy radical one of the formulas: 0 O CIr or -OCOR ⁴ in which R represents an alkyl radical having 1 to 18 carbon atoms or a phenyl radical which is optionally substituted by a chlorine atom or a nitro radical; D a chlorine or bromine atom or a cyano, trifluoromethyl, Nitro or alkylsulfonyl radical with 1 to 6 carbon atoms or a benzylsulfonyl radical and E and M each represent a hydrogen atom. 40. Image dye-producing compound according to claims 3 8 to 39, characterized in that it has the structure indicated in which X is a phenylene radical of one of the following formulas: or and where also mean: G is a hydroxy group or a hydrolyzable acyloxy group and D is an alkylsulfonyl radical with 1 to 4 carbon atoms. 409835/0947 41. Image dye- producing compound according to claims 33 to 40, characterized in that it corresponds to the specified structure in which the ballast group is one of the following. Formulas corresponds to: -CNH-Ball ¹ or -SO ₂ NH-Ball where ball ^{1 represents} the remainder of the ballast group. 42. Image dye-producing compound according to claims 33 to 41, characterized in that it has the structure indicated in which the ballast group corresponds to the following formula: ^C 5 ^H 11-t. -CONH-f 409835/0947