DE2848455A1 - PHOTOGRAPHIC RECORDING MATERIAL - Google Patents

Description

The invention relates to a photographic recording material having at least one silver halide emulsion layer applied thereon, which is a non-diffusible color former, which is an azo dye which is diffusible under alkaline conditions capable of releasing, contains or is in contact with a layer with such a compound.

It is known that photographic recording materials with a layer support and at least one silver halide emulsion layer and a color former in or adjacent to the silver halide emulsion layer are used to carry out color diffusion transfer processes. After exposure, such a recording material is treated with an alkaline developing liquid, whereby an image-wise development of the silver halide is effected and a dye is formed image-wise. The imagewise dye generation is generally effected by a carrier residue which, in the presence of alkaline developing liquid, is responsible for a change in the diffusivity of at least the dye part of the color former. It is generally known to use color formers , which are initially immobile or mobile in the developing solution, for the production of recording materials for the color diffusion transfer process. In the case of a recording material with an internal mobile color former , the alkaline developing liquid causes the image-wise release of a diffusible dye. In the case of a recording material with a mobile dye former, the alkaline developing liquid has the effect that the color former is made imagewise insoluble and thus immobile.

It is also generally known to produce photographic recording materials which, after imagewise exposure , are brought into contact with an alkaline developing liquid with the aim of bringing about an imagewise difference in the mobility of at least one part of the color former, ie to release a dye or a to cause Farbstoffrorliu ferverbindung. Examples of dye-releasing color formers of this type and photographic recording media

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rials in which such color formers are used are known, for example, from the published US patent application B 351 673, US-PS 3,980,479 and GB-PS 1,464,104 and 1,464,105.

The yellow dye-releasing compounds described in the cited patent application and the cited patents have proven to be advantageous.

It has been shown, however, that there is a need for even further improved color formers which are capable of releasing yellow dyes and which are more stable than Have exposure to heat, light and chemical reagents and are further characterized by more advantageous color tones and, finally, are even more resistant to diffusion after the development process has been carried out.

The invention was based on the knowledge that the asked Task «can be solved by using new non-diffusible color formers, the azo dyes or precursor compounds capable of releasing such azo dyes as a result of the evolution of silver halide. The new yellow azophenol dyes are characterized by electron withdrawing groups (dectron withdrawing groups) in the ortho positions to the phenolic Hydroxy radical.

The invention thus relates to photographic recording materials and recording units with such Dye-releasing compounds or color formers, as characterized in the claims.

A photographic recording material according to the invention thus consists, in the simplest case, of a layer support des At least one light-sensitive silver halide emulsion layer is applied which contains a non-diffusible color former of the structure given below or which

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is in contact with a layer that contains a color former capable of splitting off an azo dye residue, which is diffusible under alkaline conditions. Those which can be used according to the invention for the production of a recording material Color formers can be represented by the following structural formula:

I. Z ^N 7 N = N

where mean:

D an electron-withdrawing residue with a Hanunett

para sigma value of 0 or greater than 0, preferably between 0 and +1.5;

E an electron-withdrawing residue with a Hammett

para sigma of +0.3 or greater than +0.3, preferably between +0.3 and +1.5;

Z to complete an aromatic

carbocyclic or heterocyclic nucleus with at least one ring with 5 to 7 atoms required Atoms, for example those to complete a phenyl, pyridyl, naphthyl, pyrazolyl or Indolyl ring's required atoms;

G is a hydroxy radical or a hydrolyzable Vor

runner rest for this,

with the proviso that at least one of the rings has a ballast carrier residue is bound, which the diffusible azo dye under alkaline conditions as a result (either directly or vice versa) the development of the silver halide emulsion layer or layers.

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Hammett para sigma values of organic residues and methods for their determination are known, for example, from ¹¹ J. Hine, "Physical Organic Chemistry", 2nd edition, 1962, page 87; H. VanBekkura, PE Verkade and BM Wepster in "Rec.Trav.Chim.", Volume 78, page 815, 1959; PR Wells in Chem. Revs., Vol. 63, p. 171, 1963; HH Jaffe, in "Chem. Revs.", Volume 53, page 191, 1953; MJS Devar and PJ Grisdale in "J. Amer. Chem. Soc", volume 84, page 3548, 1962 and Bariin and Perrin in "Quart. Revs.", Volume 20, page 75 ff, 1966.

Particularly advantageous color formers have proven to be those of the formula I given, in which Z stands for the atoms, di · to complete an aryl radical, for example one optionally substituted phenyl radicals are required. The aryl radical, for example the phenyl radical, can have one or more substituents, for example one or more several halogen atoms, e.g. chlorine, fluorine, bromine and / or iodine atoms and / or short-chain alkyl radicals, e.g. methyl, ethyl, Propyl or butyl radicals and / or short-chain alkoxy radicals, e.g. Methoxy, ethoxy, propoxy or butoxy radicals or acid radicals or acid derivative radicals, for example ester and amide radicals, for example sulfo-, sulfonamido, sulfamoyl, carboxy, carboxamido or carbamoyl radicals, which in turn can optionally be substituted, for example by short-chain alkyl or lower aryl groups. Short-chain alkyl radicals and short-chain alkoxy radicals are to be understood here as meaning radicals with preferably 1 to 4 carbon atoms, whereas lower aryl radicals, preferably those »having 6 to 9 carbon atoms, e.g. phenyl, benzyl, tolyl, Methoxyphenyl and chlorophenyl radicals.

The use of color image modifiers of the formula given in which the ballast carrier residue is located on the ring completed by Z has proven to be particularly advantageous.

Particularly advantageous color formers are also those of given formula, in which D stands for an electron withdrawing radical, which consists of a halogen atom or a nitro, Cyano, carboxy, sulfonyl, sulfamoyl, carbamoyl or short

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chain perfluoroalkyl radical and in which E also exists for a strong electron withdrawing radical, namely a Nitro, cyano, carboxy, sulfonyl, sulfamoyl or short-chain perfluoroalkyl radical.

The sulfamoyl and carbamoyl radicals can optionally be substituted, for example by short-chain alkyl or lower aryl radicals or heterocyclic radicals. They can also form part of the ballast carrier residue which is split off from the carrier when the dye is released.

The sulfonyl radicals can also optionally be substituted, for example by short-chain or lower alkyl radicals Aryl radicals or heterocyclic radicals. They can also represent part of the remainder of the ballast carrier.

Furthermore, for example, have proven to be particularly advantageous Proven color former of the formula given, in which D stands for a halogen atom.

Particularly advantageous color formers are also those of the formula given, in which E is a carbamoyl radical corresponding to the following formula: -CON (R) ₂ * in which the two radicals R can be the same or different and can represent a hydrogen atom or a short-chain one , optionally substituted alkyl radical, for example a hydroxyalkyl, carboxyalkyl, carbamoylalkyl, sulfamoylalkyl or phenylalkyl radical, a lower, optionally substituted aryl radical, for example a hydroxyphenyl, carboxyphenyl, sulfamoylphenyl, carbamoylphenyl or methylphenyl radical or a heterocyclic radical, for example a pyridyl, benzotriazolyl or oxarinyl radical. Furthermore, the radicals R can represent part of the ballast carrier radical or, together with the nitrogen atom on which they are attached, represent a 5- or 6-membered heterocyclic ring, for example a pyridyl or oxazinyl ring.

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Particularly advantageous color formers are also those of the formula given, in which G is a hydroxy radical or is a hydrolyzable ester residue of one of the following formulas:

0 0 0

-OCR ¹ , -OCOR ¹ or OCN (R ¹ ) ₂

in which the radicals R can have the same or different meanings and can stand, for example for alkyl radicals with 1 to 8 carbon atoms or aryl radicals with 6 to 0

12 carbon atoms or radicals which, together with the -0-C-group, form the ballast carrier radical.

The azo dyes which can be produced according to the invention correspond to the given formula I with the exception that they have no ballast carrier residue. However, the dyes can have a residue or have part of a ballast carrier residue when they are released by the non-diffusible color former.

If G stands for a hydroxy radical, the dyes are azophenols, which typically have a yellow hue. G stands for a hydrolyzable precursor residue of a Hydroxyl radical, the absorption spectrum of the dye is shifted to the region of shorter wavelengths. Will be such Remainder G hydrolyzed, t.B. under the alkaline conditions of Development process, the yellow hue of the azophenol dye is obtained.

The ballast carrier residue can be very different, i.e. compounds of the given formula I can be used according to the invention ■ with the most varied of ballast carrier remnants. Depending on the nature or the type of the ballast carrier residue, it can be bound to the azo dye through various residues or links. Such links are considered to be part of the ballast carrier residue. Becomes the dye residue from the color former split off or released, the cleavage can take place at such a point that only part or all of it Link or parts of the ballast carrier residue on

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Remaining dye remains.

The ballast carrier residues can thus consist of conventional ballast carrier residues, as they are known from the literature. So can the color formers used according to the invention have, for example, ballast carrier residues, as they are from US Pat. No. 3,227,550, 3,628,952, 3,227,552 and 3,844,785 are known (in which case dyes are released by chromogenic coupling). Even For example, the carrier residues may have a configuration as is known from US Pat. Nos. 3,443,939 and 3,443,940 (In the compounds described here, dyes are released through an intramolecular ring closure). Further suitable ballast carrier remnants are, for example, from the US-PS No. 3,698,897 and 3,725,062 known (here dyes are released from hydroquinone derivatives). Reference is also made for example on the ballast carrier remains of US Pat. No. 3,728,113 (Here dyes are released from quaternary hydroquinonylmethyl salts. Finally, see US Pat. No. 3,719,489 and 3,443,941 (here there is a release of dye induced by silver ions). Ballast carrier remains are finally also from US-PS 3,245,789 and 3,980,497, CA-PS 602 607, GB-PS 1,464,104 and the literature reference "Research Disclosure ", 14447, April 1976.

In a particularly advantageous manner, the remainder of the ballast carrier can be represented by the following formula:

II (BALL-TRXG-BINDEGL.) -

where mean:

BALL is an organic ballast group of such molecular size and configuration that the compound non-diffusing in a photographic recording material during the development process in an alkaline developing liquid power;

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TRAG is an oxidizable acyclic, carbocyclic or heterocyclic radical;

BINDING REGULATION. a residue which, upon oxidation of the residue, TRAG

can be split hydrolytically, with the release or splitting off of a diffusible one Azo dye.

The link BINDEGL. For example, it can consist of a remainder of one of the following formulas:

+ NHSO ₂ -,

0 + NH-P-O-

O-alkyl

+ NHSO

SO ₂ NH-

+ NHSO ₂ (CH ₂ ) ₃ NHSO ₂ -

^h NHS

NHSO ₂ -

COOH

⁺ NHSO

^h NHSO

NHSO ₂ -

CONH-where ⁺ indicates the position of the bond to the carrier residue.

The nature of the ballast group is not critical as long as it ensures that the connection is nondiffusible. Typical ballast groups are long-chain alkyl radicals that can be bonded directly or indirectly to the compound, as well as aromatic radicals of the benzene and naphthalene series, which can be indirectly bonded to the compound or can be fused directly to the carbocyclic or heterocyclic ring . Advantageous ballast groups usually have at least 8 carbon atoms and can, for example, consist of substituted or unsubstituted alkyl radicals with 8 to 22 carbon atoms.

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or carbamoyl radicals with 8 to 30 carbon atoms, for example radicals of the following formulas:

-CONH (CH ₂ ) 4-0-C ₆ H ₃ (C ₅ H _{1 λ} ) ₂ or -CON (C ₁₂ H ₂₅ ) ₂

or keto radicals with 8 to 30 carbon atoms, e.g. those of the formulas:

-CO-C ₁₇ Η_ _ς or -CO-C _n H, (t.-C ₁ -Η- _c ) 1 / 3b 0 4 - 1ZZ5

or sulfamoyl radicals having 8 to 30 carbon atoms, e.g. of the formula

-SO ₂ NHC ₁₂ H ₂₅ .

Typical examples of ballast carrier residues of the formula II can be found, for example, in the literature reference "Research Disclosure", November 1976, pages 68-74 and April 1977, pages 32-39.

According to a particularly advantageous embodiment of the invention, the ballast carrier residue has a structure such that the diffusible azo dye is released as a direct result of the development process of the silver halide emulsion layer or silver halide emulsion layers under alkaline conditions. In such a case one can speak of a negative- working dye release. In the case of such a configuration, the ballast carrier residue can advantageously consist of a residue of the following formula :

(Ballast),,

where mean:

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ballast

D ⁽

an organic ballast group of such molecular size and configuration (e.g., a simple organic group or a polymer group) which is the compound in the photographic Recording material non-diffusing during development in an alkaline developing liquid power;

2 3

a residue of one of the formulas -OR or -NHR, in which

2
R stands for a hydrogen atom or a

hydrolyzable radical and R for a hydrogen atom or an optionally substituted alkyl radical with 1 to 22 carbon atoms, e.g. a methyl, Ethyl, hydroxyethyl, propyl, butyl, sec-butyl, tert-butyl, cyclopropyl, 4-chlorobutyl, Cyclobutyl, 4-nitroamyl, hexyl, cyclohexyl, Octyl, decyl, octadecyl, dodecyl, benzyl or phenethyl radical, with the proviso that R also partially or completely functions as a ballast radical can take over if R stands for an alkyl radical with more than 8 carbon atoms;

-NHSO ₂ L-

a corresponding radical in ortho or para position to D ';

the atoms necessary to complete a benzene or naphthalene nucleus or a heterocyclic system, ring or nucleus, for example a pyrazolone or pyrimidine ring, each with 5 to 7 atoms per ring;

a positive number of 1 or 2 and 2 if D ^{1 is} a radical of the formula -OR or if R has the meaning of a hydrogen atom or an alkyl radical with fewer than 8 carbon atoms and

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a link of one of the formulas: - ^ "X- (NR ⁴ -J) _7 _m - or -XJ-NR ⁴ -which in turn mean:

i) X is a divalent link of the formula

-R ⁵ -L '-R ⁵ -, wherein the two radicals R ⁵ η ρ

may have the same or different meanings and each stand for an alkylene radical with 1 to 8 carbon atoms, e.g. a methylene or hexylene radical or an optionally substituted phenylene radical having 6 to 9 carbon atoms, for example a methoxyphenylene radical;

ii) L ^{1 is} a divalent link, preferably an oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, ureylene, sulfamoyl, sulfinyl or sulfonyl radical;

iii) η = 0 or 1;

iv) ρ «1, if η ■ 1 and ρ» 1 or 0, if η ■ is 0, provided dai if ρ ■ is the carbon atom content of the sum of the both R radicals does not exceed 14 carbon atoms;

4th
v) R is a hydrogen atom or an alkyl radical

with 1 to 6 carbon atoms;

vi) j a »divalent link, consisting of a sulfonyl or carbonyl radical;

vii) q ■ 0 or 1 and viii) m ■ 0, 1 or 2.

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It has proven to be particularly advantageous if, in the formula III given, D ^{1 stands} for a hydroxy radical, j has the meaning of the number 2 and Y stands for the atoms which are necessary to complete a naphthalene nucleus.

Typical examples of such particularly advantageous ballast carrier residues of the last-described type are for example from the known US patent application B 351 673, the US-PS 3,928,312, FR-PS 2 284 140 and German Offenlegungsschriften 2 406 664, 2 613 005 and 2 505 248 are known.

Typical, advantageous ballast carrier residues are, for example:

NHSO

^C 15 ^H 31

NHSO

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OH

CONH- (CH ₂ ) ₄ 0

mso

^C 2 ^H 5 N-CO

' ^C 15 ^H 31

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According to a further particularly advantageous embodiment of the invention, the recording material has a color former given formula I, which has such a ballast carrier residue that the diffusible azo dye inversely to Development of the silver halide emulsion layer or layers is released under alkaline conditions. In this case, there is therefore a positive-working dye release. In such a case, the Ballast carrier residue can be, for example, a residue of the following formula:

NO ₂

IV '^ ⁰ X ° ^R?

f CC ^ ~ ⁴

Ballast f- CCN- ^ ~ X «- (NR ⁴ -J) 7 _m

where mean:

Ballast an organic ballast group of such a molecular size and configuration that the compound in a recording material during development renders nondiffusible in an alkaline developing liquid;

2
W di · door complete an optionally

substituted benzene nucleus required atoms;

R is an optionally substituted alkyl radical

preferably 1 to 4 carbon atoms;

X ^{1 is} an alkylene radical having 1 to 4 carbon atoms;

R is a Wasieritoffatom or an alkyl radical with 1 to

Carbon atoms;

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a sulfonyl or carbonyl radical;

0 or 1 and

0, 1 or 2.

Examples of advantageous ballast carrier scraps of this type are;

^C 12 ^H 25 ^SO 2

0 CH,

It I

CN- (CH ₂ ) ₃ -NHSO ₂ -

^SO 2 ^C 12 ^H 25

CN- (CH ₂ ) ₂ NHCO-

^SO 2 ^C 18 ^H 37

Furthermore, in the case of a positive-working system the ballast carrier residue can be, for example, a residue of the following formula:

C-fCH ^^ N-C-O- ^ X "-

'q-'m

where mean:

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Ballast an organic ballast group of such

Molecular size and configuration that the compound in a photographic recording material non-diffusing during development in an alkaline developing liquid is;

W to complete an if necessary

substituted quinone radicals required atoms;

r ■ 1 or 2;

R is an optionally substituted alkyl radical

with 1 to 40 carbon atoms or an optionally substituted aryl radical with 6 to 40 carbon atoms;

k «1 or 2 and ■ 2, if R is a residue with less

than 8 carbon atoms;

X "is an optionally substituted phenylene radical

with 6 to 9 carbon atoms.

R, J, q and m have the meanings already given.

Examples of ballast carrier scraps of this type are those of the following formulas:

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c = T NHSO "-

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In the case of a third embodiment, a positive-working Systems, the ballast carrier residue has a structure as it results from the following formula VI:

R ⁷

ballast

CON-t

-Cv

C-N

'q-'m

\ 2

0
C— (/

/ Il

■ R

where ballast, W, R, X '»R» J, q and m are those already given Have meaning.

Examples of ballast carrier residues of this type are residues of the following formulas:

CO-N- (CH ₂ ) ₃ -NHSO ₂ -

Further details with regard to such ballast carrier residues, as well as processes for their production can be found, for example in GB-PS 1,464,104 and 1,464,105.

In the case of a positive-working system, the ballast carrier residue finally also advantageously be a residue of the following formula:

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BaI las t-

^R O Nc-0

O A 7

where ballast, W, r, R, k, X ", R, J, q and m die already have given meaning and

K for a hydroxy radical or a corresponding hydrolyzable Forerunner remainder for this exists.

Examples of ballast carrier scraps of this type are:

OH ^C 18 ^H 37 °

C-O

NHSO ₂ -

OH CH 0

I I ·> Il

^C 12 ^H 25

With regard to further details of such ballast carrier residues and with regard to processes for their production, for example See U.S. Patent 3,980,479.

Particularly advantageous, non-diffusible color formers for the production of recording materials according to the invention can be used represented by the following formula VIII:

909850/070?

N = N

Q where mean:

G is a hydroxy radical or a hydrolyzable ester radical of one of the formulas:
0 0 0
-OCR ¹ , -OCOR ¹ or -OCN (R ¹ ) ₂

wherein the two radicals R can have the same or a different meaning and for alkyl radicals with 1 to 8 carbon atoms or aryl radicals with 6 to 12 carbon atoms or radicals which together with the grouping q

Il

-0-C-represent the ballast carrier residue;

D is an electron withdrawing radical consisting of a halogen atom or a nitro, cyano or short-chain perfluoroalkyl radical or a radical of one of the following formulas:

-SO ₂ R ⁸ , -SO ₂ N (R ⁹ ) ₂ , -COOR ⁹ or -CON (R ⁹ ) ₂

E is a strong electron withdrawing radical, consisting of a nitro, cyano or short-chain perfluoroalkyl radical or a remainder of one of the following formulas:

-SO ₂ R ⁸ , -SO ₂ N (R ⁹ ) ₂ , -COOR ⁹ or -CON (R) ₂

Q Q

P is a radical of one of the formulas -COOR, -SO ₂ N (R) ₂ or -CON (R ⁹ ) ₂ ;

y ■ 0, 1 or 2;

R is a radical as defined in claim 9

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R is a short-chain alkyl or lower aryl radical;

ο
R is in each case a hydrogen atom or a short-chain alkyl, short-chain hydroxyalkyl or short-chain carboxyalkyl radical or a lower aryl radical, it being understood that one of the radicals R can also be a radical which, together with the grouping 0

-CO-, -SO ₂ N- or

-CON- can represent a ballast carrier residue or

q where it applies that both radicals R with the nitrogen atom, on which they sit, can also represent a 5- or 6-membered heterocyclic ring;

Q is a hydrogen or halogen atom or a carboxy radical or a short-chain alkyl or short-chain Alkoxy radical, where

that at least one of the substituents G, D, E or P contains the ballast carrier radical.

In those cases in which two radicals R

q
are bonded, these radicals R can be the same or one

have different meanings from each other.

Particularly advantageous compounds of the formula VIII are, for example those in the meaning:

G is a hydroxy radical or a hydrolyzable ester radical of the formula -OCOR, where R is an alkyl radical having 1 to 8 carbon atoms or an aryl radical having 6 to 12 carbon atoms;

D is an electron withdrawing group consisting of halogen, a

Q Q

Cyano radical or a radical of the formula -SO ₂ R, in which R has the meaning given;

E is a strong electron withdrawing radical, consisting of a nitro or cyano radical or a radical of one of the formulas -SO ₂ R ⁸ , -CON (R ¹ ^ ₂ or -SO ₂ N (R ¹¹ ) ₂ , where R ⁸ is already on -

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-3T-

2848415

has the meaning given and R each represent a hydrogen atom or a short chain alkyl, hydroxyalkyl or short chain short chain carboxyalkyl group or a short-chain carbamoylalkyl, short chain Sulfamoylalkyl-, phenyl, hydroxyphenyl, carboxyphenyl, carbamoylphenyl, sulfamoylphenyl, or a mono- or bi-nuclear heterocyclic radical with 5 to 6 ring members in each ring or in which both radicals R 'form a 5- or 6-membered heterocyclic ring with the nitrogen atom on which they are attached, and with the proviso that the two radicals located on a nitrogen atom R radicals can have the same or different meanings;

Q is a hydrogen or halogen atom or a carboxy, short-chain alkyl or short-chain alkoxy radical;

P remains a ballast Ti% and

y - 1.

A particularly advantageous ballast carrier radical of the type represented by the formula III, for which P in the formula VIII can stand, is a ballast carrier radical of the following formula:

ballast

NHSO ^ R ⁵ -NR ⁴ "

in which ballast stands for a ballast group of the type already described and in which also mean:

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Y ¹ the atoms required to complete a benzene or naphthalene nucleus;

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

R is a hydrogen atom or an alkyl radical with 1 to about 6 carbon atoms;

J is a sulfonyl radical and
m * 0 or 1.

Particularly advantageous azo dyes are those of the formula VIII, with the exception that D, E and P do not have any ballast carrier residues.

Particularly advantageous azo dyes can be identified by the following Reproduce Formula X:

N-N

Q where mean:

a hydroxy radical or a hydrolyzable ester radical of the formula -OCOR
has given meaning;

remainder of the formula -OCOR, where R is the

D is an electron withdrawing group consisting of halogen or a cyano group or a group of

O Q

Formula -SO-R »" in which R has the meaning given;

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a strong electron withdrawing radical, in particular a nitro or cyano radical or a radical of one of the formulas -CON (R) ₉ , -SO ₉ R ⁸ or -SO ₉ N (R ¹¹ ) 9 »where R, R ⁸ and R are already have given meaning;

a hydrogen or halogen atom or a carboxy, short-chain alkyl or short-chain alkoxy radical;

ο 11

P is a radical of one of the formulas -COOR, -SO ₉ N (R) ₉ or -CON (R) ~ »where R and R have the meanings already given and

Examples of typical, particularly advantageous non-diffusible Color formers and azo dyes releasing azo dyes are listed in Tables I and II below.

- 34 -

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CD-CD

1 2 3 4 5

6 7

Table I:

Color formers releasing azo dyes

TRAG.

Connection TRAG 'No.

Binding position

• N-N

A B A A

C ¹ C

4 3 4 4 4

H Cl -CONHCh ₂ COOH OH H Cl -CONHCH ₂ COOh OH H F. -CONHCh ₂ COOH OH H Br -CONHCh ₂ COOH OH H Cl OH

Cl
Cl

-CONH

-CONHCH ₃
-CONHC ₄ H ₉ . _n

OH OH

Table la

Color formers releasing azo dyes

O
(O
OO
N>

Connection TRAG 'No.

2 3 4 5 6 7 8 9

10 11 12 13

Binding position

N = N

C ¹

3.5

H Cl -NO ₂ OH H Cl -CN OH H Cl -NO ₂ OH 2-Cl Cl -SO ₂ NHC ₂ H ₅ OH H Cl -SO ₂ NHC (CH ₃ ) ₃ OH H Cl -SO ₂ NHCH ₂ COOC ₂ H ₅ OH H Cl -SO ₂ NHCH ₂ COOH OH H Cl -NO ₂ OH H
H Cl
Cl -NO ₂
-SO ₂ NHC ₂ H ₅ OH
OH H Cl -NO ₇ OCOPh H Cl "SO ₂ ¹ O OH H Cl -SO ₂ N (C ₂ H ₅ ) ₂ OH

tn

as

- 36 -

to

S B 8

O O O

XXXUUUXXX

ooooooooo

K N MO <-> r> N (O

to EE K X U U

U N »- ^

Kl Μ

tO

33 in-

UX

UUUUUU

NNNNNNI

ZOOOOOO

U CO OT CO CO CO CO

I I I I I I I

\ o U

iHiHtHi-li-HrHrHCOi-l UUUUUUU I U

to

O U

XnSXScmSXX

U UX

CM (MN

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Table Ib:

Color formers releasing azo dyes

N = N

909ί link
No. TRAG ² P. ( y Q E. E. D. G α>
O 23 J SO ₂ CH ₃ 1 H TRAG Cl OH CJ
- «J 24 K SO ₂ CH ₃ 1 H -SO ₂ NHCH ₃ Cl TRAG O

Explanation of the footnotes:

Position on the phenylazo radical in which the carrier radical is bound;

the carrier residues A, B and D corresponded to the following general formula:

BALL

NHSO

where BALL has the following meaning:

CU-, ^ t

A: BALL B: BALL D: BALL

CONH (CH ₂ ) ₄ -0

-CONHCH ₉ CH ₉ - ^C 2 ^H 5

The carrier radical C corresponded to the following general formula;

OH

where X and m have the following meanings:

m-0

m - 1; X - k

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>' ^x

284I4II

The carrier E corresponded to the following formula:

0-0

The carrier F. corresponded | Γ 0 I. the following formula NO ₂ J dd CH ₃ λ I.
so ₂ ^C 12 ^H 25 ^SO 2 -1 Ztijfr PNHSO ₂ I. CH ₃ C ₁₂ H 25th

The carrier G corresponded to the following formula:

-SO ₂ NH

NHSO;

Two dye residues were thus bound to one carrier residue.

Carriers H and J conformed to the following formula:

OH

'BALL

NHS

NHSOi

where BALL was a remainder of one of the following formulas:

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H: -CONH (CH ₂ ) ₄ -O

J: -CON (C

The carrier K corresponded to the following structural formula:

^C 18 ^H 37

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Table II:

Azo dyes

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No. P. y Q D. G E. »J
ο 1
2 4-SO ₂ NH ₂
3-SO ₂ NH ₂ 1
1 H
H Cl
Cl OH
OH -CONHCH ₂ COOh
-CONHCH ₂ COOh "** 3 3-SO ₂ NH ₂ 1 H Cl OH -CONH - ^ - COOH 4th 4-SO ₂ NH ₂ 1 H Cl OH -CONH-O-COOH 5 4-COOH 1 H Cl OH -CONH-O-SO ₂ NH 6th 4-SO ₂ NH ₂ 1 H Cl OH -CONH-O-SO ₉ NH ₉ 7th 4-SO ₂ NH ₂ 1 H F. OH -CONHCH ₂ COOh 8th 3-SO ₂ NH ₂ 1 H F. OH -CONHCh ₂ COOH 9 4-SO ₂ NH ₂ 1 H Br OH -CONHCH ₂ COOh

IO
U 0 t O O O E. U U U U CM CM O X X X CJ U CJ χ aT I. O O 55 55
O O U CJ U CJ I. I. I I

CTi

to

g § g S § g

U rl H il iH iH M CJ UUUU

Ο V) • P

EC E OS

CM

CM

CM

CM

CM

55 55 55 55 55

CM CM CM CM CM CM

O O O O O CO

to ^ ^ t ^ f

co

co

co

CO

co

O 1-

909820/0707

Table Ha:

Azo dyes

N = N

80982 dye
No. P. y ο 1 5-SO ₂ NH ₂ 1 ο 2 4-SO ₂ NH ₂ 1 O 3 4-SO ₂ NH ₂ 1 4th 4-SO ₂ NH ₂ 1 5 4-SO ₂ NH ₂ 1 6th 3,5-SO ₂ NH ₂ 2 7th 3-SO ₂ NHCOCH ₃ 1 8th 4-SO ₂ NH ₂ 1 9 4-SO ₂ NH ₂ 1 10 3-COOCH ₃ 2 5-SO ₂ NH ₂

2-Cl

2-Cl

Cl OC Cl OH Cl OH Cl OH Cl OH Cl OH Cl OH SO ₂ CH ₃ OH COOH OH Cl OH

SO ₂ NHC ₂ H ₅

SO ₂ C ₂ H ₅

SO ₂ CH ₃

SO ₂ NHC ₂ H ₅

SO ₂ NHC ₂ H ₅

SO ₂ CH ₃

COOH

2843455

to

U csi

O CO

55 CJ

CSI

CSI

Z O U CO

κ aa ο ο

55 r-t U U

CSJ τ—

JQ cd H

CSJ

CM

Z K Z

«Μ. O CM CM

O O O O

CO U CO CO

I I I I

κι in ^ μ

DOOH

1/1

Ur

t - cm ro

- 45 -

§09820 / 0707

The dyes resulting from the color formers can be prepared by customary known methods, such as, for example are known from the book by Fierz-David and Blangley, "Process of Dye Chemistry", Verlag Interscience Publishers, Inc., 1949.

Some of the dyes of the formula given, in which both D and E are strong electron withdrawing radicals, cannot be prepared in the usual way, since these radicals deactivate the phenol so that it does not couple with diazonium salts. In these cases, the azophenol can be prepared by reacting corresponding arylazomalonaldehyde derivatives (Chem. Ber. 97 , 96-109, 1964) with a corresponding 1,3-disubstituted acetone.

The production can thus take place, for example, according to the following reaction equation:

CH ₂ CN

Ar-N = N-CH + C = 0> Ar-N = N

* CH ₂ -CN

The non-diffusible azo dyes which can be used for the production of recording materials according to the invention Compounds can be prepared by reacting a suitable derivative of the dye with a suitable one Derivative of the carrier, it being possible for the two compounds to be reacted by customary known methods.

Starting from recording materials according to the invention, color photographic images can be produced by the Recording material treated after imagewise exposure in such a way that an imagewise distribution of diffuse azo dye obtained as a result of imagewise exposure of the silver halide emulsion layer or layers will. Color photographic images can be produced by using the diffusible which has been released imagewise

2843455

Dye or by the in the recording material in imagewise Distribution of remaining non-diffusible color images or by using both the residual color former also of the diffusible dye produced. The released Diffusible dye can thereby be in an image-receiving sheet or an image-receiving layer to produce a transfer image diffuse. On the other hand, however, it is also possible to remove the dyestuff which has been split off from the recording material remove it and stop using it. Regardless of whether, the image-wise released diffusible dye is used or not to form a color image, the non-diffusible one remaining in the recording material can be used Use residual dye as dye image in the layer in which the dye-former was accommodated. Will If the color image produced by the non-diffusible dye is used, any remaining silver and silver halide can be used remove by customary known methods, for example by treatment with a bleach bath and then by treating with a fixer or by using a bleach-fix bath. In the event that it is the azo dye, which is split off from the non-diffusible color former, to a so-called shifted dye involves the process of producing a dye image in the recording material, more precisely the production a so-called residual dye image, a process one which the displaced dye is converted into a dye of the desired type, for example by hydrolysis.

On the other hand, however, it is also possible after the initially generated diffusible dyes removed from the material has been to use the remainder of the nondiffusible color former to produce a transfer image, namely by oxidation, e.g. by cross-oxidation or in some other way, producing a second distribution of diffusible Dye which is then transferred to a suitable image-receiving sheet or layer can be.

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2848465

The production of a color photographic image starting from a recording material according to the invention can thus be done in the following way:

a) Treatment of the imagewise exposed photographic recording material with an alkaline developing liquid in the presence of a silver halide developing agent developing each of the existing exposed silver shark ogenide emulsion layers,

b) imagewise release of the diffusible azo dye from the color former as a result of the development of the silver halide emulsion layers and

c) Allowing at least part of the in image to diffuse out Distribution of generated azo dye from the layer in which the azo dye was generated.

In a particularly advantageous manner, starting from a recording material according to the invention produce a colored transfer image in the following way:

a) Treatment of the imagewise exposed photographic recording material with at least one color former of the given formula I, in which the carrier residue corresponds to the following formula:

NHSO ₂ L—
where D ¹ , Y, L and j have the meaning already given,

909820/0707

with an alkaline developing liquid in the presence of a silver halide developing agent to develop of each of the exposed silver halide emulsion layers and oxidizing the developing agent;

b) oxidation of the color former with the oxidized silver halide developing agent;

c) splitting of the oxidized color former as a result of the hydrolysis brought about by the alkaline medium with release a diffusible azo dye as a function of the imagewise exposure of each of the silver halide emulsion layers and

d) Obtaining at least a part of the image generated Azo dye into an image receiving layer by diffusion.

After developing the recording material in the described After the transfer of the azo dye, in addition to the developed silver, azo dye remains in this in image distribution. As a result, a colored image can be made from any non-diffusible color former that is still present obtained in the recording material when the remaining silver and silver halide are removed by customary known methods is, for example, by treatment with a bleaching bath and a subsequent treatment with a fixing bath or by using a bleach-fix bath. It is also possible to use the azo dye present in imagewise distribution diffuse from the recording material into these baths instead of the dye onto an image-receiving element or to be transferred to an image receiving layer.

The recording material can be treated according to the usual known methods with an alkaline developing liquid to initiate development. In a particularly advantageous manner, a developing liquid can be applied to the recording material, for example by means of a splittable container in which the developing liquid is contained.

9Q982Ü / 0707

-49- 284845!

bring.

The developing agent required for development can advantageously be used in the developing liquid to be brought. On the other hand, however, it is also possible to use an alkaline solution to initiate the development process to be used when the developing agent is in a photographic material, an image receiving element or a So-called developing sheet is accommodated, in which case the alkaline solution only activates the developing agent serves.

According to a particularly advantageous embodiment of the invention, the recording material consists of a so-called recording unit, which is designed to be developed by passing it through a gap created by two pressures exercising members is formed, for example by the gap, the pressure of two in a self-developing camera exercising members is formed. Such a recording unit consists advantageously of:

1) a photographic recording member or element as described;

2) an image receiving layer and

3) Means for distributing alkaline developing liquid in the recording unit, for example a splittable container which is designed in such a way and in which Way is accommodated in the recording unit that it is split up when a force is applied and its contents distributed in the recording unit.

Such a recording unit is also characteristic a content of a silver halide developing agent.

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-so- 2I484SS

The image receiving layer of such a unit can be located on a special layer support which is designed in such a way that that it can be applied to the exposed recording material after the exposure of the recording part. Such Image receiving elements are known, for example from U.S. Patent 3,362,819. When recording units are used a splittable container is produced, this is usually with respect to the photosensitive part of the recording material and the image receiving element arranged in such a way that that when a pressure force is applied, for example when pressure is exerted by members in a so-called self-development camera the contents of the container between the image-receiving layer and the outermost layer of the photographic material is distributed. After development has taken place, the image-receiving element can be separated from the recording material.

However, the image receiving layer can also be an integral part the recording unit and between the support of the recording material and its outermost light-sensitive Be housed silver halide emulsion layer. Such a recording unit with an integrated image receiving layer is for example from BE-PS 757 960 known. In the case of such a recording unit, the support is the photographic one Material transparent and coated with an image receiving layer, a practically opaque light-reflecting one Layer, e.g. a TiO2 layer and the light-sensitive layer or layers Layers.

After imagewise exposure of the recording material, a splittable container with alkaline developing liquid and an opaque developing sheet are applied to it.

- 51 -

909820/0707

-SI-

284845S

By the action of the pressure-exerting members in the self-developing camera, the container is split open, so that its content is distributed over the light-sensitive part of the recording unit when it is removed from the camera. The developing liquid develops each of the exposed silver halide emulsion layers, as a result of which Development process image dyes are generated, which diffuse into the image receiving layer, with the production of a positive, right-side recognizable image that can be viewed through the transparent support on the opaque reflective background. Regarding further details referred to BE-PS 757 960.

A recording material according to the invention can also have a structure as known from BE-PS 757 959 is. The recording units described in this patent are also those with an integrated image receiving layer. In the case of such recording units, the substrate is the recording material transparent and coated with an image-receiving layer, a practically opaque, light-reflecting layer and the or the photosensitive layers. Adjacent to the top layer of the photosensitive material is a splittable container with alkaline developing liquid and an opacifier arranged. A cover sheet composed of a transparent carrier and a neutralizing layer and a control layer applied thereon is then applied to the photosensitive material and the splittable container. The recording unit is exposed through the transparent cover sheet in a self-developing camera and then from the camera through the pressure of a couple Links formed gap deducted. The pressure-exerting members split the container, whereby the developing liquid and opacifying agent are distributed over the negative part of the recording unit and make it light-insensitive. The developing liquid develops each one

S09820 / 07Ö?

28A8A5S

of the silver halide emulsion layers, as a result of the Development image dyes are generated which diffuse into the image receiving layer, with the generation of a positive, right-side recognizable image that can be viewed through the transparent support on the opaque reflective layer can. For further details, reference is made to the aforementioned BE-PS 757 959.

Further advantageous recording materials with an integrated image receiving layer, for their production the described New color formers can be used, for example from US Pat. Nos. 3,415,644, 3,415,645, 3,415,646, 3,647,437 and 3 635 707 known. In the case of most of these recording materials there is a photosensitive silver halide emulsion layer on an opaque support and an image receiving layer is on a separate transparent support arranged, which is applied to the layer furthest from the opaque support. Advantageously, are on the transparent support further a neutralizing layer and a control layer arranged below the image receiving layer.

A recording material according to the invention can also be used, for example, in the context of an image reversal process, as is known, for example, from GB-PS 904 364, page 19, lines 1 to 41. In this case, the color formers are used in combination with physical development nuclei in a seed layer adjacent to the photosensitive negative silver halide emulsion layer. Furthermore tnthält the recording material or the recording unit is a silver halide solvent, preferably in a splittable container with the alkaline processing liquid.

A recording material according to the invention or one according to the invention Recording unit can be used to produce

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2849455

positive monochrome or multicolored images. In the case of a three-color system, each silver halide emulsion layer is a color former or a dye assigned releasing compound that is capable of releasing a dye that has a predominant spectral absorption has within the range of the visible spectrum, in contrast to the corresponding silver halide emulsion layer is sensitive. This means that the blue-sensitive silver halide emulsion layer has a yellow or a yellow dye-providing color former, the green-sensitive silver halide emulsion layer is assigned a magenta or magenta dye-providing color former, and the red-sensitive silver halide emulsion layer a cyan or a cyan dye-supplying color former is assigned, the one yellow dye supplying color former consists of a color former of the formula I given. The individual color formers or dyes Releasing compounds can be in the silver halide emulsion layers themselves or in layers attached thereto be housed.

The optimum concentration of color former in the individual case can vary, depending on the concentration used in the individual case special connection and the desired results. For example, the color formers used according to the invention present in the form of layers that have been produced starting from coating solutions or coating compounds, which for example 0.5 to 8% by weight of color former distributed in a hydrophilic film-forming naturally occurring or synthetic polymer, e.g. gelatin, polyvinyl alcohol and the like, forming a layer which is permeable to aqueous alkaline developing liquids.

For the development of the recording materials according to the invention Various conventionally known silver halide developing agents can be used so long as the & becomes one Oxidation of the color former or releasing image dyes

909020/0707

Connections are enabled. The developer compounds can be accommodated in the recording material itself in which case they are activated by an alkaline developing liquid. Typical developer compounds which can be used, for example, to develop recording materials according to the invention are:

N-methylaminophenol

1-phenyl-3-pyrazolidone

1-phenyl-4,4-dimethyl-3-pyrazolidone

Aminophenols

1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone

N, N-diethyl-ε-phenylenediamine N, N, N ¹ , N'-tetramethyl-p-phenylenediamine

3-methyl-N, N-diethyl-p_-phenylenediamine and 3-methoxy-N-ethyl-N-ethoxy-p_-phenylenediamine.

Preferably, the non-chromogenic developer compounds are used, since they pose a risk of discoloration the image receiving layer is avoided.

When developing a recording material according to the invention, the silver halide developing agent is used in advantageously, during development, silver halide oxidizes and reduces to metallic silver. The oxidized developing agent then in turn oxidizes the color former. That The reaction product of the oxidation process is then subjected to alkaline hydrolysis, whereupon the hydrous compound in image-wise distribution releases diffusible azo dye, which then diffuses into the image receiving layer to form a dye image. The diffusible compound is transferable in alkaline developing liquids due to their own diffusibility or by binding one or more solubilizing residues, for example carboxy, sulfonamide, hydroxyl or Morpholino residues.

909820/0707

Customary known negative-working or direct ones are suitable for the production of recording materials according to the invention positive silver halide emulsions. When using direct positive silver halide emulsions, for example so-called internal image emulsions, as they are used in the context of internal image reversal processes or when using veiled, direct positive emulsions, for example solarizing emulsions, in the unexposed areas are developable, positive images are obtained in the image dye-receiving layer in those cases in which the image dye is released as a direct result of the development process. After the recording material or the recording unit has been exposed, the alkaline developing liquid penetrates the various layers, introducing the Development of the exposed photosensitive silver halide emulsion layers. Those in the recording material or the The developer compound present in the recording unit then develops each of the silver halide emulsion layers in the non- exposed areas, since the silver halide emulsion layers are direct positive layers, whereby the developing agent is oxidized imagewise, corresponding to the unexposed areas of the direct positive silver halide emulsion layers. The oxidized developer compound then oxidizes the color formers, whereupon the oxidized color formers undergo a base-catalized reaction imagewise release of dyes as a result of imagewise exposure of the silver halide emulsion layers. At least some of the diffusible dyes released in imagewise distribution then diffuses into the image-receiving layer creating a positive image of the original. After sufficient contact with the alkaline developing liquid, a pH-reducing layer of the recording material or of an image-receiving element advantageously ensures that the pH of the recording material or of the image-receiving element is stabilized of the produced image is reduced.

909820/0707

Internal image silver halide emulsions suitable for the production of recording materials according to the invention are, for example known from the reference "Research Disclosure", November 1976, pages 76 to 79.

In the case of a multilayer color photographic recording material according to the invention, the individual silver halide emulsion layers can be arranged on a support in the usual order. That is, the blue-sensitive silver halide emulsion layer is the first layer with respect to the exposure side, followed by the green-sensitive layer and the red-sensitive layer. Optionally, a yellow dye layer or a yellow colloidal silver layer may be present between the blue-sensitive layer and the green-sensitive layer to filter out or absorb blue radiation that may have passed through the blue-sensitive silver halide emulsion layer. If necessary, however, the selectively sensitized silver halide emulsion layers can also be arranged in a different order on the support. For example, the blue-sensitive silver halide emulsion layer can be the first layer with respect to the exposure side, followed by the red-sensitive layer and the green-sensitive layer.

For producing inventive Aufzeichnungsaaterialien or recording units with splittable containers commonly known splittable container can be used wi · si · example, from the US Patent 2,543,181, 2,643,886, 2,653,732, 2,723,051, 3,056,492, 3,056,491 and 3,152,515 are known.

The use of a pH-reducing substance in the recording material or the recording unit increases the stability of the transferred image. In an advantageous manner, the substance reducing the pH brings about a reduction in the pH in the image layer from about 13 or 14 to at least 11, preferably to 5 to 8, within a short period of time

909820/0707

after soaking up the developing liquid. Suitable substances and their mode of action are, for example, from the magazine Research Disclosure, July 1974, pages 22-23 and July 1975, pages 35-37.

In an advantageous manner, a so-called control layer or inert spacer layer can also be arranged over the layer reducing the pH value, which controls the pH value reduction, namely as a function of the speed, with the alkali diffuses through this inert layer. Examples of such control layers and how they work can also be found in the "Research Disclosure" reference already cited.

Commonly known aqueous solutions of alkaline compounds can be used as the alkaline developing liquids for developing recording materials according to the invention e.g. solutions of alkali metal hydroxides or alkali metal carbonates, e.g. sodium hydroxide, sodium carbonate or of amines, e.g. diethylamine, preferably with a pH above 11, the developing solutions preferably being a Developer compound included. Suitable alkaline developing liquids and substances for their preparation are known, for example, from the literature reference "Research Disclosure", November 1976, pages 79 and 80.

If a recording material according to the invention or a recording unit according to the invention contains one for alkaline Solutions permeable, practically opaque, light-reflecting layer, this can have a composition as it is customary is used in corresponding known recording materials and is described in more detail, for example, in the journal "Research Disclosure", November 1976, page 82.

For the production of the recording materials according to the invention and recording units can also use conventional

909020/0707

Known support can be used, which are correspondingly dimensionally stable. Typical known flexible substrate materials for the production of recording materials according to the invention are described in more detail, for example Research Disclosure, Nov. 1976, page 85.

The terms "non-diffusible" and "non-diffusible" are used herein in their usual photographic sense used, i.e. these terms denote compounds that do not work in practice in the presence of an alkaline medium migrate or diffuse through organic colloid layers of a photographic material, preferably then not when the recording materials are developed in a medium with a pH of 11 or above. The same applies to the term "immobile". In contrast, “diffusible” compounds include compounds to understand which have the property of being effective through the colloid layers of photographic materials in the presence of a alkaline medium in the presence of "non-diffusible" compounds to diffuse. The term "mobile" has the same meaning.

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

First, the production of color formers which can be used according to the invention will be described in more detail.

- 59 -

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2848435

Production example 1

Synthesis of compound 1 of Table I a

OH

Under a nitrogen atmosphere, 1.80 g (5 mmoles) of 2-chloro-4- (4-fluorosulfonylphenylazo) -6-nitrophenol were added to a slurry of 3.0 g of ground sodium carbonate in 25 ml of dry dimethyl sulfoxide, whereupon 2.55 g ( 5.2 «moles) of 4-amino-N- / ~ 4-di-t-pentylphenoxy) butyl_7-1-hydroxy-2-naphthamide were added. The reaction mixture was heated to 90 ⁰ C. After a reaction time of 2 hours, a further 3.0 g of ground sodium carbonate were added, whereupon the reaction mixture was stirred ^{at 90 ° C. overnight.} After cooling to room temperature, the reaction mixture was poured onto a mixture of ice and hydrochloric acid, whereupon a green precipitate separated out, which was filtered off, washed with water and then air-dried. The isolated precipitate was then dissolved in 80 ml of tetrahydrofuran and a slurry was prepared by adding anhydrous magnesium sulfate. This was filtered, whereupon the filtrate was poured into 800 ml of hexane. The deposited precipitate was filtered off, washed with hexane and air-dried. The yield of reaction product was 2.73 g, corresponding to 66 % of theory.

909820/0707

2SAS45S

The dye was then purified on a chromatography column using 70 ml of chloroform and silica gel. A first component was first removed by eluting with 10 % hexane in chloroform. The purified product was then obtained by eluting with chloroform. It had a melting point of 148 to 150 ^° C. The extinction coefficient, e, was 3.22 χ 10 ⁴ .

Establishing the intermediate connections :

4-Amino-N - / "4- (2,4-di-t-pentylphenoxy) -butyl_7-1-hydroxy-2-naphthamide

1-Hydroxy-N- ^ ~ 4- (2,4-di-t -pentylphenoxy) -butyl_7-2-naphthamide was treated with diazotized p-anisidine (e.g.

^ VN ®Cl ^e )

coupled. The azo group of the compound produced was then reduced to the corresponding amine _{with sodium dithionite (Na 2 SO.).}

2-chloro-4- (4-fluorosulfonylphenylazo) -6-nitrophenol

7.5 g (23 Amole) solid 2-chloro-4- (4-fluorosulphonylphenylazo) phenol were quickly added under vigorous stirring to a mixture of 15 ml concentrated nitric acid and 15 ml of concentrated sulfuric acid, cooled to -30 ⁰ C. After stirring for 13 minutes, the reaction mixture was poured onto 400 ml of ice water with vigorous stirring. The deposited precipitate was filtered off and washed with water. When the precipitate was dried on a funnel, the solid mass became soft and tarry. After the tarry components had been dissolved in acetic acid and carefully and slowly diluted with water, a fine precipitate separated out and was filtered off. This procedure was repeated with the filtrate until the precipitate obtained was no longer solid

909820/0707

Mass farewell. The combined solids were then air dried. The yield was 3.1 g, corresponding to 37 l of theory. The melting point of the compound obtained was 129 to 133 ^° C.

2-chloro-4- (4-fluorosulfonylphenylazo) phenol

17.5 g (0.1 mole) of sulfanilyl fluoride was dissolved in 75 ml of a warm methanol solution saturated with HCl, and the resulting solution was cooled in a methanol-ice bath. 7.0 g (0.1 mol) of sodium nitrite dissolved in 25 ml of water were then added dropwise, whereupon the solution was stirred for a further 5 minutes. The diazonium salt solution was then added dropwise to a solution, cooled in an ice bath, of 12.8 g (0.099 moles) of o-chlorophenol in 150 ml of pyridine. The reaction mixture was then stirred for an additional 15 minutes after which it was poured onto an ice-hydrochloric acid mixture. The deposited precipitate was filtered off, washed with water and air-dried. The yield was 20.0 g, corresponding to 64 % of theory. The melting point of the compound was 133 to 134 ^° C.

Production example 2

Synthesis of compound 2 of Table I a OH

CONH (CH ₂ )

NHSO

90 9820/0707

The compound was prepared according to the procedure described in Example 1 from 2-chloro-6-cyano-4- (3-fluorosulfonylphenylazo) phenyl acetate. The crude brown reaction product was purified using a chromatography column. It was fed into a silica gel column in chloroform, the individual components being separated from one another with 5% acetone in chloroform. The purified dye was eluted with acetone. The yield of reaction product after evaporation of the solvent was 17 %. The melting point of the compound was 183 to 186 ° C. e »3.1 χ 10 ⁴ .

Preparation of the intermediate compounds: 2-chloro-6-cyano-4- (3-fluorosulfonylphenylazo) phenyl acetate

22.5 g (0.063 moles) of 3-chloro-5- (3-fluorosulfonylphenylazo) -2-hydroxybenzaldehyde oxime were added to 150 ml of acetic anhydride, followed by heating to 95 ° C. Then 3.0 g of sodium acetate was added. After 2 1/2 hours the reaction mixture was poured into 750 ml of water and the whole was stirred at room temperature until the anhydride was completely hydrolyzed. The deposited precipitate was filtered off. The filtered solid became rubbery on standing. It was dissolved in 75 ml of chloroform, and the solution was placed on a silica gel column. Eluting with 10 % hexane in chloroform gave the desired dye as the first component. After removal of the solvents under reduced pressure, an oil was obtained which solidified on standing but did not crystallize. The yield of reaction product was 16.8 g, corresponding to 70 % of theory.

3TChIQr-S- (3-fluorosulfonylphenylazo) -2-hydroxy-benzaldehyde oxime

23.8 g (0.07 moles) of 3-chloro-5- (3-fluorosulfonylphenylazo) -2-hydroxy-benzaldehyde were added to 250 ml of ethanol, whereupon 5.04 g (0.072 moles) of hydroxylamine hydrochloride as well

909820/0707

2.88 g (0.072 moles) of sodium hydroxide was added. The reaction mixture was then heated to reflux temperature for 30 minutes after which time it was allowed to cool to room temperature. The mixture was then poured onto a mixture of ice and hydrochloric acid, whereupon a precipitate separated out, which was filtered off, washed with water and dried in a vacuum oven at 55 ° C. The yield of reaction product was 22.5 g, corresponding to 90 % of theory.

3- chloro-5- (3-fluorosulfonylphenylazo) -2-hydroxybenzaldehyde

21.1 g (0.099 mole) m-Aminobenzolsulfonylfluoridhydrochlorid was dissolved in 300 ml of a hot 10 iigen slurried hydrochloric acid solution and then cooled to 0 ⁰ C. Further, 7.0 g (0.1 mole) of sodium nitrite was dissolved in 30 ml of water, and the solution was added dropwise to the acidic solution. In order to avoid coagulation of the slurry, it was necessary to stir vigorously. The diazonium slurry was then slowly added at ⁰ ° C. to 500 ml of pyridine containing 16.0 g (0.10 moles) of 3-chloro-2-hydroxybenzaldehyde. The mixture was then stirred for 30 minutes and then slowly added to 1500 ml of a mixture of ice and hydrochloric acid. The precipitate obtained coagulated to form a lump. The supernatant liquid was decanted off, whereupon the lumpy, tarry solid mass was crushed and slurried in a 50% HCl solution. The solid mass was then filtered off, washed with water and air dried. 21.1 g of reaction product were obtained. After standing for 72 hours, another 2.8 g of reaction product were obtained from the decanted solution. The overall yield was 23.9 g, corresponding to 70 % of theory.

- 64 -

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m-aminobenzene sulfonyl fluoride hydrochloride

41.0 g (0.20 moles) of m-nitrobenzenesulfonyl fluoride was dissolved in 200 ml of dry tetrahydrofuran and a palladium-carbon catalyst was added. The mixture was then shaken under hydrogen for 6 hours at room temperature. It was then filtered and the solvent was removed under reduced pressure. An oil was left behind. This was dissolved in benzene, through which dry hydrogen chloride gas was bubbled. The precipitate was filtered off, washed with additional benzene and dried in a vacuum oven at 55 ⁰ C. The yield of reaction product was 42.1 g, corresponding to 100 % of theory. The melting point of the compound was 198 to 199 ° C.

3-chloro-2-hydroxybenzaldehyde

A sodium hydroxide solution of 266 g sodium hydroxide (6 _S 65 moles) in 1000 »1 of water was placed in a 3000 ml round-bottomed flask equipped with a mechanical stirrer" dropping funnel (250 ml) and reflux condenser. The solution was heated to 60 ° C. Then, 126 g (98 moles O _s) o_-chlorophenol "added which dissolved quickly. Now 262 grams of chloroform (2.20 moles) was slowly introduced over a period of one hour. After stirring at 60 ^° C. for a further 2 hours, the temperature was ^{increased to 80 °} C. for 16 hours. The excess chloroform was then distilled off, whereupon the reaction mixture was acidified by adding 6N sulfuric acid. The mixture was then subjected to steam distillation. 6 liters of the distillate were then extracted with ether, whereupon the resulting ethereal solution over MgSO. was dried. The slurry was then filtered and the solvent was distilled off under reduced pressure. A yellow oil was obtained which consisted of the desired reaction product and 3-chloro-4-hydroxybenzaldehyde. The oil was then poured into 500 ml of hexane with vigorous stirring, a white precipitate of 3-chloro-4-hydroxy-

909820/0707

benzaldehyde farewell. The yield was 8 %. The hexane filtrate was evaporated under reduced pressure, leaving behind an oil which crystallized out after standing for 24 hours at room temperature. The yield of 3-chloro-2-hydroxybenzaldehyde was 8.01 g, corresponding to 5 % of theory. The melting point of the compound was 51 to 53 ° C.

Absorption and light stability of dyes released from compounds in Table 1 a and II a

Each of the dyes was placed in a viscous solution so that viscous solutions containing per liter: 5 × 10 ^-3 moles of dye /, 20 g of sodium hydroxide (0.5 M) and 30 g of hydroxyethyl cellulose.

The solutions were then spread between a polyester film coversheet and an image receiving element. The image receiving element consisted of a polyester backing with a layer of a mixture applied thereon Gelatine and a mordant, consisting of a copolymer of styrene, N-vinylbenzyl-N-benzyl-NjN-dimethylammonium sulfate and divinylbenzene. Gelatine and copolymer were each coated at a thickness of 2.2 g / m 2 applied in the form of a latex to the polyester layer support.

Each from the cover sheet, the viscous dye solution and the receiving element was then sandwiched through guided the gap formed by a pair of pressure-exerting members, which was so large that the dye solutions in one Layer thicknesses of 0.1, 0.2 or 0.4 ym were distributed. To After a transfer time of 2 minutes, the image-receiving elements were peeled off, washed and dried. Measurements of the The pH on the surface indicated that the final pH was about 8. Thus, in each case, there were three image traps that allow a choice of 3 densities. One of these was used for performing fade tests and for a spectrum analysis is used.

909020/0 7 07

The following Table III gives absorptions and light stability data of the compounds of Table I a Released dyes · Table IV gives the corresponding data for the dyes, those of compounds of Table II a were released. In Table III, Z stands for the proportion of the carrier component, which is after the dye its split remained.

The hue of the dyes results from the wavelength of the maximum optical density (λ) of the absorption spectrum and the "half bandwidth" (1/2 BB), which is the width of the spectrumb
represents.

maximum optical density (λ) of the absorption spectrum

[1/2
Spectrum band at half the density of the peak at λ

The light stability was determined by exposing the specimens to simulated average northern daylight. The test duration was 21 days. A high-intensity 6000 W xenon arc lamp unit was used, with which the test specimens were exposed to 528 U lux at 21 ° C. and 45% relative humidity. The optical density was measured at X _m _. both before (D) and after

Πια Λ Ο

(D) exposure.

- 67 -

Π 0 9 8 2 0/0 7 0 7

Dye of
Connection no. Rest of trag. Table III 118 1.06 Light stability
D D loss 0.20 1 4-SO ₂ NH ₂ absorption
Xmax 1/2 BB
(nm) (nm) 143 ⁺ 1.55 0.86 0.04 2 3-SO ₂ NHCOCH ₃ 424 117 0.93 1.51 0.12 3, 8, 9 3-SO ₂ NH ₂ 440 109 1.48 0.81 0.12 4th 5-SO ₂ NH ₂ 418 100
107 1.73
1.51 1.36 0.22
0.17 CCt 6th
7th 3-SO ₂ NH ₂
3-SO ₂ NH ₂ 446 1.51
1.34 ! 0982 11 3.5 - / - SO ₂ NHSCH ₂ ) ₃ 437
439 116 1.88 0.40 ο SO ₂ NH ₂ I ₂ 101 1.22 1.48 0.09 O 12th 4-SO ₂ NH ₂ 442 95 1.86 1.13 0.13 -a 13th 3-SO ₂ NH ₂ 461 1.73 14th 4-SO ₂ NH- ^ C ₆ H ₄ - 454 > 150 ⁺⁺ 1.31 0.07 SO, NH-
in the M 109 1.70 1.24 0.11 15th 5-SO ₂ NH ₂ 441 145 ⁺⁺ 1.85 1.59 0.23 21st 4-SO ₂ NH ₂ 443 1.62 4 20

There was a secondary absorption peak in the ultraviolet range that did not affect the visible hue, however the 1/2 BB affected.

Determined by extrapolating part of the absorption curve below 400 nm

Table IV 1/2 BB Light stability D. Density loss dye Absorption (un-
blocked color
material ^D o 1.17 0.35 No. Max (nm) 109 1.52 0.78 0.08 116 0.86 0.84 0.11 1 452 103 0.95 1.28 0.05 2 456 100 1.33 0.93 0.09 3 446 107 1.02 0.79 0.07 4th 438 105 0.86 link No. 2) 5 444 dye from 1.71 0.29 6th 447 > 150 ⁺ 2.00 1.74 0.23 7 (see Table III, 11O ⁺ 1.97 1.52 0.10 8th 418 101 1.62 1.56 0.20 9 386 > 1S0 ⁺ 1.76 1.06 0.17 11 440 108 1.23 12th 383 13th 440

Determined by extrapolating part of the absorption curve below 400 nm

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example 1

It became a multicolor photosensitive material with an integrated image receiving layer produced in that the layers listed below in the specified order on a transparent polyethylene terephthalate) film backings were applied. The numerical values given in brackets relate in each case, provided nothing else is stated on g / m.

1. An image-receiving layer made from a latex made from a copolymer from styrene, N-vinylbenzyl-N-benzyl-N-benzyl-N, N-dimethylammonium sulfate and divinylbenzene (2.2) and gelatin (1.1);

2. a reflective layer of titanium dioxide (16) and gelatin (2,6);

3. an opaque layer of carbon black (1.9) and gelatin (3.3);

4. a layer containing the cyan dye releasing compound (0.59) of the following formula:

OH

C ₂ H ₅
CONHCIUCH-O— (' ^)

^C 15 ^H 31 SO. » CH,

OH

and gelatin (1,1);

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5. A red sensitive, internal direct positive image gelatin silver bromide emulsion (1.3 silver and 1.3 gelatin), 16 g of potassium Z-octadecylhydroquinone-S-sulfonate per mole of silver and 3.8 mg of the nucleating agent i-p-formylhydrazinophenyl-3-phenyl-2-thiourea per mole of silver;

6. an intermediate layer of gelatin (1,6) and 2,5-di-sec-dodecylhydroquinone (1.3);

7. a layer of a magenta dye releasing agent Compound (0.54) of the following formula:

CONH (CH ₂ ) ₄ 0- (S.

SO ₉ NHC (CH,)

L J

OH

and gelatin (1,2);

8. A green sensitive, internal direct positive image gelatin silver bromide emulsion (1.25 silver and 1.3 gelatin), 16 g potassium - ^ - octadecylhydroquinone-S-sulfonate per mole of silver and 34 mg of the nucleating agent 1-acetyl-2 {4- / 5-amino-2- (2,4-di-tpentylphenoxy) benzamido_7phenyl} hydrazine per mole of silver and 2.7 mg of i-forinylhydrazinophenyl-S-phenyl ^ -thiourea per MeI silver;

9. an intermediate layer of gelatin (1,6) and 2,5-di-sec-dodecylhydroquinone (1.3);

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10. a layer of yellow dye releasing compound 22 (0.65) of the following formula:

and gelatin (1.45);

11. a blue-sensitive inner image gelatin silver bromide emulsion (1.25 silver and 1.3 gelatin), 16 g of Kalin '"' 2-octadecylhydroquinone-2-sulfonate per mole of silver and 24 mg of the nucleating agent 1-acetyl-2- {4- / ~ 5-amino-2- (2,4-di-tpentylphenoxy) benzamido_7phenyljhydrazine per mole of silver and the nucleating agent i-p-formylhydrazinophenyl-3-phenyl-2-thiourea per mole of silver;

12. a top layer of gelatin (0.9) and 2,5-didodeceylhydroquinone (0.11).

The recording material produced was then exposed through a multicolored test object with graduated density levels by means of a tungsten lamp. The recording material was developed by forming a "sandwich" from the recording material, a splittable container with developing liquid and a cover sheet, which was passed through the gap formed by two pressure-exerting members. The temperature during development was 23 ^° C. The developing liquid and the cover sheet were off

909820/0707

Example 2 of U.S. Patent Application Serial No. 6 76 947 known composition.

After about 3 hours, sensitometric curves were recorded using a reflection densitometer. The following results were obtained:

Maximum density minimum density Red Green Blue Red Green Blue

2.10 2.16 2.27 0.20 0.24 0.30

Production example 3

3-chloro-2-hydroxy-5- (4-sulphamoylphenylazo) benzamidoacetic acid (Dye 1 of Table II)

CONHCH ₂ CO ₂ H

NN- (' V ^ -SO ₂ NH ₂

(A) Ethyl 2- (3-chloro-2-hydroxybenza »ido) acetate

1.1 g (11 mmol) of glycine ethyl ester were dissolved in 10 K of dry tetrahydrofuran with stirring at room temperature. Then 1.0 g (1/2 moles) of S-chlorosalicyloyl chloride dissolved in 5 ml added dropwise to dry tetrahydrofuran. A precipitate of glycine ester hydrochloride separated out almost immediately. After one hour the mixture was poured onto a mixture of ice water (50 ml) and concentrated HCl (2 ml). The oily suspension obtained soon solidified into a thick, white solid mass. This was filtered off, washed and recrystallized from aqueous ethanol. That

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28A8A55

The reaction product was obtained in a yield of 1.15 g, corresponding to 88 % of theory. The melting point of the compound was 103 ^° C.

C ₁₁ H ₁₂ ClNO ₄ Calculated: C, 51.26; FI: 4.66; N: 5.44 Found: C: 51.38; H: 4.54; N: 5.28 I.

(B) 3-chloro-2-hydroxybenzamidoacetic acid

0.8 g (3 mmol) of ethyl 2- (3-chloro-2-hydroxybenzaraido) acetate were added to 25 ml of a 10% NaOH solution at room temperature, whereupon the mixture was stirred for one hour, during which time it was dissolved. The solution was then acidified with concentrated HCl, whereupon the desired compound precipitated. This was separated off, washed and recrystallized from aqueous ethanol. The yield of the reaction product was 0.6 g corresponding to 85% of the Theorie.Der melting point of the compound was 178 ⁰ C.

C ₉ H ₈ ClNO ₄ Calculated: C: 47.06; H: 3.49; N: 6.10; Cl: 15.47 Found: C: 46.59; H: 3.47; N: 6.24; Cl: 15.68 %

(C) Dye 1 of Table II

0.34 g (2 mmol) of 4-aminobenzenesulphonamide were dissolved in 5 ml of a 3N hydrochloric acid solution, whereupon the solution was cooled to ^{0 ° C.} Then 0.15 g (2.2 mmol) of sodium nitrite was dissolved in 2 ml of water, and this solution was added dropwise to the solution prepared first. The resulting solution was then stirred for a further 30 minutes at ⁰ ° C., after which 0.1 g of urea was added to decompose excess nitrous acid.

0.46 g (2 mmoles) of 3-chloro-2-hydroxybenzamidoacetic acid were dissolved in 10 ml of water containing 0.09 g (4.5 mmoles) of sodium hydroxide and 5 g of ammonium acetate . The solution then became

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28A8455

^{cooled to 0} ° C., whereupon the diazonium salt solution was added dropwise with stirring. The mixture was then stirred for a further hour at 0 to 5 ^° C. and then acidified by adding dilute hydrochloric acid. The precipitated dye was filtered off and recrystallized from aqueous acetic acid. The dye was obtained in a yield of 0.5 g, corresponding to 60 liters of theory. The melting point was 28O ⁰ C. λ (cationic mordant)

Iu el Jw

454 no.

C ₁₅ H ₁₃ ClN ₄ O ₅ S Calculated: C, 43.64; H: 3.15; Cl: 8.61; N: 13.58;

S: 7.78

Found: C: 43.45; H: 3.12; Cl: 8.53; N: 13.62;

S: 7.66 %

Production example 4

3-chloro-2-hydroxy-5- (3-sulphamoylphenylazo) benzamidoacetic acid (Dye 2 from Table II)

CONHCH ₂ CO ₂ H

.SO ₂ NH ₂

The diazonium salt of 3-aminobenzenesulphonamide was reacted with 3-chloro-2-hydroxybenzamidoacetic acid in the manner described in Example 3. The dye was obtained in a yield of 75 \. The melting point was 227 ° C.

λ (cationic mordant): 436 nm.

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28A8A55

_1n H ₁ ^ ClIf ₁ (KS Calculated: C: 43.64; H: 3.15; Cl: 8.61; N: 13.58;

S: 7.78

Found: C: 43.55; H: 3.31; Cl: 8.50; N: 13.45;

S: 7.40 %

Production example 5

4- / ~ 3-chloro-4-hydroxy-5- (4-sulphamoylphenylcarbamoyl) phenyl azo / benzoic acid (dye 5 from Table II)

(A) 3-chloro-N- (4-sulphamoy! Phenyl) salicylamide)

1.8 g (10.5 mmol) of 4-aminobenzenesulphonamide were in 25 ml dissolved in dry tetrahydrofuran containing 1.33 g (11 mmoles) of dimethylaniline. With stirring became the solution at room temperature 2 g (10.5 mmol) of S-chlorosalicyloyl chloride, dissolved in 10 ml of dry tetrahydrofuran was added. After 2 hours the mixture was added to 200 ml of water with a Content of 5 ml of concentrated HCl given.

The deposited precipitate was filtered off and recrystallized from aqueous dimethylformamide. The yield of reaction product was 1.72 g, corresponding to 91 % of theory. The melting point of the compound was 246 to 248 ^° C.

O ₄ S Calculated: C: 47.78; H: 3.37; Cl: 10.87; N: 8.58;

S: 9.8

Found: C: 48.02; H: 3.51; Cl: 10.73; N: 8.50;

S: 9.82 %

909820/0 7 07

(B) Dye 5 of Table II

This dye was made from the diazonium salt of 4-aminobenzoic acid and 3-chloro-N- (4-sulphamoylphenyl) salicylamide, respectively the procedure given in Example 3, Part (C), with the exception, however, that the Kujjiungsf eaktion was carried out in pure pyridine and not in sodium hydroxide. The pyridine solution of the dye was diluted in with ice Given HCl.

The reaction product was recrystallized three times from aqueous dimethylformamide. The compound was obtained in 40% yield. The melting point of the compound was above 300 ^° C. (dec).

λ (cationic mordant): 420 nm.

^(: 2O ^H 15 ^ClN 4 ^O 6 ^{S Calculated: C:} 50.58; H: 3.16; Cl: 7.48; N: 11.80 Found: C: 50.40; H: 3.31; Cl : 7.80; N: 11.94.

Production example 6

3-chloro-N- (4-sulphonamidophenyl) -5- (4-sulphonamidophenylazo) - salicylamide (dye 6 from Table II)

N-N

SO NH

it £

SO ₂ NH ₂

The dye was prepared by reacting the diazonium salt of 4-alinobenzene sulphonamide with 3-chloro-N- (4-sulphamoylphenyl) salicylamide in the manner described in Example 5

909620/0707

The reaction product obtained was recrystallized from aqueous dimethylformamide. The yield of reaction product was 64 I. The melting point of the compound was above 300 ^° C.

λ (cationic mordant): 433 nm.

C ₁₉ H ₁₆ ClN ₅ O ₆ S ^ Calculated: C: 44.75; H: 3.14; N: 13.74; S: 12.56

Found: C: 44.92; H: 3.29; N: 13.69; S: 12.55 %,

Production example 7

3-chloro-5- {4- / 3- (2,4-di-t-pentylphenyloxytetramethylenecarbamoylj- ^ l-hydroxynaphth-1-ylsulphamoyl 7 phen ylazo} -2- hydroxybenzamidoacetic acid (Compound 1 of Table I)

OH

Cl. I ^ ^ ONfICH ₂ CO ₂ H

COiNH (CH,), 0

SO ₂ NH (/ X) OH

(A) 3-chloro-2-hydroxy-5- (4- fluorosulphonylphenylazo) benzamide) acetic acid

3 g (17 mmol) of 4-aminobenzenesulphonyl fluoride were obtained by means of a mixture of 5 ml of concentrated HCl and 20 ml of ethanol and a sodium nitrite solution of 1.2 g of sodium nitrite (15 mmol) in 5 ml of water.

The resulting solution was then added dropwise to a solution of 3-chloro-2-hydroxybenzamidoacetic acid from part (B) of Example 3 (3.8 g, 17 mmoles) in 100 ml of water containing

gnqg ') Γ) / 070?

of 1.5 g (35 mmol) of sodium hydroxide and 10 g of ammonium acetate added at Ü ° C with stirring. After one hour, the precipitated reaction product was filtered off, washed and recrystallized twice from acetic acid. The reaction product was in a yield of 4.0 g, corresponding to 58 l of Theory received. The melting point of the compound was 237 C.

C ₁₅ II _n ClFN ₅ O ₀ S Calculated: C: 13.32; H: 2.65; N: 10.11;

Cl: 8.51; S: 7.70

Found: C: 43.25; H: 2.70; N: 9.96;

Cl: 8, H); S: 7.9 7 %.

(ü) Compound I of Table I.

^ f II K (-9 niMole) sodium bicarbonate were added to 20 ml of dry, degassed methyl sulphoxide at 90 ° C. under a nitrogen atmosphere and with stirring over a period of 15 minutes. Now 2.36 g (5 mmol) of 1 - [(Z, \ - I) i-tert. -amylphenoxy) -n-butylcarbamoyl} -4-aniino-I-naphthol was added, whereupon the mixture was heated for a further 15 minutes. Thereupon 2 g (5 mmoles) of 3-chloro-2-hydroxy-5- (1-fluorosulphonylphenylazo) benzamidoacetic acid were added all at once, and heating was continued until it was determined by a thin chromatography analysis that that the implementation was finished.

After the resulting red solution had been cooled, it was added to 200 ml with up to dilute HCl, whereupon the precipitated reaction product was filtered off and washed with water. The reaction product was then taken up in 50 ml of ethyl acetate and washed three times with water. The organic phase was then dried over anhydrous magnesium sulfate and the solvent was evaporated. A light brown semi-solid mass was obtained. A small amount of the compound obtained was then triturated with ether, whereby Compound 1 was obtained in the form of an orange-colored solid. The yield of reaction product was 2 g, corresponding to SO I the

909-20 / 0701

Theory. The melting point was 230 to 235 ° C (dec.) · Never compound softened at 100 ⁰ C.

C ₄₆ H ₅₂ ClN ₅ O ₉ S Calculated: C, 62.3; H: 5.9; N: 7.9; S: 3.0;

Cl: 4.0

Found: C: 61.9; H: 6.3; N: 7.5; S: 3.4; Cl: 3.6 "..

Production example 8 S- (S- / S-N ^ N-didodecylcarbamoyl ^ -hydroxynaphth-i-

ylsulphamoyl / phenyl azo} -2-hydroxybenr.ami des si g acid (Compound 2 of Table I)

CONHCH ₀ CO ₀ H

(A) 3-chloro-2-hydroxy-5- (3-fluorosulphonylphenylazo) benzamidoacetic acid

The diazonium salt of 3-aminobenzenesulphonyl fluoride and 3-chloro-2-hydroxybenzamidoacetic acid, prepared as described in Example 3, Part (B), were reacted in the manner described in Example 7, Part (A). The desired compound was obtained in a 77% yield. The melting point of the compound was 237 ^° C.

909820/0707

₁₅₁₁₃ O ₆ S Calculated: C, 43.32; H: 2.65; Cl: 8.54;

N: 10.11; S: 7.70

Found: C: 42.97; H: 2.69; Cl: 8.42;

N: 9.91; S: 7.50 %.

(B) Compound 2 of Table I.

4.2 g (50 mmol) Natriurabicarbonat were added to 20 ml of dry, degassed dimethylsulphoxide at 105 ⁰ C under a nitrogen atmosphere. After stirring for 15 minutes, 2-70 g (5 mmoles) of 2- (di-n-dodecylcarbamoyl) -4-amino-1-naphthol were added all at once, followed by stirring for a further 10 minutes with heating. Thereupon were all at once 2.08 g (5 mmoles) of 3-chloro-2-hydroxy-5- (3-fluorsulphonylphenylazo) benzamidoessigsäure added and again another 4 hours is heated with stirring at 105 ⁰ C for. After the resulting red-brown solution had cooled, it was added to 200 ml of dilute HCl . The brown precipitate which had separated out was filtered off and then taken up in 50 ml of ethyl acetate. The organic phase was then washed three times with water and dried over anhydrous MgSO _4. The volume was then brought to 500 ml by adding more ethyl acetate. Then 100 g of Florisil (60 to 100 mesh) was added. The mixture was then stirred for 15 minutes during which time the dye deposited on the Florisil. The Florisil was then filtered off and washed with ethyl acetate until the eluent was practically colorless. The Florisil was then extracted three times with a mixture of methanol and 30 % ethyl acetate, making a total volume of 600 ml. The solvent was then removed in vacuo, whereupon the orange-red gummy product that had formed was taken up in 100 ml of ethyl acetate and filtered through a griddle. The ethyl acetate was then removed in vacuo, resulting in a red glass-like mass. This was dissolved in 20 ml of methanol and 5 ml of dimethyl sulphoxide, and the solution was added dropwise to 200 ml of water with 1 ml of concentrated HCl. The orange-colored solid precipitate was filtered off, washed and dried. The yield at

909820/0707

The reaction product was 2.8 g, corresponding to 60 l of theory. C _cn H, _o ClN _c 0 _o S Calculated: C: 64.27; H: 7.28; Cl: 3.43; N: 7.50;

YOU Oo Oo

S: 3.43

Found: C: 64.48; H: 7.45; Cl: 3.53; N: 7.23; S: 3.89 I.

Production example 9

5- {4 - / "3- (2,4-Di-t-pentylphenoxytetramethylenecarbamoyl) -4-hydroxynaphth-1-ylsulphamoyl 7phenylazo} -3-fluoro-2-hydroxy benzamidoacetic acid (Compound 3 of Table I)

CONHCH ₂ CO ₂ H

NN- ('\ SO ₂ NH

CONH (CH ₂ ) ₄ 0 OH

(A) 3-fluoro-2-hydroxybenzamidoacetic acid

10.3 g (100 mmol) of glycine ethyl ester were added with stirring Room temperature dissolved in 50 ml of dry tetrahydrofuran.

To the obtained solution was added dropwise 10.8 g (50 mmol) of acetyl-S-fluorosalicyloyl chloride dissolved in 25 ml of dry Tetrahydrofuran added. A precipitate of glycine ester hydrochloride separated out immediately. After one hour the mixture was poured into a hydrochloric acid solution diluted with ice. The precipitated semi-solid precipitate was separated and treated with 30 ml of a 3N sodium hydroxide solution. After one hour the solution was by the addition of

909820/0707

concentrated hydrochloric acid and chilled in a refrigerator. The reaction product which precipitated out was recrystallized from aqueous ethanol. The yield was 7.3 g, corresponding to 68 % of theory. The melting point of the compound was 205 to 208 ^° C.

C ₉ H ₈ FNO ₄ Calculated: C: 50.70; H: 3.76; F: 8.92; N: 6.57

Found: C: 50.42; H: 3.81; F: 9.27; N: 6.43 %.

(B) 3-fluoro-2-hydroxy-5- (4-fluorosulphonylphenylazo) benzamidoacetic acid

1.65 g (9.4 mmol) of 4-aminobenzenesulphonyl fluoride were with a mixture of 3 ml of concentrated hydrochloric acid, 12 ml of ethanol and 3 ml of a sodium nitrite solution containing 0.7 g Sodium nitrite diazotized. Excess nitrous acid was then destroyed by adding urea.

The resulting diazonium salt solution was then added dropwise at ⁰ ° C. to a solution of 2.0 g of the compound described under (A) and 50 ml of water containing 0.75 g (18.8 mmol) of sodium hydroxide and 10 g of ammonium acetate.

After one hour the solution was concentrated by the addition of Acidified hydrochloric acid, whereupon the reaction product separated and from a mixture of acetic acid, Dimethylformamide and water in a volume ratio of 5: 1: 1 was recrystallized.

The yield of reaction product was 2.8 g, corresponding to 75 % of theory. Mp »245 ^° C (dec).

C ₁₅ II ₁₁ FN ₃ O ₆ S Calculated: C: 45.11; H: 2.76; F: 9.52; N: 10.53

Found: C: 45.30; H: 3.06; F: 10.19; N: 10.67 %.

909820/0707

(C) Compound 3 of Table I.

2.5 g (30 mmol) of sodium bicarbonate were at 95 ° C under a Nitrogen atmosphere in 10 ml of dry, degassed dimethyl sulphoxide stirred in. After 15 minutes there was 2.45 g (5 mmoles) of the 4-aminonaphthol used in Example 7, Part (B) was added all at once while continuing to heat and stir. After 10 minutes, 2.0 g (5 mmoles) of des Dye from part (B) was added all at once, followed by heating again with stirring for an additional 90 minutes. the The cooled solution was then added to 100 ml of a hydrochloric acid solution diluted with ice, whereupon the precipitated light brown solid reaction product was filtered off and washed with water. The crude compound 3 was then added in 30 ml Dissolved ethyl acetate, whereupon the solution was washed three times with 20 ml of water each time. The organic phase was then over Magnesium sulfate dried and evaporated. A semi-solid red-brown mass was left behind. This was stirred with cold ether, whereby Compound 3 was obtained in the form of a yellow powder.

The yield was 1.8 g, corresponding to 41 % of theory. The connection softened at 165 ^° C. The melting point was 210 ^° C.

C ₄₆ H ₅₂ FN ₅ O ₉ S Calculated: C: 63.52; H: 5.98; F: 2.19; N: 8.06;

S: 3.68

Found: C: 63.17; H: 5.72; F: 2.20; N: 7.98;

S: 4.38.

Preparation example 10

3-Bromo-5-4- / ~ 3- (2,4-di-t-pentylphenyloxytetramethylenecarbamoyl) -4-hydroxynaphth-1-ylsulphamoyl-7phenylazo-2-hydroxybenzamidoacetic acid (compound 4 of Table I)

909820/0707

ONHCH ₂ CO ₂ H

NN— (f \ —SO ₂ NH

CONH (CH ₂ ). OH

(A) 3-Bromo-2-hydroxy-5- (4-fluorosulphonylphenylazo) benzamide) acetic acid

The following compounds were reacted with one another according to the procedures described in Example 9 (B):

2.6 g (15 mmol) of p-aminobenzenesulphonyl fluoride 1.2 g (17 raMoles) sodium nitrite

4 g (15 mmoles) of the coupler from Example 1 (B) 1.2 g (30 mmoles) sodium hydroxide

10 g ammonium acetate

The reaction product obtained was recrystallized from aqueous acetic acid.

The yield of reaction product was 4.5 g, corresponding to 67 % of theory. The connection softened at 160 ⁰ C.

215 ^U C (dec).

Calculated: C: 39.13; H: 2.39; Br: 17.39;

N: 9.13; F: 4.13; S: 6.96

Found: C: 38.74; H: 2.30; Br: 17.28;

N: 9.35; F: 4.14; S: 6.72%.

(B) Compound 4 of Table I.

2.0 g (4.3 «moles) of the dye from Part (A) were added 2.2 g (26 mmoles) of sodium bicarbonate and 2.13 g (4.3 mmoles) of des 4-aminonaphtholes of part (B) of Example 7 in a procedure as described in part (C) of Example 9 umge-

909820/0707

puts.

The yield of compound 4 was 2.1 g, corresponding to 53 % of theory.

C ₄₆ H ₅₂ FN ₅ O ₉ S Calculated: C: 59.35; H: 5.59; Br: 8.60; N: 7.53;

S: 3.44

Found: C: 58.44; H: 5.65; Br: 8.35; N: 7.52;

S: 3.67.

Preparation example 11

N- (Benzotriazol-5-yl) -3-Chlor-S-4- / ~ 3- (2,4-di-t-pentylphenoxytetramethylenecarbamoyl) -4-hydroxynaphth-1-ylsulphamoyl 7-phenylazosalicylamide (Compound 5 of Table ΙΊ

^tC 5 ^H 11

N = N

.CONH (CH ₂ ) ₄ 0 OH

I ^C 5 ^H 11

(A) 6- / ~ 3-chloro-2-hydroxy-5- (4-fluorosulphonylphenylazo) -benzamido-1,2,3-benzotriazole

The dye was prepared according to the procedure described in Example 7 manufactured.

(B) Compound 5 of Table I.

3.0 g (36 mmoles) of sodium bicarbonate were suspended with stirring and under a nitrogen atmosphere at 95 to 100 ⁰ C in 30 ml of dry dimethyl sulphoxide. After 15 minutes were in a

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Male 3.1 g (6.3 mmoles) of 2 - {(2,4-di-tert-amylphenoxy) -n-butylcarbamoyl} -4-amino-1-naphthol admitted. After a further 15 minutes, 3 g (6.3 mmol) of the as described above under (A) Dye produced added, whereupon the mixture was stirred under nitrogen until a Thin layer chromatography analysis indicated the completed reaction.

After cooling, the mixture was poured into 300 ml of a hydrochloric acid solution diluted with ice. The precipitated crude reaction product was then filtered off and washed thoroughly with water. The reaction product was then dissolved in ethyl acetate, and the solution was washed three times with water and then dried over anhydrous magnesium sulfate. The solvent was then removed in vacuo and the residual red gummy product was triturated with ether. In this way, the compound was obtained in good purity. The yield of reaction product was 4.8 g, corresponding to 80 % of theory.

C ₅₀ H ₅₃ ClN ₈ OS Calculated: C, 63.53; H: 5.61; Cl: 3.76;

N: 11.86; S: 3.39

Found: C: 62.93; H: 5.91; Cl: 3.43;

N: 11.75; S: 3.34 * ..

Example 2

Proportions of the azo dye releasing compounds 1 and of Table I were in diethyl lauramide in a ratio of Dissolved 1: 1, whereupon the solutions were dispersed in gelatin. The dispersions obtained in this way were then in non-spectrally sensitized, but chemically sensitized silver halide emulsions are incorporated, which are then applied to polyethylene terephthalate film supports were applied in such a way that on a support surface of 1 dm 5.4 χ 10 ~ moles of one Azo dye releasing compound, 9.25 mg of silver and 53.8 mg of gelatin accounted for.

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Sections of the recording materials produced were then imagewise exposed and developed by laminating the recording materials together with image-receiving elements using developing liquids having a pH of 10.3, 11.3 or 13.8. The image-receiving elements contained a layer containing a cationic mordant. The contact times were varied from 2 to 4 minutes. In this way, negative images were formed in the image receiving layers. At all pH values the images showed good density and resolution. D. at a pH value of 10.3 and a pH value of 13.8 it was very low and at a pH value of 12.3 it was only slightly higher. The hues and bandwidths of the image dyes were excellent. In addition, they were extremely stable to the effects of light, heat and the processing chemicals. A fading test lasting 20 days resulted in a maximum degree of fading of 4 %. When the recording materials were stored at comparatively high temperatures, there was no change in the hue of the dyes or in the image density.

The following table shows the composition of the developing liquids used.

pH 13.8 pH 12, G pH 10.3 water 1 liter 1 liter 4-hydroxymethyl-4-methyl- 1 liter G 1-phenyl-3-pyrazolidone 5.0 g 0.2 g NaOH 60.0 g 0.2 G Hydroxyethyl cellulose 28.0 g 24.0 g KBr 5.0 g 20.0 G 5-methylbenzotriazole 1.2 g G 0.1 g t ^ -butylhydroquinone 0.2 g 0.24 K ₃ PO ₄ -H ₂ O 11-aminoundecanoic acid 57.6 4.0 g K ₂ CO ₃ 7.6 30.0 g Benzyl alcohol 10 ml The pH was de by addition of about 7 g NaHCO, a
posed.

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Example 3

It became a multicolor photosensitive material with an integrated image receiving layer produced in that the layers listed below in the specified order on a transparent polyethylene terephthalate) film substrate were applied (the numerical values given in brackets relate, unless nothing

2 otherwise stated, on a coating thickness in g / m):

1. An image-receiving layer made from a latex made from a copolymer from styrene, N-vinylbenzyl-N-benzyl-N.N-dimethylammonium sulfate and divinylbenzene (2.2) and gelatin (1.1);

2. a reflective layer of titanium dioxide (16) and gelatin (2,6);

3. an opaque layer of carbon black (1.9) and gelatin (3.3);

4. a layer with a cyan dye releasing layer Compound (0.59) of the following formula:

SO ₂ CH ₃

SO ₂ NH NN

OH

and gelatin (1,3);

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5. a red sensitive, direct positive gelatin silver bromide emulsion (with 1.35 silver and 1.35 gelatin), 16 g potassium 2-octadecylhydroquinone-2-sulfonate per mole of silver and 20 mg of the nucleating agent 1-acetyl-2- {4- / ~ 5-amino-2- (2,4-di-t-pentylphenoxy) benzamido_7phenyl} hydrazine per mole of silver and 0.47 mg of the nucleating agent 1-p_-formylhydrazinophenyl-3-phenyl-2-thiourea per mole of silver;

6. an intermediate layer of gelatine (1.6) and 2.5-di-sec-dodecy / hydroquinone (1.3);

7. a crimson dye releasing layer Compound (0.54) of the following formula:

)H

CON (nC ₁₈ H ₃₇ ) ₂

CH ₃ SO ₂ NH

SO ₂ NHC

and gelatin (1,2);

8. a green sensitive, direct positive gelatin-silver bromide emulsion layer (with 1.25 silver and 1.3 gelatin), 16 g of potassium 2-ocbdecylhydroquinone-5-sulfonate per mole of silver as well 30 ml of the nucleating agent 1-acetyl-2- {4- ^ ~ 5-amino-2- (2,4-di-tpentylphenoxy) -benzamido_7phenyl} hydrazine per mole of silver and also 0.65 mg of the nucleating agent 1-formylhydrazinophenyl-3-phenyl-2-thiourea per mole of silver;

9. an intermediate layer of gelatin (1,6) and 2,5-di-sec-dodecylhydroquinone (1.3);

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28A8455

10. A layer containing the yellow dye releasing compound 7 according to the invention (0.65) of the following formula

and gelatin (0.86);

11. a blue sensitive gelatin-silver bromide direct positive emulsion layer (with 1.25 silver and 1.3 gelatin), 16 g of potassium 2-octadecylhydroquinone-2-sulfonate per mole Silver and 20 mg of the nucleating agent 1-acetyl-2- {4- / ~ 5-amino-2- (2,4-di-_t-pentylphenoxy) benzamido_7phenyl} hydrazine per mole of silver and 0.56 mg of the nucleating agent 1-p_-formylhydrazinophenyl-3-phenyl-2-thiourea per mole of silver;

12. a top layer of gelatin (0.9).

Two sections of the prepared recording material were then exposed through a multicolored test object with graduated density levels using a tungsten lamp. Based on that exposed material, a splittable container with a developing liquid and a developing cover sheet then a sandwich is formed, which is guided through the gap formed by two superposed pressure-exerting members became. In doing so, the splittable container was split open and the developing liquid contained in it was over the Recording material distributed. The development took place at a temperature of 23 C.

909820/0707

The composition of the developing liquid corresponded to the developing liquid described in Example 9 of BE-PS 853,612. The structure of the cover sheets used with two Control layers corresponded to the structure of the cover sheet described in the same example of the Belgian patent will.

In the case of one recording material, a blue sensitometric D / log Ε curve was recorded after 3 hours by means of a reflection densitometer. The other developed material was incubated in the dark for 14 days at a temperature of 32 ^° C. and a relative humidity of 50%. A blue sensitometric curve was then recorded for this material as well.

The increase in the density of the incubated material above the mean scale point where the original curve had a density of 1.0 is a measure of the diffusion of the dyes into the receiving layer after the actual development process. One excessive diffusion after development results in darkening of the high highlight areas in a color photographic Recording. The blue D / log Ε curve became the post-diffusion of the yellow dye in the recording material was determined. The recording material showed an increase in density of 1.00 before incubation to 1.09 after incubation.

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Claims (1)

H.Bartels
Dipl.-Chem. Dr. Brandes EASTMAN KODAK COMPANY, 343 State Street, Dr.-Ing. Hero Rochester, New York State, United Physics Wolff 8 Munich 22, Thierschstrasse Tel. (089) 293297 Telex 0523325 (patwod) Photographic recording material Telegram address: ° wolffpatent, munich Postal check account Stuttgart 7211 (BLZ 60010070) Deutsche Bank AG, 14/286 (BLZ 60070070) Office hours: 8 a.m. to 12 p.m., 1 p.m. to 4.30 p.m. except saturdays PATENT CLAIMS October 23, 1978: 25/2 \ y. Photographic recording material having a layer support and at least one silver halide emulsion layer applied thereto which contains a non-diffusible color former which is capable of releasing an azo dye which is diffusible under alkaline conditions or which is in contact with a layer containing such a color former, characterized in that the recording material Contains color former of the following formula: Z \) _{N = N} _ / \ —G ^w MT where mean: D an electron withdrawing residue with a Hammettpara sigma value from 0 or greater than 0, preferably between 0 and +1.5; E is an electron withdrawing residue with a Hammettpara sigma value from +0.3 or greater than +0.3, preferably from +0.3 to +1.5; Ö0982Ö / 07Ö7 2148455 G is a hydroxy group or a hydrolyzable precursor group for a hydroxy group; Z to complete an aromatic carbocyclic or heterocyclic nucleus with a or more rings of 5 to 7 atoms required, with the proviso that at least one of the rings has a ballast carrier residue, which under alkaline conditions as a function of the development of the Silver halide emulsion layer or silver halide emulsion layers able to release a diffusible azo dye. Recording material according to Claim 1, characterized in that it contains a color former of the structural formula given, in which D stands for a halogen atom or a nitro, cyano, carboxy, sulfonyl, sulfamoyl, carbamoyl or perfluoroalkyl radical and E stands for a nitro, cyano, carboxy, sulfonyl, sulfamoyl, carbamoyl or a perfluoroalkyl radical. Recording material according to Claim 1, characterized in that it contains a color former of the formula given in which E is a carbamoyl radical of the formula -CON (R \, where R the meaning of a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms, an aryl radical with 6 to 9 carbon atoms or has a heterocyclic ring or is part of the ballast carrier radical, or in which the radicals R together with the nitrogen atom, on which they sit, form a 5- or 6-membered heterocyclic ring. Recording material according to Claim 1, characterized in that it contains a color former of the formula given in which G is a hydrolyzable ester radical of one of the formulas -OCOR, -OCOOR or -OCON (R ¹ ), in which R ^{1 has} the meaning of an alkyl radical 1 to 8 carbon atoms or an aryl radical with 6 to 12 carbon atoms or a radical which, together with the -OCO group, represents the ballast carrier radical. 909820/0707 5. Recording material according to claim 1, characterized in that it contains a color former of the formula given in the Z represents the atoms necessary to complete a phenyl ring. 6. Recording material according to claim 1, characterized in that the ballast carrier residue corresponds to the following formula: (BALL-TRÄG-BINDEGL) -which mean: BALL is an organic residue of such a molecular size and configuration that the compound does not diffuse during development in an alkaline medium; WEAR an oxidizable acyclic, carbocyclic or heterocyclic radical and BINDEGL a residue that is hydrolytically cleavable upon oxidation of the carrier residue, releasing the diffusible azo dye. 7. Recording material according to claim 1, characterized in that it contains a color former of the formula indicated, in which the ballast carrier residue corresponds to the following formula: (Ballast). NHSO ₂ L- where mean: 809820/0707 2948455 _ A mm ballast -NHSO ₂ L- An organic carrier residue of such a molecular size and configuration that the compound does not diffuse during development in an alkaline medium; a residue of one of the formulas -OR or -NHR ³ , 2 wherein R stands for a hydrogen atom or a hydrolyzable radical and R denotes a hydrogen atom or optionally one has substituted alkyl radicals with 1 to 22 carbon atoms; is in the ortho or para position too D: the atoms required to complete a benzene or naphthalene nucleus or the atoms necessary to complete a heterocyclic nucleus, the has one or two rings each with 5 to 7 ring members; a positive number from 1 to 2, where that j is - 2 when D ^{1 is} a radical of the formula 2 % -OR is or when R is a hydrogen atom or is an alkyl group with fewer than 8 carbon atoms and a link of one of the following formulas: ^ X- (NR ^ -J) - ^ j- or -XJ-NR ⁴ -which mean: 909820/0707 2,455 X is a divalent radical of the formula -R -L'jR -, wherein the two Rs have the same or a different meaning can and each represent an alkylene radical having 1 to 8 carbon atoms or an optionally substituted phenylene radical with 6 to 9 carbon atoms; L ^{1 is} a divalent oxy, carbonyl, carboxamido, carbamoyl, sulfonamide, ureylene, sulfamoyl, sulfinyl or sulfonyl radical; η ■ 0 or 1; ρ »1 if η ■ 1 and ρ ■ 1 or 0 if η ■ 0, provided that if ρ - is the number of carbon atoms of the Sum ¹ is; Sum of the two radicals R does not exceed 4th R is a hydrogen atom or an alkyl radical with 1 to 6 carbon atoms; J is a divalent sulfonyl or carbonyl radical; q ■ 0 or 1 and m 0, 1 or 2. 8. Recording material according to claim 7, characterized in that it contains a color former of the formula given in which D ^{1 is} a hydroxy radical, j is 2 and Y is the atoms required to complete a naphthalene nucleus. ÖU9820 / 0707 214145 * 9. Recording material according to claim 1, characterized in that that it contains a color former of the following formula: where mean: G is a hydroxy radical or a hydrolyzable one Ester radical of one of the formulas -OCOR ', -OCOOR ¹ or -OCON (R) ₂ i in which each radical R ^{1 is} an alkyl radical with 1 to 8 carbon atoms or an aryl radical with 6 to 12 carbon atoms or a radical which together with the -OCO group represents the ballast carrier residue; D is a halogen atom or a nitro, cyano or Perfluoroalkyl radical or a radical of one of the following formulas -SO ₂ R ⁸ , -CON (R ⁹ ) ₂ , -SO ₂ N (R ⁹ ) ₂ or -COOR ⁹ ; a nitro, cyano or perfluoroalkyl radical or a radical of one of the following formulas: "SO ₂ R, -SO ₂ N (R ⁹ ) ₂ , -CON (R) ₂ , or -COOR ⁹ ;" R is a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms, an aryl radical with 6 to 9 carbon atoms, a heterocyclic radical or a radical which, together with the -CON group, represents the Ballst triger radical, or both radicals R together with the nitrogen atom on which they are attached, a heterocyclic radical; 909820/0707 2841415 a radical of one of the formulas -COOR, -SO ₂ N (R) ₂ or -CON (R ⁹ ) ₂ ; Y «0, 1 or 2; R is an alkyl radical with 1 to 4 carbon atoms or an aryl radical with 6 to 9 carbon atoms; R is in each case a hydrogen atom or an alkyl, hydroxyalkyl or carboxyalkyl radical in which the alkyl group has 1 to 4 carbon atoms, an aryl radical having 6 to 9 carbon atoms or together with the group remainder with 6 to 9 carbon atoms or «in remainder R a remainder, 0
-CO-, -SO ₂ N- or -CON- forms a residue that represents the ballast carrier residue represents or both radicals R together with the nitrogen atom on the sit necessary for the completion of a 5- or 6-membered heterocyclic Ring's required atoms; Q is a hydrogen or halogen atom or a carboxy, alkyl or alkoxy radical with 1 to 4 C atoms, with the proviso that at least one of the radicals G, D, E or P has the ballast carrier radical or forms the ballast carrier radical. 10. Recording material according to claim 9, characterized in that that P is a ballast carrier residue of the following formula: 909820/0707 where mean: Ballast an organic residue of such a molecular size and configuration that the compound does not diffuse during development in an alkaline medium; Y * the atoms required to complete a benzene or naphthalene nucleus; R is an alkyl radical with 1 to 8 carbon atoms or an optionally substituted phenylene radical having 6 to 9 carbon atoms; R represents a hydrogen atom or an alkyl radical 1 to 6 carbon atoms; J is a sulfonyl radical and w ■ 0 or 1. 11. Recording material according to claim 1, characterized in that it contains a color former of the following formula: 909820/0707 2148455 where mean: Ballast an organic residue of such molecular size and configuration that the compound contributes the development of the material renders it non-diffusible in an alkaline medium; G is a hydroxy radical or a hydrolyzable one Ester radical of the formula -OCOR ¹⁰ , in which R ^{10 stands} for an alkyl radical with 1 to 8 carbon atoms or an aryl radical with 6 to 12 carbon atoms; D is a halogen atom; E is a radical of one of the formulas -SO ₂ N (R) - or -CON (R ¹¹ K, where R ^{11 is} a hydrogen atom or an alkyl, hydroxyalkyl or carboxyalkyl radical with alkyl groups of 1 to 4 carbon atoms, where the radicals R can be identical or different and Q is a hydrogen or halogen atom. 12. Recording material according to claim 1, characterized in that that it contains a color former that the diffusible azo dye in reverse function of the development of Releases silver halide emulsion layer or silver halide emulsion layers under alkaline conditions. 13. Recording material according to claim 1, characterized in that that it contains a color former which releases the diffusible azo dye as a direct function of the development of the silver halide emulsion layer or silver halide emulsion layers under alkaline conditions. 009820/0707 2IAIAI5 14. Recording material according to claim 1, characterized in that it consists of a recording unit with: (A) a support with one or more silver halide emulsion layers applied thereon, which have a Contain color formers or are in contact with a layer with such; (b) an image receiving layer and (c) an alkaline developing liquid and agents for distributing them within the recording unit and (d) a silver halide developing agent, with the proviso that the color former consists of a non-diffusible compound as described in claims 1 to 13, consists. 909820/0707