DE1229389B - Color photographic material and method for producing positive color images - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

G03c

German class: 57 b -18/08

Number: 1229 389

File number: E 26719IX a / 57 b

Filing date: March 28, 1964

Opening day: November 24, 1966

The invention relates to a color photographic material and processes for developing same.

Color photographic materials for manufacture of color images by a direct positive process are known. Such procedures generally require a series of sometimes complicated, but at least very time-consuming operations to to receive positive color images. In the usual known processes, a black and white development is first used carried out in order to produce a negative image in the exposed material, then takes place a reversal exposure followed by development with a preferably aromatic, primary amine to form insoluble dye images in the areas of development, and finally a bleaching process, to remove the developed silver.

There are also color photographic processes are known in which dye images on a recording or Receiving material will be transmitted. These methods have the particular advantage that the Color images free of residual color coupler compounds as well as others resulting from development are unwanted products. These processes, commonly referred to as "diffusion transfer processes" however, they also have the disadvantage that several stages and several Treatment baths with large volumes of liquid are required. In addition, as a result of lateral Diffusion of the dye-forming components often only color images of poor quality and in particular blurred images are obtained.

In order to eliminate the disadvantages of the diffusion transfer methods mentioned, it is already - z. B. from the German Auslegeschrift 1147 843 - a method for producing color photographic images became known, in which the development of the exposed halogen silver practically simultaneously with the The dye images produced are transferred to a pickled receiving material by diffusion and high quality positive images, particularly sharp dye images, in a single wet pass supplies. However, the process is limited to the production of color images by the diffusion transfer process limited.

The invention is therefore based on the object of creating a color photographic material which has the advantages of the known method, but is not only suitable for producing color photographic images by the diffusion transfer process, but also enables color images to be produced by the reversal process. Those of Er-Color Photographic Material and Processes
for producing positive color images

Applicant:

Eastman Kodak Company, Rochester, N.Y.

(V. St. A.)

Representative:

Dr. W. Wolff, H. Bartels

and Dipl.-Chem. Dr. J. Brandes, patent attorneys,

Stuttgart, Lange Str. 51

Named as inventor:

Charles Robert Barr, Rochester, N.Y. (V. St. A.)

Claimed priority:

V. St. v. America April 1, 1963 (269 346) -

The problem underlying the invention can be achieved by developing a color photographic material which consists of a carrier and at least two color-forming units arranged on it, which are sensitive to different spectral ranges of the visible spectrum and of one consisting of a hydrophilic colloid barrier layer are separated from each other, and the invention is characterized in that the color-forming units consist of

1. a light-sensitive emulsion consisting of a hydrophilic colloid and a silver halide,

2. one not in contact with the silver halide of the light-sensitive emulsion diffusible hydroquinone compound represented by the following formula

L-B

in which: R and R _{1 are} hydrogen atoms or

609 728/362

3 4

the phenolic groups blocking, brought by material, a mordant for acidic dyes

Residues that can be split off by alkali, —S— -containing receiving layer diffuse, while in

a connecting monothio residue, R 'a diffuse case, in which that in the unexposed developable

dable heterocyclic residue which is not diffusible with the dye formed with the emulsion,

connected to it Monothiorest a mercaptan 5 the developed silver in a known manner by a

can form, L can be a hydrogen atom or a bleaching treatment can be removed so that a

acidic, solubilizing group and B an inert, positive image of the object to be imaged

diffusion-preventing organic group present in the photographic material itself

3. an unexposed developable emulsion is formed. .

consisting of a hydrophilic colloid and a ¹⁰ _Ayr ^Die . ^f f ^ ^Μ ί ^α ί ™ ^Emheite f of ^the pliotographic water-insoluble metal salt, which will be useful without exposure material of the invention; se.her reduced to metal with a color developer solution | ^este , ^Ut ' ^{that 2} ^ f * becomes the feared, highly sensitive and emulsion is developed and that an emulsion-'. development-inhibiting mercaptan before development

4. a non-diffusible, with the water ₁₅ i _ung the unexposed developable emulsion unlöslichenMetallsalzinKontaktstehendenKupp- under substantially simultaneous formation of diffundieler, leaders of the following formulas or non-diffusible image dye rejuvenation ρ γ / j £ GM runs, cleaved from the Hydroclunonverbindung

ⁿ will. This can be achieved by the fact that the light

° the 2o sensitive emulsion (component A) and the one in the

Π. BY (K ₃ , L) _n light-sensitive emulsion or a hydroquinone compound present in an adjacent layer

in which: F means a dye residue which, from (component B), is located spatially further away from the carrier in the spectrum of visible light than the unexposed wavelengths are selectively absorbed and has a dissolvable emulsion or a halosilverizing acid residue, Y a emulsion with an azo, mercuri-, oxy-, alkylidene- binding for the light-sensitive emulsion, developing faster than for the redu-monothio, dithio or azoxy radical, K ₂ , a convertible metal salt in the unexposed developable coupler radical 5-pyrazolones, a pheno- emulsion and / or by using hydroquinone compounds, ic couplers or a coupler with more open 30 reacting faster than the coupler, ketomethylene group, the coupler radical being in.

the coupling positions with the connecting The couplers and the hydroquinone compounds of the

Radical Y is connected, η the number 1 or 2, when Y given general formula are common

is an alkylidene radical, or the number 1 if Y is a constituent of the photographic according to the invention

Azo, mercuri, oxy, monothio, dithio or 35 materials. The hydroquinone compound can

Is azoxy radical, and in which B and L are the specified either in the light-sensitive emulsion or in

have the same meaning, one which is adjacent to the light-sensitive emulsion

Be arranged layer, and the color-forming coupler

and that the barrier layer can be a water-insoluble compound either in the unexposed delivery Contains that with a mercaptan a water- 40 windable emulsion or in one to this emulsion is able to form insoluble salt. be arranged adjacent layer.

When such a color photographic material becomes the photographic material of the invention can

exposed imagewise according to the invention, one of three of the described color-forming units is produced

latent image (negative image) of developable halo, the light-sensitive emulsions of which are red,

silver in the light-sensitive emulsion (compo- 45 green- or blue-sensitive and their couplers

element A) of each color-forming unit. Will the exposing image dyes with one to the color of the spectral

tete emulsion then in an aromatic, primary sensitivity of the corresponding color-forming

Amine-containing alkaline, color-developing unit provide complementary color. However it is

Solution developed, so the Hydroquinonever- also possible that the emulsions in question differently

bond (component B) are sensitized through the development 50.

reaction formed oxidized amine under free The in the spontaneously developable emulsion layer become a diffusing, development-inhibiting or in a layer adjacent to this layer the mercaptans, which image-wise to the non-present color-forming couplers are diffusion-resistant, exposed, developable emulsion (component C) but composed so that it diffuses with the oxide and the development in those prepared color developers depending on the application, the purpose of the material in the photosensitive emulsion either to form a formed latent image (negative), inhibits diffusing or a non-diffusing image or prevented. In contrast, the metal salt of the dyes will convert.

unexposed developable emulsion in the areas, the acidic, solubilizing groups associated with the

their development not by the developable 60 diffusible image dyes described above

Inhibitory mercaptan is prevented (positive), couplers to be delivered are linked, are the cause

Metal reduced, and there by the development that the dyes in the presence of alkali

The oxidized amine formed settles with the presence of liquid developer solutions in the photographic

Coupler (component D) with dye formation. Material can diffuse. The solubilizing

If the dye formed is a diffusing dye, groups preferably consist of the dyes

substance, this preferably acidic dye can be composed of carboxyl, sulfone, and

the unexposed developable emulsion practically acidic, ionizable sulfonamido or oxysubstituted

at the same time, image-wise, in one of the photographic groups.

5 6

It has proven to be advantageous if the dye and 2 908 573 (magenta couplers) and 2,875 057 substance residues F describe the couplers from azo, azomethine, indo and 2 908 573 (yellow couplers),
aniline, indophenol, anthraquinone, and the like. Those in the photographic material of the Erfin dye residues which used dung in the visible part of the spectrum, freely selectively absorb a development inhibitor. These color-setting hydroquinone compounds break down the substance residues contain acidic, solubilizing group-inhibiting mercaptans, which are contained in pen. the layers of the color-forming unit is diffusible If a coupler of the formula I is oxidized, very likely in the following way: The color developing agent is reacted, so the coupler is in the light-sensitive emulsion layer or in the dye residue with the link Y io a hydro-connecting point present in an adjacent layer is split. In the process, an acidic quinone compound is released from the dye which diffuses during development and can diffuse imagewise onto an oxidation product of an aromatic receiving layer. An acidic, dissolvable primary amine to the corresponding quinone oxylizing group on the dye gives this dated and then the mercaptan from the quinone the necessary diffusibility and enables it to be split off.

at the same time that the dye molecule is in the receiving The substituent R 'can be selected from a large number

layer in the form of a pickling compound are fixed by photographically inert heterocyclic residues,

can. The coupling remainder of the coupler (K ₃ ,) couples the diffuse in the layers of the color-forming unit

are capable of forming mercaptans with the oxidation product of the color-developing agent,

means and forms a dye which is present in the material ao. Suitable heterocyclic radicals are, for. E.g .: 1-phenyl-

cannot diffuse because it prevents the diffusion tetrazolyl, oxazolyl, oxadiazolyl, diazolyl, thia-

changing group B in a non-coupling position diazolyl, benzoxazole / - benzothiazolyl, pyrimidyl,

contains bound. With this type of (color-forming) pyridinyl and quinolinyl radicals, while the through

Couplers is the color of the diffusing dye alkali can be split off residues R and R ₁ except from water

due to the color of the preformed dye residue, substance atoms, preferably from acetyl, mono-, di-

correct, while the color of the reaction product or trichloroacetyl residues, mono-, di- or trifluoro-

from the oxidized color developer and the coupling acetyl residues, butyryl, pyruvyl, alkoxalyl, nitro

the remainder of the coupler for the color of the diffundie benzoyl or cyanobenzoyl residues and perfluoroacyl

generating dye image is unimportant. remnants, exist.

When color-forming couplers of the formula II having 30 diffusion-preventing groups are preferred oxidized color developer are reacted, containing the couplers disclosed below, The coupler at the the coupling radical will consist of long-chain alkyl groups or more Coupler molecule with the link Y connecting shorter alkyl groups with 8 to 22 carbon atoms, Place cleaved and a diffusing dye made directly or indirectly with the coupler in question oxidized color developer and the coupling 35 molecule are connected, as well as from aromatic Part of the coupler is formed, which imagewise points to a residue of the benzene and naphthalene series, which directly Receiving layer diffuses. The dye owes or indirectly through a cleavable, but otherwise its diffusibility of an acidic, solubilizing non-functional bond with the coupler group, which are bound via a photographically inactive binding.

member in a non-coupling position with the 40 The part of the coupler coupling for the photographic material of the invention or the halide silver emulsions used are usually part of the color developer molecule. The developing photographic halogen silver emulusion-preventing group of the coupler diffusion, such as silver chloride, silver bromide, silver, however, does not. In this type of color-forming bromide iodide, silver chloride bromide and silver chloride couplers, the color of the diffusing image color is 45 bromide iodide emulsions. As a dispersant for the substance by the color of the reaction product from the halogen silver in the preparation of the emulsions oxidized developer and the coupling remainder of the gelatin or another intended for photographic coupler is used. Purposes known hydrophilic colloid; Gelatin If the coupler radical (K ₂ ,) in the color-forming is preferred. Hydrophilic colloids can also contain couplers consisting of a 5-pyrazolone radical, containing, as usual, an anilino group in the non-light-sensitive layers of these preferably in the 3-position or, in the photographic material according to the invention, an alkoxy group. When the coupler remainder (Kp) can be used in the.

color-forming couplers from a cyan. The present emulsions can incorporate the general

Dye-forming phenolic coupler residues contain additives used in such products,

this preferably contains in the 2-position a fully sub-55 such. B. optical sensitizers, the sensitivity

substituted amido group - CONH - X, where X is an enlarging material, antifoggant, coating

Denotes an alkyl group or a phenyl group. Also processing aids, gelatine hardeners, plasticizers,

when the link Y is incorporated in the color-forming ultraviolet absorber and the like.

Couplers of the formula II is an azo group, are preferred in the unexposed developable emulsion a phenyl group as a diffusion-preventing group, the metal salts water-insoluble, preferably light residue used of either an oxy or a sensitive silver salt, such as silver chloride, silver amino group in the 2 position. bromide, silver iodide, silver bromide iodide, silver chloride-characteristic, when coupling with oxidation bromide iodide, silver citrate, silver oxalate, silver phosphate, Products of color developing agents are not diffuse Silver steara ^ Silver ferrocyanidejSilver cyanide and silver earths Cyan, magenta and yellow dyes 65 thiocyanate.

forming couplers suitable for the invention are Other suitable salts are palladium bromide,

for example, in U.S. Patents 2,895,826, palladium cyanide and cupric bromide. Such

2,474,293 and 2,908,573 (cyan couplers), 2,600,788 metal salts can be obtained by adding developing agents

7 8

germinate into the emulsion to be developed unexposed. 1. N-Ethyl-N - (/? - oxäthyl) -4- (o-sulfobenzylidene-Such additives are known. Suitable developing amino) aniline, sodium salt,
germs consist of colloidal precious metals, 2. N, N-diethyl-4- (2,4-dioxybenzylideneamino) -like colloidal silver or gold, colloidal metal- 3-methylaniline and
sulfides, colloidal metaUselenides and metals · 5 _{3 N} _ethyl-3-methyl-N-03-methylsutfonamd
teUund such as B ^ lead sulfide, nickel sulfide, cadmium 4- (2-sulfobenzyHdenarmno) -aniline, sodium salt, sulfide, silver sulfide, silver selenide, silver tellund, copper- '
sulfide, zinc sulfide and mercury sulfide. As physics, development nuclei can be added to the photographic emulsions, further metals developers can be activated by adding the proteinate, e.g. B. silver proteinate, further sodium-related photographic material is immersed in an aqueous sulfide, colloidal sulfur and such organic alkaline solution or by using a sulfur compound such as thiourea and xan aqueous alkaline solution on the surface of the thate. When the physical material is distributed. In general, such development nuclei are used to develop the added developers either unexposed in the photosensitive emulsions, if the usual »developer-adjacent layers are present in the 15 borrowed halogen silver emulsion layers or in the developer mixes.
solvent «used for the metal salts, such as B. Am- Of the above-described emulsion layers, monium thiosulphate and alkali thiosulphates, ammonium are at least two and preferably three color and alkali thiocyanate, ammonium and alkali sulphite-forming units, which are different and the like visible spectrum are sensitive, the light-sensitive, water-insoluble The topmost color-forming unit is preferably to develop salts unexposed, consists in being selectively sensitive to blue light. Between the emulsion with light or with chemical reduction blue-sensitive, color-forming unit and the agents, such as. B. alkali borohydrides, according to the color-forming units for this purpose, a known technique is usually vorzuverschleiern. 25 yellow dye layer or a Carey Lea silver ent-To the exposed photographic material of the holding layer, which serves to develop the invention, can emit a large number of blue radiation, possibly from the topmost alkaline color developer solutions, the aromatic, blue-sensitive Layer is allowed to contain primary amines. They serve to sorb. However, in accordance with this, the exposed halosilver in the light- 30 of normal practice the spatial arrangement of the sensitive emulsions (component A) can be de-red-, green- and blue-light-sensitive, color-forming units and the metal salt in the unexposed units in the photographic material of the windable emulsion (component C) to an invention can be varied widely. To reduce such metal. Phenyl-multilayer photographic materials, such as lenediamine color developers, are particularly suitable. The color developer can also contain other intermediate layers or sub-layers of either an alkaline photographic stripping layer.

In order to ensure the effectiveness of the material, or in the photographic development-inhibiting mercaptan compounds, the material is added. from the hydroquinone compounds according to the invention ■ If the color developer is made free in the photographic 40, is added to a single color-forming emulsion, it is convenient to keep it in one unit, barriers are to be used in the form of the emulsions practically between each color-forming unit arranged, stable, such. B. in the form of Schiff's bases. These barrier layers contain a water-insoluble salt of the primary amine developer compound in question or a metal which is capable of forming a water-based agent. Such Schiff bases are made by forming an insoluble salt with mercaptans. Preferred conversion of primary amine developer compounds are silver halides, such as those with aromatic aldehydes of the benzene or silver chloride, silver bromide, silver iodide, silver bromide-naphthalene series, the hydroxyl, carboxyl or iodide, silver chloride bromide iodide, etc., used. Other sulfonic acid groups are shown. These Schiff bases in the barrier layers according to the invention have the general formula 50 suitable compounds which react with mercaptans R - N = CH - R ', where R is an aryl radical, such as yaw, are colloidal metals, such as colloidal silver z. B. a phenyl radical, referred to, which in ortho- or and colloidal gold and colloidal metal sulfides, para-position by a hydroxyl group, an un-selenide and -telluride, such as. B. lead sulfide, nickel-substituted or a substituted amino group sulfide, cadmium sulfide, silver sulfide, copper sulfide, zinc of the formula —NHR "or —N (R") ₂ , where R "is a sulfide, mercury sulfide, silver selenide, silver telluride · lower alkyl radical with 1 to 6 carbon atoms and the like. The photosensitive silver salts containing is substituted, and R 'is an aryl group such as barrier layers are made to represent essentially a phenyl or naphthyl group, which is less photosensitive than the photosensitive group such as a carboxyl- or sulfone-sensitive emulsions in the color-forming monoic acid group, or by a lower alkoxy group 60. Such barrier layers also serve to be substituted Unit to another farfc converting 2-amino-5-diethylaminotoluo l and forming unit migrate, where the color developer o-sulfobenzaldehyde are produced. Other ships could cause paint contamination. Antic bases, as such or in the form of salts 65 oxidants, such as. B. n-octadecylhydroquinone and / or sulfur dioxide complexes, for incorporation into other phenolic antioxidants and, if the exposed material relevant to the photographic material of the invention are suitable after diffusion, include: - - transfer processing is to be processed ¹ - not

diffusing photographic color couplers that use non-diffusible dyes when coupling with oxidized, aromatic amines can be placed in the barrier layers so that a Migration of the oxidized color developer is prevented.

The receiving or receiving layer used to receive the diffused dye images can either be a special sheet attached to the photographic material during processing is pressed, or it can consist of a layer that is integral with the photographic material Whole forms.

If the recording layer consists of a special recording sheet, the image development and the Image transfer can be effected in such a way that before the exposed material and the receiving layer be brought into effective contact with one another, either the photographic material or the photographic material and the pickled receiving sheet are bathed in the developing solution will. In another embodiment, a viscous developer mixture can be added between the photographic Material and the receiving sheet brought and in a certain amount in contact with the exposed Be the surface of the photosensitive material.

The use of viscous developer mixtures is described in U.S. Patents 2,543,181,2 559,643, 2,647,049, 2,647,056, 2,661,293, 2,698,244, 2,698,798 and 2,774,668.

When the receiving layer for the diffusing dye images with the light-sensitive material Forms a whole, such a material can consist of a carrier, a pickling agent arranged thereon containing colloid layer and the various emulsion layers applied over it, as described above exist. If easy-to-dissolve emulsions are used, e.g. B. those that Contain polyvinyl alcohol or an alkali-soluble cellulose ether phthalate as a binder, or if a wet or dry stripping layer containing such binders between the emulsions and the receiving layer is provided, the developed emulsion layers can be easily separated from the das final dye image-bearing receiving layer are separated. The recording layer can be similar originally associated with the outer surface of the emulsion. In this case it is preferred by the The support of the photosensitive material is exposed through it, unless the receiving layer is itself transparent. Such photographic materials can be developed in the same manner as those which do not have recording layers forming a whole with the photographic material contain.

The receiving layers in the photographic materials of the invention can be any of the usual ones Contain mordants for acidic dyes. Thus, the receiving layer can e.g. B. Mordants, such as Polymers of aminoguanidine derivatives of vinyl methyl ketone, as described in U.S. Patent 2,882,156. Other mordants include polymeric 2-vinylpyridine methiop-toluenesulfonate and similar compounds as described in U.S. Patent 2,484,430, and cetyltrimethylammonium bromide

Particularly effective mordant mixtures are described in French patent 1 361293.

The pickling mixtures described in the cited patent consist of at least one hydrophilic organic colloid, which is a finely divided uniform dispersion of droplets or spheres a high-boiling, water-immiscible organic solvent, wherein a cationic, non-polymeric organic mordant for acidic dyes is dissolved. The described Pickling mixtures can also consist of at least one

ίο consist of hydrophilic organic colloid, the one finely divided uniform dispersion of particles of a salt of an organic, acidic mixture which contains free acid components and a cationic, non-polymeric organic mordant compound for acidic dyes. Useful cationic or basic organic mordant compounds for acidic dyes include: quaternary ammonium and phosphonium compounds and ternary sulfonium compounds, wherein to the N, P or S onium atom at least one hydrophobic ballast group, such as. B. a long chain Alkyl group or a substituted alkyl group. In addition, the recording layer or the recording sheet alone is sufficient to hold the dye in the form of a stain compound determine how it is when using a sheet or a layer of a polyamide or a similar polymeric material is the case.

Both the dye image receiving sheets and the photographic materials of the invention may contain ultraviolet absorbing substances. The ultraviolet absorbers in the recording sheets protect the stained dye images from fading and copying out by ultraviolet rays Light. In the photographic materials, ultraviolet absorbers can serve as filters to reduce the ultraviolet sensitivity to reduce. Suitable ultraviolet absorbing substances are, for. B.-in the Belgian Patent 630118.

If necessary, in addition to a positive color image, a negative image intended for storage can be used getting produced. To produce such a color negative, an ordinary photographic one is used Color coupler of the type which produces a non-diffusing dye when reacted with an oxidized color developer forms, together with the hydroquinone compound which splits off the development-inhibiting mercaptan used. In this embodiment, diffusible dyes become releasing couplers selected that do not form colored, non-diffusible dyes during the process.

Also becomes a receiving layer for the diffused positive dye image is used, which is based on a particular, i.e. H. of the photographic material separate recording sheet is arranged. After the positive image is transferred to the receiving sheet the remaining negative material is fixed in sodium thiosulfate solution. The silver can be with a Bleach bath, e.g. B. an alkali ferricyanide solution, remove. Suitable photographic color couplers which non-diffusing dyes are phenolic 5-pyrazolone and open-chain ketomethylene coupler compounds, as described in U.S. Patents 2,640,776, 2,407210, and 2,474,293 are.

The drawings show cross-sections of photographic materials of the invention.

The F i g. 1 shows a photographic material in which each color-forming unit has a developing

«09728/362

Inhibiting mercaptan-releasing hydroquinone compound in a light-sensitive halogen silver emulsion contains and in which the unexposed developable emulsion consists of a physical development nucleus containing metal salt.

The F i g. Fig. 2 shows a photographic material of the invention in which each color-forming unit has a Development-inhibiting mercaptan-releasing hydroquinone compound in the light-sensitive halogen silver emulsion contains and in which the unexposed developable emulsion consists of a veiled Halogen silver emulsion consists.

The photographic material of FIG. 1 contains three color-forming elements arranged on a carrier 10 Units that are sensitive to different areas of the visible spectrum. In detail a metal salt layer 11 containing physical development nuclei is applied to the carrier 10, which also contains a coupler which forms a cyan dye. Above layer 11 is one Applied halogen silver emulsion, which is sensitive to red light and a hydroquinone compound contains, which splits off a development-inhibiting mercaptan. Above layer 12 is a Barrier layer 13 applied, which contains a compound that is able to with mercaptans an insoluble To form salt. Over the layer 13 is a metal salt layer containing physical development nuclei 14, which further contains a coupler which forms a magenta dye. About the Layer 14 is a halogen silver emulsion layer 15 which is sensitive to green light, applied which contains a hydroquinone compound that splits off development-inhibiting mercaptan. About the Layer 15 is applied a barrier layer 16 which contains a compound that has an insoluble salt Forms mercaptans and which further contains a yellow filter material. Layer 16 is a physical one Metal salt layer 17 containing development nuclei is applied, which further comprises a yellow dye forming coupler contains. Finally, over the layer 17 is a halosilver emulsion layer 18 which is sensitive to blue light and which contains a hydroquinone compound that development-inhibiting mercaptan splits off.

The photographic material of FIG. 2 contains arranged on a photographic support 20 three color-forming units of the invention facing different regions of the visible spectrum are sensitive. It is on the carrier 20 is a

ίο veiled halogen silver emulsion layer 21 applied, which contains a coupler that forms a magenta dye. Over layer 21 is a silver halide emulsion layer 22, which is sensitive to green light and a hydroquinone compound contains, which splits off a development-inhibiting mercaptan. Over the layer 22 is a barrier layer 23 which contains a compound capable of forming an insoluble salt with mercaptans. Above the layer 23 is a veiled halogen

Also disposed is silver emulsion layer 24 which contains a coupler which forms a cyan dye. On that followed by a halogen silver emulsion layer 25 sensitive to red light and a hydroquinone compound contains, which splits off a development-inhibiting mercaptan. Layer 25 follows as Next layer is a barrier layer 26 that contains a compound that interacts with a mercaptan forms insoluble salt and which contains a yellow filter material. Above layer 26 is a veiled one Halide silver emulsion layer 27 is applied which contains a coupler which forms a yellow dye. This is followed by layer 28, a halogen silver emulsion layer which is sensitive to blue light and contains a hydroquinone compound that splits off a development-inhibiting mercaptan. Above Finally, a protective layer 29 is arranged on the layer 28 as the last layer. As a development inhibitor Hydroquinone compounds which split off mercaptans are for the invention, for. B. the following Connections suitable:

2- {4- [3- (4-tert-amyl-x-sulfophenoxy) -benzamido] -phenethyl} -x- (l-phenyl-5-tetrazolylthio) -

hydroquinone, sodium salt

ν—:

Il
ν—:

: —S

C ₆ H ₅

CH ₂ CH ₂

• -V NHCO

SO ₃ Na

5- [4- (3,5-Disulfobenzamido) phenethyl] -2-methyl-3- (1-phenyl-5-tetrazolylthio) hydroquinone, disodium salt

N == N
C ₆ H ₅ -NN

OH

CH ₂ CH ₂ NHCO

CH ₃

SO ₃ Na

SO ₃ Na

OH

2- {4- [2- (2,4-Di-tert-amylphenoxy) -5- (3,5-disulfobenzamido) -benzamido] -phenethyl} -x- (1-phenyl-5-tetrazolylthio) -hydrochmone , Disodium salt (dihydrate)

SO ₃ Na · H ₂ O

N-N

v_

c - s

N -N ^x
C ₆ H ₅

CH ₂ CH ₂ - ^ NHCO

SO ₃ Na · H ₂ O

2- {4- [3- (4-tert-amyl-x-sulfophenoxy) -benzamido] -phenethyl} -x- (l-phenyl-5-tetrazolylthio) -hydroquinone diacetate, Sodium salt (dihydrate)

Ν —Ν

C-S

N - W
C ₆ H ₅

CH ₂ CH ₂ - <> - NHCO - γ - α

CsHii-t SO ₃ Na · 2 H ₂ O

2- [4- (3,5-Disulfobenzamido) -phenäthyl] -x- (l-phenyl-5-tetrazolylthio) -hydroquinone, disodium salt (dihydrate)

OH SO ₃ Na · H ₂ O

SO ₃ Na · H ₂ O

2- [4- (3,5-Disulfobenzamido) -phenäthyl] -x- (2-benzoxazolylthio) -hydroquinone, disodium salt (dihydrate)

OH SO ₃ Na · H ₂ O

, -.

C -

SO ₃ Na · H ₂ O

OH

The following is the preparation of a hydroquinone compound of the invention (compound I).

2 - {4 - [3 - (4 - tert-amyl - χ - sulfophenoxy) - benzamido] -phenethyl} -x- (l-phenyl-5-tetrazolylthio) -,

hydroquinone, sodium salt

A solution of 8 parts of intermediate 5, described below, in 100 parts by volume of methyl alcohol was refluxed under nitrogen for 3 hours. Became the clear amber solution then a solution of 1 part sodium bicarbonate in 20 parts by volume of water was added. The clear reaction mixture was evaporated to dryness in vacuo, whereby 7 parts of a yellow-brown colored powder were obtained.

Intermediate 1 4-trifluoroacetamidophenethylhydroquinone

143 parts of 4-aminophenethylhydroquinone were added to 600 parts by volume of trifluoroacetic anhydride. The clear mixture was refluxed on a water bath for 5 minutes and then slowly Poured into 3000 parts by volume of water. The product fell in the form of a yellow-brown colored solid Material that was filtered off and dried.

Intermediate 2 4-Trifluoroacetamidophenethylbenzoquinone

40 parts of intermediate 1 were dissolved in 1000 parts by volume of acetone and 600 parts by volume of water

added. To this solution, a solution was added dropwise 60 parts by volume of concentrated sulfuric acid in 100 parts by volume of water in 20 minutes dropwise at -1O ⁰ C and thence to the sulfuric acid solution is also added dropwise and at -5 ° C in 20 minutes a solution of 18 parts of potassium dichromate in 100 Parts by volume of water are added. The mixture obtained was stirred for a further 5 minutes and then 2000 parts by volume of water were added, whereupon the product separated. This mixture was stirred for 1 hour before the solid product was filtered off and dried.

Intermediate 3

jc- (1-phenyl-5-tetrazolylthio) -2- (4-trifluoroacetamidophenethyl) hydroquinone

To a solution of 48.5 parts of intermediate 2 in 500 parts by volume of chloroform 27 parts of 1-phenyl-5-mercaptotetrazole under nitrogen with stirring admitted. The mixture was refluxed under nitrogen for 3 hours. That Product had deposited in the form of a white, solid material. This was filtered off and dried.

Intermediate 4

2- (4-aminophenethyl) -x- (l-phenyl-5-tetrazolylthio) -

hydroquinone

30th

To a solution of 25 parts of intermediate 3 in 500 parts by volume of 90% ethyl alcohol 25 parts by volume of 20% sodium hydroxide solution were added under nitrogen. The clear reaction mixture became Left to stand overnight at room temperature (also under nitrogen) and then in 2000 parts by volume Poured dilute acetic acid. The yellow-brown colored solid material which separated out was filtered off and dried.

40 intermediate 5

2- {4- [3- (4-tert-amyl-x-chlorosulfonylphenoxy) -

benzamido] -phenäthyl} -x- (l-phenyl-

5-tetrazolylthio) hydroquinone

45

To a solution of 16 parts of intermediate 4 and 5 parts of N, N-dimethylaniline in 500 parts by volume of dry acetone was added with stirring at 40 ⁰ C a solution of 16 parts of 3- (4-tert-Amylx-chlorosulfonylphenoxy) benzoyl chloride in 50 Parts by volume of dry acetone added. The clear reaction mixture was refluxed for 4 hours and then poured into 500 parts by volume of water. The excreted rubber-like material was dissolved in 500 parts by volume of benzene and poured into 500 parts by volume of cyclohexane. The precipitated solid white material was filtered off and dried.

The following color-forming couplers are examples of non-diffusing ones useful in the present invention Coupler compounds which diffuse on coupling with the oxidation products of color developers release or form acidic dyes.

Couplers VII to XVI below are substituted in the coupling position by preformed yellow dyes, the couplers carrying the diffusion-preventing groups are split off and diffusible when the couplers in question react with oxidized color developers.

l-Oxy-4- {3- [4- (N-ethyl-N- / S-sulfoethylamino) -2-methylphenylazo] -phenylazo} -N - [(5- (2,4-di-tert-amylphenoxy ) -butyl] -2-naphthamide, Sodium salt

OH

GsHii-t

/ C ₂ H ₅

C ₂ H ₄ SO ₃ Na

l-Oxy-4- {4- [l- (4-sulfophenyl) -3-methyl-4-pyrazole-

5-onylazo] -3-sulfophenylazo} -N - [(5- (2,4-di-tert-amylphenoxy) -butyl] -2-naphthamide, Disodium salt

OH

- CONH (CHa) ₄ - O - ^

C ₅ H _n -t

C ₅ Hn

(VIII)

SO ₃ Na

SO ₃ Na

l-Oxy-4- {3- [4- (N-ethyl-N - /? - carboxyäthylamino) -2-methylphenylazo] -phenylazo} -N- [r5- (2,4-di-tert-amylphenoxy) -butyl] -2-naphthamide, Sodium salt

OH

C ₂ H ₅ COONa

17 18

1-Oxy-4- (2,4-dinitrophenylthio) -N- [f5- (2,4-di-tert-amylphenoxy) butyl] -2-naphthamide

CONH (CHa) ₄ -O- ^> -QHu-t

CsHii-t

NO ₂

NO ₂

1-Oxy-4- {4- [1- (4-sulfophenyl) -3-methyl-4-pyrazol-5-oneylazo] -3-sulfophenylazo} -N- {4- [a- (2,4-di -tert.-amylphenoxy) -butyramido] -phenäthyl} -2-naphthamide, Dipotassium salt

C ₂ H ₅

l-Oxy-4- {4- [3-methyl-4- (l, 5-disulfo-3-naphthylazo> l-pyrazol-5-onyl] -phenylazo} -N- {4- [a- (2, 4-di-tert-amylphenoxy) -butyramido] -phenäthyl} -2-naphthamide, Dipotassium salt

C ₂ H ₅

C ₅ H _u -t

SO ₃ K

SO ₃ K

609 728/362

20th

l-Oxy-4- {4- [3-methyl-4- (l, 5-disulfo-3-naphthylazo) -l-pyrazol-5-onyl] -phenylazo} -N- [o- (3-pentadecylphenoxy) -butyl] -2-naphthamide, Disodium salt

COHN (CH ₂ ) ₄

(XIII)

SO ₃ Na

l- (p-tert-butylphenoxyphenyl) -3- [a- (4-tert-butylphenoxy) propionamido] -4- (2-bromo-4-methylamino-

5-sulfo-1-anthra-9,10-quinonylazo) -5-pyrazolone

tC ₄ H ₉

= C-NHCO-CH-O

C ₄ H ₉ t

CH ₃

CH ₃ HN 0 SO ₃ H

a- {3- [a- (2,4-Di-tert-amylphenoxy) -acetamido] -benzoyl} -a- {3- [4- (N-ethyl-N- / S-sulfoäthylainino) -l- methylphenylazoj-phenylazoj-l-methoxyacetanilide, Sodium salt

t-QHu

OCH ₂ CONH

CsHn-t

C ₂ H ₅
C ₂ H ₄ SO ₃ Na

21

22nd

1-Oxy-4- {4- [1- (4-sulfophenyl) -3-carboxy-4-pyrazol-5-oneylazo] -3-sulfophenylazo} -N- {4- [a- (2,4-di -tert.-amyl-

phenoxy) butyramido] phenethyl} -2-naphthamide

OH

SO ₃ H

CONHC ₂ H ₄ -

C ₂ H ₅
NHCOCHO

/ V

CsHu-t

(XVI)

CO ₂ H

OH

Each of Couplers XVII to LII below contains 1-oxy-4- (4-octadecyloxyphenylazo) -2-naphthoic acid an acidic, solubilizing group in a non-coupling position and forms upon coupling with oxidized color developer with cleavage of a diffusion-preventing group from the coupling Position a diffusible dye.

Couplers XVII through XXXV below form diffusible cyan dyes.

CO ₂ H

l-oxy-4-stearoyloxymercuri-2-naphthoic acid OH

CO ₂ H

45

(XVII)

HgOCOCi ₇ H ₃₅

l-oxy-4-dodecyloxy-2-naphthoic acid

OH

CO ₂ H

(XVIII)

(XIX)

l-Oxy-4- (4-octadecyloxyphenylazo) -N - [/ S- (3,5-disulfobenzamido) ethyl] -2-naphthamide),

Dikahum salt

CONH (CH ₂ ) ₂ NHCO

OCi ₈ H ₃₇

SO ₃ K

SO ₃ K
(XX)

23

l-Oxy-N-C / S-sulfoethyrM - ^ - octadecyloxyphenylazo) -2-naphthamide, Potassium salt

OH

CONHCH ₂ CH ₂ SO ₃ K

OCi ₈ H ₃₇

(XXI)

1-Oxy-4- (4-octadecyloxyphenylazo) -3 '-carboxy- 15 4'-oxy-2-naphthanilide

(XXII)

-Oxy-3 ', 5' -dicarbomethoxy-4-dodecyloxy-2-naphthanilide

35

OH

CO ₂ CH ₃

CONH

(XXIII)

40

CO ₂ CH ₃

OCi ₂ H ₂₅

(The carbomethoxy groups hydrolyze when dispersed by the action of acid.)

24

l-Oxy-4- (2-oxy-4-pentadecylphenylazo) -N-ethyl- ', 5'-dicarboxy-2-naphthanilide

COOH

COOH

(XXIV)

1-Oxy-4-octadecyloxy-N-ethyl-3 ', 5'-dicarboxy-2-naphthanilide

OH

COOH

(XXV)

l-Oxy-4- (3-octadecylcarbamylphenylthio) -N-ethyl-3 ', 5'-dicarboxy-2-naphthanilide

OH

C ₂ H ₅

COOH

CON

COOH

(XXVI)

CONHCi ₈ H ₃₇

4,4'-p-octadecyloxybenzylidene-bis- (l-oxy-N-ethyl-3 ', 5'-dicarboxy-2-naphthanilide)

OH

OH

HOOC

COOH

COOH

(XXVII)

25th

1-Oxy-S-acetamido ^ -octadecyloxy-S-phenylazo-2-naphthoic acid

C ₆ H ₅ -N = N OH

COOH

(XXVIII)

CH ₃ COHN O

C18H37

2- (3,5-Disulfobenzamidoj-5-methyl-4- (4-octadecyl-15 oxyphenylazo) phenol, dipotassium salt

1-Oxy ^ -P-octadecylcarbamylphenylthio) -N-methyl-N - (/ 9-carboxyethyl) -2-naphthamide

CH ₃
CO - N - CH ₂ - CH ₂ - COOH

(XXXII) CONHCi ₈ H ₃₇

1-Oxy-4- (3-octadecylcarbamylphenylthio) -N-isopropyl-3 ', 5' -dicarboxy-2-naphthanilide

OH

SO ₃ K

OH

20th

SO ₃ K

(XXIX) 25

OCi ₈ H ₃₇

CH ₃ CH CH ₃ CO-N

COOH

COOH (XXXIII)

CONHCi ₈ H ₃₇

2- (3,5-Disulfobenzamido) -4- (4-oxy-2-pentadeeyl-30 phenylazo) -5-methylphenol, dipotassium salt

5- (3,5-disulfobenzamido) -4- (4-octadecyloxyphenylazo) -2-heptafluorobutyramidophenol, Dipotassium salt

OH

SO ₃ K

CH ₃

(XXX)

35

40

45 KO3S

<f ~~ \ —C0NH
KO ₃ S

OH

NHCOC ₃ F ₇

(XXXIV)

2- (3,5-dichlorosulfonylbenzamido) -5-methyl-50 4- (4-nitrophenylthio) phenol

CH ₃

SO ₂ Cl

55 0 - Ci ₈ H ₃₇

2,5-bis- (3,5-disulfobenzamido) -4- (4-octadecyloxyphenylazo) -phenol, Tetrapotassium salt

CONH

KO ₃ S

SO ₂ Cl

60

(XXXI)

NO ₂

65 O - Ci ₈ H ₃₇

(The sulfochloride groups hydrolyze during
of dispersion.)

Couplers XXXVI through XLVII form diffusing magenta dyes.

609 728/362

I 229 389

28

l-phenyl-3- (3-sulfobenzamido) -4- (4-octadecyloxyphenylazo) -5-pyrazolone, Sodium salt

C ₆ H ₅ Ni

/ N = C NHCO

^ C-CH

SO ₃ Na (XXXVI)

l-phenyl-3- (3,5-disulfobenzamido) -4- (4-octadecyloxyphenylazo) -5-pyrazolone, Disodium salt

SO ₃ Na

C ₆ H ₅ N

ON = N -f V-OCi ₈ H ₃₇

IO

1- [4- (4-tert-butylphenoxy) phenyl] -3- (3,5-disulfobenzamido) -4- (4-octadecyloxyphenylazo) -5-pyrazolone,

Dipotassium salt

SO ₃ K

tH ₉ C ₄

(XXXVIII)

SO ₃ K OCi ₈ H ₃₇

1-phenyl-3- (3,5-disulfobenzamido) -4- (4-oxy-2-pentadecylphenylazo) -5-pyrazolone, dipotassium salt

SO ₃ K

C ₆ H ₅

(XXXIX)

1- (p-Sulfophenyl) -3-carboxymethyl-4- (4-oxy-2-pentadecylphenylazo) -5-pyrazolone, sodium salt

/, --Χ / N = C CH ₂ COOH

NaO ₃ S ζ > n (I.

^N = ^ ^X C CH (XL)

0 N

OH

1- (4-sulfophenyl) -3-carboxy-4- (4-oxy-2-pentadecylphenylazo) -5-pyrazolone, sodium salt

/ N-C COOH

NaO ₃ S-

OH

(XLI)

Ci ₅ H ₃ I.

1-Phenyl-3- (3,5-disulfobenzamido) -4- [4- (3-methyl-5-pentadecyl) -pyrazolylazo] -5-pyrazolone, dipotassium salt

SO ₃ K

/ N = C NHCO ^ ^>

C ₆ H ₅ N

SO ₃ K

(XLII)

29 30

1- (4-sulfophenyl) -3- (4-sulfoanilino) -4- (2-oxy-4-pentadecylphenylazo) -5-pyrazolone, dipotassium salt

KO ₃ S

SO ₃ K

(XLIII)

OH

1- (4-sulfophenyl) -3- (4-sulfoanilino) -4- (2-amino-4-pentadecylphenylazo) -5-pyrazolone, dipotassium salt

KO ₃ S

SO ₃ K

(XLIV)

1- [4- (3,5-Dicarboxybenzamido) phenyl] -3-ethoxy-4- (3-octadecylcarbamylphenylthio) -5-pyrazolone COOH

\ ~ J * y CONH

COOH

- CONHCi ₈ H ₃₇ l- (4-sulfophenyl) -3- (4-sulfoanilino) -4- (3-octadecylcarbamylphenylthio) -5-pyrazolone, disodium salt

NaO ₃ S

SO ₃ Na

(XLVI)

CONHCi ₈ H ₃₇

4,4 '- (4-Octadecyloxybenzylidene) -bis- [1-phenyl-3- (3,5-disulfobenzamido) -5-pyrazolone], tetrapotassium salt

SO ₃ K

C ₆ H ₅ N

OCi ₈ H ₃₇

(XLVII)

C ₆ H ₅ N

SO ₃ K The couplers XLVIII to LII listed below form diffusing yellow dyes.

31 32

α-Benzoyl-α- (4-oxy-2-pentadecylphenylazo) -4- (3-sulfobenzamido) acetanilide, sodium salt

C ₆ H ₅

OH

NHCO

SO ₃ Na

(XLVIII)

C15H31

α-Benzoyl-α- (4-oxy-2-pentadecylphenylazo) -4- (3,5-disulfobenzamido) acetanilide, dipotassium salt

C ₆ H ₅ -

Il ■ c-

-CH

N N

OH

Il ■ c-

NHCO

SO ₃ K

(XLIX)

α-Benzoyl-α- [4- (3-methyl-5-pentadecyl) -pyrazolylazo] -4- (3,5-disulfobenzamido) -acetanilide, dipotassium salt

C ₆ H ₅

Il ■ c-

N N

-CH-

Il -c-

CH ₃ if ^xx | Ci ₅ H ₃ I.

N-NH

NHCO

SO ₃ K

α-Benzoyl-α - ^ - octadecylcarbamylphenylthio) -3,5-dicarboxyacetanilide

a-Pivalyl-a-iS-octadecylcarbamylphenylthio) -4-sulfoacetanilide, Potassium salt

C ₆ H ₅ C-CH-C-NH ^> (LI) (CHs) ₃ -CC-CH-C-

L ^ CONHCi ₈ H ₃₇

CONHCi ₈ H ₃₇

Diffusing dyes are formed when using the non-diffusing couplers listed above VII to LII in the photographic material of the invention deal with oxidized p-phenylenediamine developers, namely Ν, Ν-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, N-ethyl-ß-methanesulfonamidoethyl-3-methyl-4-aminoaniline and other Ν, Ν-dialkyl-p-phenylenediamine developers, such as which are described by B e η t in Journal of the American Chemical Society, 73, pp. 3100 to 3125 (1951), realize.

Couplers LIII through LXI are non-diffusing couplers used in the photographic material of Invention can be used when the color developing agent has an alkali-solubilizing group contains.

Couplers LIII to LVI below form diffusing blue-green dyes. 34

1-Oxy-2 ', 5'-dibutoxy-4- [4- (sulfomethyl) phenylazo] -2-naphthanilide

OH

OC4H9

CONH

OC4H9

CH2SO3H

1-Oxy-4- (4-octadecyloxyphenylazo) -N-methyl-2-naphthanilide

OH

CH ₃

CON

Couplers LVII to LIX listed below form diffusing magenta dyes.

1-phenyl-3-methyl-4- (4-octadecyloxybenzylidene) -5-pyrazolone

(LIII)

N (

30th Il

= C-CH ₃

- C = CH - / \

(LVII)

1-Hydroxy ^ -dodecyloxy ^ -naphthanilide OH

CONH

35

N- /

OC12H25

1-Oxy-4- (2-amino-4-octadecylphenylazoxy) -2-naphthamide

CONH ₂ 4,4-thiobis (1-phenyl-3-methyl-5-pyrazolone) CH ₃ CH ₃

N = C C = Nx

c — c — s — c— <

ir ι ii

OH HO (LVIII)

4,4'-dithiobis (1-phenyl-3-methyl-5-pyrazolone) CH ₃ CH ₃

(LIV) a -χ / N = CC = Nx

/ \ / ^ C * CC C ^ Γ ¹ /

Il I I Il

OH HO (LIX)

: n

Couplers LX and LXI listed below form diffusing yellow dyes.

a, a '- (4-octadecyloxybenzylidene) -bis- [a-benzoylacetanilide]

60

(LV)

65

609 728/362

α, α'-dithiobis- [benzoylacetanilide]
OO

Il Il j

C - CH - C - NH -

S.
S.
C - CH - C - NH - <^

(LXI)

Color developers suitable for the invention which contain solubilizing groups and those in conjunction provide diffusing image dyes with the non-diffusing couplers described above, are z. B. the following:

4-Ammo-N-ethyl-3-methyl-N - (/ 3-sulfoethyl) aniline,

4-Amino-N-ethyl-3-methoxy-N - (/? - sulfoethyl) -aniline,

4-Amino-N-ethyl-N - (/ 3-oxyethyl) -aniline,

4-amino-N, N-diethyl-3-oxymethylaniline,

4-amino-N-methyl-N- (j8-carboxyethyl) -ariiHn,

4-Amino-N, N-bis - (/ J-oxyäthyl) -aniline,

4-Amino-N, N-bis - (/ S-oxyethyl) -3-methylaniline,

3-ethamido-4-amino-N, N-bis - (/? - oxyethyl) aniline,

4-Amino-N-ethyl-N- (2,3-dioxypropyl) -3-methyl aniline sulfate,

4-Amino-N, N-diethyl-3- (3-oxypropoxy) aniline.

When the above-mentioned couplers were incorporated into exposed silver halide emulsions which were developed in contact with a pickled receiving layer with an alkaline color developer solution containing the developing agent 4-amino-N-ethyl-N- (β- oxyätR'yl) -aniline, the dye images obtained from the couplers on the receiving layer had the colors for the individual couplers shown in the following table.

number
of the coupler colour number
of the coupler colour VII
VIII
IX.
X
XI
XII
XIII
XIV
XV
XVI
XVII
XVIII ....
XIX
XX
XXI
XXII yellow
yellow
yellow
Orange yellow
yellow
yellow
yellow
yellow
yellow
yellow
Blue green
Blue green
Blue green
Blue green
Blue green
Blue green XXX
XXXI ....
XXXII ...
XXXIII ..
XXXIV ...
XXXV ...
XXXVI ...
XXXVII ..
XXXVIII ..
XXXIX ..
XL. '
XLI
XLII
XLIII ....
XLIV ....
XLV Blue green
Blue green
blue green
Blue green
Blue green
Blue green
Purple
Purple
Purple
Purple
Purple
Purple
Purple
Purple
Purple
Purple

number
of the coupler colour number
of the coupler colour XXIII
XXIV ....
XXV
XXVI ....
XXVII ...
XXVIII ...
XXIX .... Blue green
Blue green
Blue green
Blue green
Blue green
Blue green
Blue green XLVI ....
XLVII ....
XLVIII ...
XLIX ....
L.
LI
LII Purple
Purple
yellow
yellow
yellow
yellow
yellow

The following describes the preparation of couplers of the invention.

Coupler VII

l-Oxy-4- {3- [4 (N-ethyl-N- / S-sulfoethylamino) -2-methylphenylazo] -phenylazo} -N - [<5- (2,4-di-tert-amyl-

phenoxy) butyl] -2-naphthamide, sodium salt

17 g of the one described below were added to 200 ml of concentrated sulfuric acid at 10 ° C. with stirring Intermediate C was added and added dropwise to the resulting solution in 30 minutes at -5 ° C below Stir a solution of 3.5 g of sodium nitrite in 35 ml of concentrated sulfuric acid (i.e. nitrosyl sulfuric acid solution) added. This solution was stirred for a total of 2 hours, after which time it became crushed Ice was poured. The solution thus obtained was then added to a solution of 21 g of l-oxy-N - [<5- (2,4-di-tert-amylphenoxy) -butyl] -2-naphthamide (U.S. Patent 12 474 293) in 21 pyridine over the course of 30 minutes added with stirring at 0 to 5 ° C. After standing at room temperature for 12 hours, the The reaction mixture was mixed with 1.5 kg of crushed ice and acidified with hydrochloric acid. That in form a red colored solid material precipitated product was isolated, washed with water and Recrystallized twice from glacial acetic acid.

Coupler VII, Intermediate A

N-ethyl-3-methyl-N-GS-sulfoethyl) aniline, , Sodium salt

A mixture of 675 g of N-ethyltoluidine and 528 g of sodium 2-bromoethanesulfonate was heated for 3 ¹ I for ₂ hours at 160 to 190 ° C., whereupon the mixture was cooled and 1200 ml of water were added. The solution obtained was made alkaline with sodium hydroxide and the precipitated solid product was isolated, washed with acetone and ether and recrystallized from 2.5 liters of ethyl alcohol. Yield 420 g of product.

Coupler VII, Intermediate B

, 5- {N-ethyl-N- [3-niethyl-4- (3-nitrophenylazo) phenyl] amino} ethylsulfonic acid, Sodium salt

A cold diazonium solution obtained from 14 g of m-nitroaniline and 7.5 g of sodium nitrite -f 200 ml of 6η hydrochloric acid was added ^{at 0} ° C. to a solution of 27 g of intermediate A in 250 ml of water. The mixture was neutralized against Congo red paper with sodium acetate. The neutralized mixture was then cooled for 2 hours, which after

Solid material precipitated 6 _½ this time was collected, washed with cold water and recrystallized from 360 ml of water, a green product being obtained.

Coupler VII, Intermediate C

/ 3- {N- [4- (3-aminophenylazo) -

3-methylphenyl] -N-äthylatnino} -ethylsulfonic acid,

Sodium salt

To a solution of 41 g of intermediate B in 21 water was at 90 ° C over the course of 30 minutes a solution of 40 g of 60% ^em sodium sulfide in 150 ml of water. The mixture was then cooked 2 ¹ Z ₂ hours, with about half of the water present was distilled off. The remaining mixture was filtered and placed in a refrigerator overnight. The then precipitated solid material was collected and recrystallized from 200 ml of ethyl alcohol.

Coupler XIII

l-Oxy-4- {4- [3-methyl-4- (l, 5-disulfo-3-naphthylazo) -

1 - pyrazole - 5 - onyl] - phenylazo} - N - [S - (3 - pentadecyl-

phenoxy) butyl] -2-naphthamide, disodium salt

A solution of 6.5 g of sodium nitrite in 93 ml of water was added a solution of 49.5 g of intermediate E in 300 ml of 5 ° / oig ^he added sodium carbonate solution, the mixture to 10 ⁰ C and then cooled to a well stirred mixture of 75 ml of hydrochloric acid and 150 g of ice were added. After I ¹ Z ₂ hours, the diazonium suspension thus obtained was added in portions with vigorous stirring to a solution of 44 g of intermediate C in a mixture of 1500 ml of ethyl alcohol and 55 g of potassium carbonate in 360 ml of water. To

2 hours the crude product is filtered off, triturated with boiling ethyl alcohol and finally dissolved in 1500 ml of ethyl alcohol and 1500 ml of 3 ° Z _o potassium carbonate solution. The dark orange colored solution was filtered and acidified with acetic acid. The precipitated solid material was filtered off, rubbed in acetone and benzene, extracted twice with hot water and finally recrystallized from a 1: 1-η-propyl alcohol-water mixture. 40 g of product with a melting point of> 270 ^° C. were obtained.

Coupler XIII, Intermediate A

j- (3-pentadecylphenoxy) butyronitrile

A mixture of 4 g of sodium hydroxide and 31 g of 3-pentadecylphenol in 100 ml of xylene was refluxed for 6 hours, during which time 1.8 ml of water distilled off (azeotropically). To the mixture, 11 g of j-chlorobutyronitrile was added dropwise over one hour, and the reaction mixture was then refluxed for 7 hours. The xylene was then distilled off over the course of 12 hours and the remaining oil was poured into 25 ml of dilute hydrochloric acid. The solid wax which separated out was collected and recrystallized from 100 ml of acetonitrile, 23 g of product with a melting point of 46 to 47 ^° C. being obtained.

6c Coupler XIII, Intermediate B

(5- (3-pentadecylphenoxy) butylamine

A mixture of 5 g of intermediate A,

3 ml of ethyl alcohol, 5 ml of liquid anhydrous ammonia and 0.1 g Raney nickel was 12 hours at 100 ⁰ C under a hydrogen pressure of 154 heated at. The cooled solution was filtered and concentrated in vacuo. The remaining oil was distilled at 165 ° CZ9 μ, the product passing over.

Coupler XIII, Intermediate C

1-Oxy-N - [(5- (3-pentadecylphenoxy) butyl] -2-naphthamide

A mixture of 5 g of phenyl-l-oxy-2-naphthoate and 7 g of intermediate B was ¹ Z heated in vacuo for ₂ hr at 15O ⁰ C. The phenol distilling off from the reaction mixture was collected. The remaining oil was poured into 100 ml of petroleum ether, a crystalline, solid material separating out. This was collected and recrystallized from 90 ml of ethyl alcohol. Were obtained 8 g of product, mp. 64 to 66 ⁰ C.

Coupler XIII, Intermediate D

l- (4-nitrophenyl) -3-methyl-

4- (l, 5-disulfo-3-naphthylazo) -5-pyrazolone,

Disodium salt

To a solution of 2.8 g of 1- (4-nitrophenyl) -3-methyl-5-pyrazolone, 0.5 g of sodium hydroxide and 7 g of sodium acetate in 40 ml of water, a diazonium solution was added ^{at 20 ° C. in the course of 20 minutes} from 1.1 g of 2-amino-1,5-naphthalenedisulfonic acid, disodium salt, 1.4 g of sodium nitrite, 2 ml of concentrated sulfuric acid and 10 ml of water. The mixture was stirred at room temperature for 1 hour and then heated on a steam bath until all of the solid material was dissolved. The solution was ^{cooled to 5 °} C. and the precipitated solid material was filtered off. 4.5 g of product were obtained.

Coupler XIII, Intermediate E

l- (4-aminophenyl) -3-methyl-

4- (l, 5-disulfo-3-naphthylazo) -5-pyrazolone,

Disodium salt

To a mixture of 31 g of Intermediate D and 32 mL of water was stirred at 9O ⁰ C in the course of 20 minutes a solution of 18 g 60 ⁰ Z _o added sodium sodium sulfide in 40 ml of water. The mixture was then further heated for 2 hours under reflux, then cooled to 50 ⁰ C and acidified with acetic acid. The precipitated solid material was filtered off with suction and recrystallized from 250 ml of 10 "sodium chloride solution, 15 g of product, melting point> 250 ° C., being obtained.

Coupler XVII
1-oxy-4-stearoyloxymercuri-2-naphthoic acid

To a solution of 9.4 g of l-oxy-2-naphthoic acid (Journal of America Chemical Society, p. 799 [1942]) in 200 ml of dioxane was a solution of 38 g of mercury (II) stearate in 500 ml of dioxane was added and the mixture was heated on a steam bath for 5 hours. This caused a white solid material to precipitate which was filtered off, washed with hot methyl alcohol and dried. Yield 30g of product.

Coupler XVIII
l-oxy-4-dodecyloxy-2-naphthoic acid

To a suspension of 2 g of 1,4-dioxy-2-naphthoic acid (Journal of America chemical Society, 64, p. 799

[1942]) in 40 g of lauryl alcohol was at 90 ° C for 11 hours introduced dry hydrogen chloride with stirring. The clear reaction solution became overnight left to stand at room temperature and the solid white material which then separated out was filtered off, in Suspended 50 parts by volume of petroleum ether, filtered off again and dried. 1.25 g were obtained Product, m.p. 135 to 136 ° C.

Coupler XXI

I -Oxy- N - (// - sulfoethyl) -4- (4-octadecyloxyphenylazo) -

2-naphthamide, potassium salt

To a solution of 51 g of potassium hydroxide and 63 g of intermediate A in 350 ml of water and 1700 ml of ethyl alcohol, a diazonium solution was added at 5 ° C in the course of one hour, which consists of 72 g of intermediate B, 120 g of p-toluenesulfonic acid and 30 g of isoamyl nitrite in 2 liters of n-propyl alcohol was. The mixture was stirred at room temperature for 5 hours, after which 3 liters of water were added and reflux the mixture. The hot solution was filtered with glacial acetic acid acidified and chilled. The precipitated solid material was filtered off from 1.5 liters of n-butyl alcohol recrystallized and dried. 60 g of product were obtained, melting point 228 to 230 ° C.

Coupler XXI, intermediate A I -oxy-N - (/ S-sulfoethyl) -2-naphthamide, potassium salt

A mixture of 132g phenyl- (l-oxy-2-naphthoate),

I1 ethyl alcohol, 57.5 g taurine, 300 ml water and 28 g of potassium hydroxide were refluxed for 15 hours. The solution was then cooled down precipitated solid material collected, washed with ethyl alcohol, recrystallized from water and dried. Yield 71 g of product, melting point 284 to 286 ° C.

Coupler XXI, Intermediate B

4-octadecyloxyaniline

39 g of 4-nitrophenyloctadecyl ether (Journal of America Chemical Society, 73, p. 458 [1951]) and 0.5 g of 10% palladium on charcoal catalyst in 300 ml of ethyl alcohol were at 50 ° CV for ₂ hours under hydrogen under a pressure of 3 , 5 at heated.

The catalyst was filtered off from the warm solution and the solution was cooled. The precipitated solid material was filtered off with suction and dried. Were obtained 32 g of product, mp. 78 to 81 ^C C.

Coupler XXX

2- (3,5-disulfobenzamido) -

4- (4-oxy-2-pentadecylphenylazo) -5-methylphenol, dipotassium salt

To a solution of 21 g of 2- (3,5-dichlorosulfonylbenzamido) -5-methylphenol in 50 ml of pyridine and 10 ml of water, a solution of 16 g of 4-amino-3-pentadecylphenol, 7 g of isoamyl nitrite, 10 ml of concentrated hydrochloric acid and 100 ml of n-propyl alcohol prepared diazonium solution was added and the resulting mixture was stirred at room temperature for 12 hours. The mixture was then poured into 400 ml of saturated potassium chloride solution. The solid, gummy material which separated out was collected, rubbed twice in methyl alcohol and dried. Were obtained 11 g roduct ^D.

Coupler XXXVI

l-phenyl-3- (3-sulfobenzamido) -

4- (4-octadecyloxyphenylazo) -5-pyrazolone,
Sodium salt

To a solution of 3.6 g of Intermediate B ίο below and 2 g of sodium hydroxide in 55 ml of 9O ° / pc alcohol ethyl alcohol was added at ⁰ ° C with stirring, a of 3.6 g of 4-Octadecyloxyanilin (Intermediate B of coupler XXI), 5 , 7 g of p-toluenesulfonic acid, monohydrate, and 1.5 g of isoamyl nitrite in 100 ml of n-propyl alcohol are added to the diazonium solution. The mixture was further stirred at room temperature for 2 hours, after which 25 ml of water were added and acidified with acetic acid. 100 g of sodium chloride were then added to this solution at 90 ° C. and the resulting solution was filtered and cooled. The precipitated solid matter was collected, washed with water and dried. 6 g of product were obtained, melting point 198 to 200 ° C.

Coupler XXXVI, Intermediate A

1-phenyl-3- (3-chlorosulfonylbenzamido) -5-pyrazolone

To a solution of 88 g of l-phenyl-3-amino-5-pyrazolone in 400 ml of diethyloxalate, 120 g of m-chlorosulfonylbenzoyl chloride were added at 90 ° C. with stirring. The mixture was ^{heated for 1} l for ₂ hours, cooled to 20 ° C., the solid material which had separated out was filtered off, rubbed with water and ethyl acetate and dried. 98 g of product were obtained, melting point 176 to 177 ° C.

Coupler XXXVl, intermediates
1-phenyl-3- (3-sulfonbenzamido) -5-pyrazolone

A mixture of 58 g of Intermediate A and 250 ml of 10 ° / ₀ 'ger sodium hydroxide solution was 2 hours at room temperature. The resulting solution was acidified with concentrated hydrochloric acid, a solid precipitate separating out. The precipitate was filtered off, washed with water and dried, 23 g of product, melting point 292 ° C. (decomposition), being obtained.

Couplers XXXVII and XXXVIII were each made according to that given for Coupler XXXVI above Process prepared using the appropriate intermediates.

Coupler XXXIX

1-phenyl-3- (3,5-disulfobenzamido) -4- (4-oxy-2-pentadecylphenylazo) -5-pyrazolone
Dipotassium salt

To a solution of 5 g of l-phenyl-3- (3,5-disulfobenzamido) -5-pyrazolone, Dipotassium salt which is prepared using the procedure given above for Intermediate B of Coupler XXXVI of the corresponding intermediates was prepared in 20 ml of 50% pyridine at 20 ° C Diazonium solution added, which consists of 3 g of 4-amino-3-pentadecylphenol, 1.5 g of isoamyl nitrite, 2 g of concentrated hydrochloric acid and 20 ml of n-propyl alcohol were obtained was. The mixture was stirred for 12 hours at room temperature and then poured into 100 ml

poured saturated potassium chloride solution. The precipitated solid material was filtered off and ^{recrystallized from 50 ml of 60% strength em} ethyl alcohol.

Couplers XL through XLIV were each made after that for coupler XXXIX above using the appropriate intermediates.

Coupler XLV

l- [4- (3,5-dicarboxybenzamido) phenyl] -

3-ethoxy-4- (3-octadecylcarbamylphenylthio) -

5-pyrazolone

A mixture of 7.8 g of the intermediate product H, »5 25 ml of ethyl alcohol, 15 ml of 2 normal aqueous sodium hydroxide solution and 35 ml of water was stirred at 85 ° C for 15 minutes. The solution was cooled to room temperature and with 1: 2 concentrated HCl water acidified. ao

The precipitated solid material was filtered off, washed with water and acetonitrile and removed Recrystallized methanol. Obtained 4 g of product, m.p. 200 to 202 ° C.

Coupler XLV, Intermediate A
1- (4-nitrophenyl) -3-ethoxy-5-pyrazolone

31 g of 4-nitrophenylhydrazine, 100 ml of ethyl alcohol and 38 g of ethyl / 9, j8-diethoxyacrylate were refluxed for ¹ Z ₂ hours. A solution of sodium ethylate, which had been prepared from 4.6 g of sodium and 100 ml of ethyl alcohol, was then added and the mixture was refluxed for a further 20 minutes. The solution was then acidified with glacial acetic acid and the precipitated solid material was filtered off. After recrystallization from 250 ml of n-butyl alcohol, 31 g of product, melting point 153 to 154 ° C., were obtained.

40

Coupler XLV, intermediate B
1- (4-aminophenyl) -3-ethoxy-5-pyrazolone

15 g of intermediate A in 150 ml of ethyl alcohol were at a hydrogen pressure of 3.5 at using palladium animal charcoal reduced as a catalyst. The catalyst was filtered off and the solution poured into 500 ml of water. The precipitated product was filtered off and air-dried. Were received 8.2 g of product, m.p. 121-122 ° C.

Coupler XLV, Intermediate C
Triethyl trimesate

A mixture of 37 g of trimesic acid (Proceedings of the North Dakota Academy of Science, 8, p. 54 [1954]; Chemicae Abstracts [1955], 8898 b), 100 ml ethyl alcohol, 50 ml benzene and 1 ml concentrated Sulfuric acid was added for 24 hours using a 15 cm packed column attached to the reaction flask and refluxed with a water separator. The residue was cooled and the product which has crystallized out is filtered off and dried. The yield of triester was 38 g, Mp. 133 to 135 ° C.

55

60 42
Coupler XLV, intermediate D

Diethyl ester of trimesic acid
(3,5-dicarbethoxybenzoic acid)

To a solution of 147 g of intermediate C above in 21 ethyl alcohol was added with stirring 250 ml of 2 η sodium hydroxide solution in 500 ml of ethyl alcohol are added. The resulting mixture was 30 minutes boiled under reflux and then stirred for 12 hours at room temperature. The eliminated solid Material was filtered off and recrystallized from a mixture of 500 ml of ethyl alcohol and 500 ml of water, 80 g of product, melting point 153 to 155 ° C., were obtained.

Coupler XLV, Intermediate E
3,5-dicarbethoxybenzoyl chloride

300 g of intermediate D and 2 l of thionyl chloride were refluxed for 2 hours and then concentrated in vacuo.

250 ml of dry benzene were added to the residue and the mixture was again concentrated in vacuo. The acid chloride obtained was used without further purification for the preparation of the intermediate product F used.

Coupler XLV, intermediate F.

1- [4- (3,5-Dicarbethoxybenzamido) phenyl] -3-ethoxy-5-pyrazolone

A mixture of 6.6 g of intermediate B and 8.5 g of intermediate E and 100 ml of dry acetonitrile was refluxed for 5 hours. The mixture was cooled to room temperature, the precipitated solid material was filtered off, dried and recrystallized from glacial acetic acid. Were obtained 10 g of product, mp. 200-201 ⁰ C.

Coupler XLV, intermediate G
3-octadecylcarbamylphenylsulfenyl chloride

In a suspension of 8 g of 3,3'-Dioctadecylcarbamyldiphenyldisulfid in 120 ml of anhydrous KohlenstofftetrachloridwurdetrockenesChlorl ^ ¹ hours at room temperature initiated, said AND ALL solid material dissolved, and finally a clear pale yellow solution was obtained. This solution was concentrated in vacuo to a volume of 50 ml to remove excess chlorine.

The resulting solution of sulfenyl chloride in carbon tetrachloride was used as such for the following Reaction, d. H. the production of the intermediate product H, is used.

Coupler XLV, intermediate H

1- [4- (3,5-dicarethoxybenzamido) phenyl] -

3-ethoxy-4- (3-octadecylcarbamylphenylthio) -

5-pyrazolone

A mixture of the above sulfenyl chloride solution and 9.35 g of intermediate F in 200 ml dry dioxane was stirred at room temperature for 2 hours, then under reflux for 1 hour heated and concentrated in vacuo.

609 728/362

The residue was recrystallized from ethyl alcohol to obtain 8.5 g of product, mp. 158 ⁰ C were bis 156 was obtained.

Coupler XLVI

l- (4-sulfophenyl) -3- (4-sulfoanilino) -

4- (3-octadecylcarbamylphenylthio) -5-pyrazolone,

Disodium salt

A suspension of 25 g of Intermediate B in 100 ml ethyl alcohol and 200 ml of 2 ° / ₀ sodium hydroxide solution was stirred V ₂ hour at room temperature; during this time all solid material dissolved. The solution was cooled, acidified with 5 ml of acetic acid and concentrated in vacuo. The crude residue obtained was recrystallized from methyl alcohol, 10 g of product, melting point> 250 ° C., being obtained.

Coupler XLVI, Intermediate A

1- (4-fluorosulfonylphenyl) -3- (4-fluorosulfonylanilino) -5-pyrazolone

To 450 ml fluorosulfonic ° C with stirring, 80 g of l-phenyl-S-S-anilino-pyrazolone was added and after solution at 5O ⁰ C stirred for a further ₂ hours at 4V. 5 It was then poured onto 2 kg of crushed ice. The precipitated solid material was collected, washed with water, filtered and dissolved in 2 liters of ethyl acetate. This solution was washed with 5% sodium bicarbonate solution, water and saturated saline solution. The solution was then concentrated in vacuo and the residue was recrystallized from acetonitrile. 36 g of product were obtained, melting point 290 ° C. (decomposition).

Coupler XLVI, Intermediate B

l- (4-fluorosulfonylphenyl) -

3- (4-fluorosulfonylanilino) -

4- (3-octadecylcarbamylphenylthio) -5-pyrazolone

A mixture of Intermediate G of Coupler XLV (made from 24.5 g of the disulfide) and 25 g of intermediate A in 330 ml of dry carbon tetrachloride was added at 55 ° C for 12 hours touched.

The solution was then concentrated in vacuo and the residue was recrystallized from 300 ml of ethyl acetate, 25 g of product, melting point 209 to 211 ° C., were obtained.

Coupler XLVII

4,4 '- (4-octadecyloxybenzylidene) -

bis- [l-phenyI-3- (3,5-disulfobenzamido) -

5-pyrazolone], tetrapotassium salt

A solution of 1.9 g of intermediate A was added to a refluxing solution of 5.2 g of l-phenyl-3- (3,5-disulfobenzamido) -5-pyrazolone, dipotassium salt, in 45 ml of ethyl alcohol and 20 ml of water and 0.5 g of piperidine in 35 ml of ethyl alcohol were added. The solution was ^{refluxed for 1} J for ₂ hours and then cooled to room temperature. The precipitated solid material was isolated and ^{recrystallized from 90 0} ZoIgS ¹ Ti ethyl alcohol. 5 g of product were obtained.

Coupler XLVII, Intermediate A
4-octadecyloxybenzaldehyde

To a solution of 23 g of sodium metal and 122 g of 4-oxybenzaldehyde in 500 ml of ethyl alcohol 333 g of 1-bromooctadecane were added. The mixture was refluxed with stirring for 20 hours cooked, with a solid material precipitating. This was filtered off and the filtrate in vacuo constricted. The remaining material was then distilled at 253 ° C / lmm, with 250 g Product were obtained.

Coupler XLVIII

a-Benzoyl-'x- (4-oxy-2-pentadecylphenylazo) -4- (3-sulfobenzamido) acetanilide, Sodium salt

To a solution of 4.5 g «-Benzoyl-4- (3-chlorosulfonylbenzamido) -acetanilide in 12 ml of 90% pyridine was a diazonium mixture at 20 ° C, which from 3.2 g of 4-amino-3-pentadecylphenol, 1.4 g of isoamyl nitrite, 2 ml of concentrated hydrochloric acid and 20 ml n-propyl alcohol was obtained, added. The received Solution was stirred for 12 hours at room temperature and then in 50 ml of saturated sodium chloride solution poured. The precipitated solid, yellow-colored material was isolated and extracted twice Recrystallized ethyl alcohol, 2.2 g of product being obtained.

The XLIX coupler was designed for the Coupler XLVIII procedure given above using the appropriate intermediates manufactured.

Coupler LI

α-Benzoyl-α - ^ - octadecylcarbamylphenylthio) -3,5-dicarboxyacetanilide

A solution of 3-octadecylcarbamylphenylsulfenyl chloride was added at 50 ° C. to 7 g of intermediate A in 100 ml of dioxane (Intermediate G of Coupler XLV, prepared from 8.1 g of the disulfide) in 100 ml of dioxane was added. The mixture obtained was stirred for 12 hours and then concentrated in vacuo. The gummy residue was in

100 ml of ethyl alcohol dissolved, then 13 ml of 2 normal aqueous sodium hydroxide solution added and the mixture Heated to 40 ° C for 1 hour. It was then acidified with concentrated HCl, the precipitated

solid material isolated and recrystallized twice from ethyl alcohol, 2 g of product, melting point 140 to 142 ° C.

Coupler LI, Intermediate A
'x-Benzoyl-SS-dicarbomethoxyacetanilide

To a refluxing mixture of 102 g of ethyl a-benzoylacetate and 5 g of sodium acetate 105 g of dimethyl 5-aminoisophthalate were added in 100 ml of xylene. The solution was then Boiled under reflux for 3 hours and then concentrated to half the original volume and cooled to room temperature. The precipitated solid material was collected and made from methyl alcohol recrystallized, 40 g of product, melting point 165 ° to 167 ° C., being obtained.

The following examples illustrate embodiments of the invention.

45 46

Example 1 X-sulfophenoxy) -benzamido] -phenäthyl} -x- (l-phenyl-

5-tetrazoIylthio) hydroquinone containing gelatin

A color film essentially similar to that shown in FIG. 1 silver bromide iodide emulsion and contained about

The construction shown was prepared by adding 100 mg of gelatin, 75 mg of silver and 60 mg of ^{0.09 m 2}

on a compound I provided with a backing layer.

Cellulose acetate film backing successively the following layers 16
Layers were applied that numbered the

Layers of FIG. 1 correspond. The layer consisted of one of the couplers

l- (2,4,6-trichlorophenyl) -3- {3 - [«- (2,4-di-tert-amyl-

Schicn 11 ₁₀ phenoxy) -acetamido] -benzamido} -4- (p-methoxyphe-

The layer consisted of a zinc sulfide nucleus nylazo) -5-pyrazolone and the potassium salt of 2-octa-

(ZnS), the coupler l-oxy-4- (3-octadecylcarbamyldecyl-5-sulfohydroquinone containing gelatin-sil-

phenylthio) -N-ethyl-3 ', 5'-dicarboxy-2-naphthanilid berjodidemulsion and contained about 0.09 m ^{2 of} the

and the antioxidant, 1-octadecyl-S-sulfohydroquinone, layer 100 mg gelatin, 50 mg silver, 66 mg coupler

Potassium salt, containing gelatin-chlorosilver emul- 15 and 30 mg of sulfohydroquinone. The yellow pyr

sion and contained 100 mg of azolone coupler on about 0.09 m ^{2 of} the layer. This layer was used in the present case

Gelatin, 40 mg silver, 2.7 ■ 10 ~ ⁷ g ZnS, 50 mg case as a light filter to make the blue image exposure

Coupler and 15 mg of antioxidant. The phenolic limit the layer 18.
Coupler of this layer was included in the implementation

the oxidized color developing agent in the non-20 layer 17

development-inhibited areas of the layer 11. The layer consisted of a zinc sulfide seed

diffusing blue-green indoaniline dye image. (ZnS), the coupler χ - Benzoyl - ■% - (3 - octadecylcarb-

... ... amylphenylthio) -3,5-dicarboxyacetanilide and that

Layer 12 potassium salt of 2-octadecyl-5-sulfohydroquinone as

The layer consisted of a red-sensitive gelatin-chlorosilver emulsion containing 25 antioxidants.

Hydroquinone compound I, {4- [3- (4-tert-amyl-x-sulfosion and contained 100 mg gelatin ^{per 0.09 m 2,}

phenoxy) -benzamido] -phenäthyl} -x- (l-phenyl-5-tetra- 50 mg silver, 1.1 · 10 ~~ ^e g ZnS, 100 mg coupler and

zolylthio) hydroquinone containing gelatin silver 15 mg of sulfohydroquinone. The matchmaker of this

bromide iodide emulsion and contained on a 0.09 m ² layer produced a diflfun

of the layer 100 mg of gelatin, 75 mg of silver and 60 mg of 30 mg of the yellow azomethine dye,
the compound I. The hydroquinone compound of these

Layer and layers 15 and 18, layer 18 oxidized
with oxidized color developer in the exposure The layer consisted of a hydroquinone area with the formation of a quinone, from which the compound I, 2- {4- [3- (4-tert-amyl-x-sulfophenoxy) -um a mercaptan , ie in the present case phenyl-benzamido] -phenäthyl} -x- (1-phenyl-5-tetrazolylthio) -mercaptotetrazole, which contained the enthydroquinone-containing blue-sensitive gelatin development of the halide silver in the neighboring silver bromide iodide emulsion and contained approximately areas of layers 11, 14 and 17 inhibited or 0.09 m ^{2 of} the layer 100 mg gelatin, 75 mg silver suppressed. and 30 mg of compound I.

Layer 13 ⁴ ° The ^ iIm became a colored picture object

exposed and the exposed material together with

The layer consisted of a non-diffuse paper receiving sheet that had a gelatin layer

ding purple-red colored filter dye 1-Oxy- with a mordant such as cetyltrimethylammonium-

4 '- (4-tert-butylphenoxy) -4-phenylazo-2-naphthamide bromide contained in a color developer solution of the

and the antioxidant 2-octadecyl-5-sulfo-hydro- 45 immersed in the following composition:
quinone, potassium salt, containing silver iodide emulsion

and contained 100 mg ascorbic acid 200 mg on about 0.09 m ^{2 of the layer}

Gelatin, 50 mg silver, 30 mg filter dye and 4-amino-N-ethyl-N-ß-oxyethylaniline sulfate 4 g

30 mg of antioxidant. The silver iodide of this layer is 4-amino-N-ethyl-N- / 3-methylsulfon-

and the layer 16 was used to diffuse the 50 amidoethyl-2-methylaniline sulfate Ig

Mercaptans from layers 12 and 15 upwards Sodium carbonate, monohydrate 40 g

to prevent. Aminoethanol 2 ml

",. , Potassium bromide 500 mg

bcnicnt 14 sodium thiosulfate, pentahydrate 200 mg

The layer consisted of a zinc sulfide seed 55 6-nitrobenzimidazole nitrate 5 mg

(ZnS), the coupler l-phenyl-3- (3,5-disulfobenzamido) - made up to the liter with water,

4- (2-oxy-4-n-pentadecylphenylazo) -5-pyrazolone, Di- _p H adjusted to 11.0,
potassium salt and 2-octadecyl-5-sulfohydroquinone,

Potassium salt, containing gelatin-chlorosilver emul- The exposed film and the recording sheet were sion and contained on about 0.09 m ^{2 of} the layer 100 mg 60 then about 5 minutes at 29 ° C together (in Kon gelatin, 40 mg silver, 5, 5 · 10 ~ ^e g ZnS, 50 mg cycle) pressed. The exposed coupler and 15 mg of the sulfohydroquinone developed. This halogen silver in layers 12, 15 and 18, and pyrazolone coupler, produced a diffusing purple azomethine dye image in these layers, which was red-colored with the hydroquinone compound I. with that formed in the development reaction

ς 1, · y. _t ic ⁶ 5 oxidized color developer oxidized, creating a

Layer ID made development-inhibiting mercaptan free

The layer consisted of a green-sensitive, which was the development of neighboring

the hydroquinone compound I, 2- {4- [3- (4-tert-amyl surfaces of the emulsion containing the nuclei

47 48

layers 11, 14 and 17 prevented. The remaining gelatin, 49 mg of silver, 5.4 × 10 ^-6 g ZnS, 50 mg

Developer solution migrated to the positive surfaces and couplers. 15 mg of the hydroquinone. The previous

11, 14 and 17 and caused the physical in-plane coupler to be incorporated in color development

Development of silver halide present, with diffusing purple-red azomethine dye image.

simultaneously diffusing blue-green, purple-red and 5

Yellow dye images were generated that were derived from rail 15

The layers concerned were imaged by diffusion. The layer consisted of a green-sensitive,

the pickled recording sheet to form a colored hydroquinone compound 2- {4 - [(4-tert-amyl-.r-

fair, positive reproduction of the original sulfophenoxy) -benzamido] -phenäthyl} -x- (l-phenyl-

were transferred. Io 5-tetrazolylthio) hydroquinone containing gelatin

Silver bromide iodide emulsion and contained about

^Bei P ^{iel 2} 0,09m ² of the layer of gelatin 100mg, 75mg silver

A color film substantially similar to that shown in FIG. 1 and 30 mg of the hydroquinone compound.
structure shown was produced by _,. , ₁ ,
on a cellulose acetate film support the layer 16 in succession
following layers, the numbered layers The layer consisted of one of the yellow filters in F i g. 1 were applied. dye l- (2,4,6-trichlorophenyl) -3- {3 - [«- (2,4-di-tert.-

amylphenoxy ^ acetamidoj-benzamidol ^ -ip-methoxy-

Not 11 phenylazo) -5-pyrazolone and the antioxidant 2-octa-

The layer consisted of a zinc sulfide seed containing 20 decyl-S-sulfohydroquinone, potassium salt

(ZnS), the coupler 1-oxy-4- (3-n-octadecylcarbamyl gelatin silver iodide emulsion and contained to about

phenylthio) -N-ethyl-3 ', 5'-dicarboxy-2-naphthamide 0.09m ^{2 of} the layer 100mg gelatin, 50mg silver,

and in addition 2-octadecyl-5-sulfohydroquinone, Ka- 66 mg of yellow filter dye and 30 mg of the hydro-

lium salt (as an antioxidant), containing gelatin quinones. The filter dye on this layer was used to

Silver thiocyanate emulsion and contained on about 0.09m ² 25 the blue image exposure to be applied to layer 18

limit the layer 100 mg gelatin, 30 mg silver, 2.7 x 10- 'g.

ZnS, 50 mg of coupler and 15 mg of the hydroquinone. Layer 17
The phenolic coupler provided this layer

the reaction with the oxidized color developing The layer consisted of a zinc sulfide seed

agent in the non-developmentally inhibited areas 30 (ZnS), the coupler jc-benzoyl-a- (3-octadecylcarb-

the layer 11 a diffusing blue-green indo-amylphenylthio) -3,5-dicarboxyacetanilide and 2-octa-

aniline dye image. containing decyl-5-sulfohydroquinone, potassium salt

<ioh ' ht 19 gelatin-silver thiocyanate emulsion and contained

_{about 0.09 m 2 of the layer 100 mg of gelatin;} 40 _mg

The layer consisted of a red-sensitive, the 35 silver, 7.2 × 10 ^-7 g ZnS, 100 mg coupler, and 15 mg hydroquinone compound I, 2- {4- [3- (4-tert-amyl; c- of The coupler of this layer sulfophenoxy) -benzamido] -phenäthyl} -x- (1-phenyl- produced a diffusing gelatin-yellow azomethine dye image containing 5-thiazolylthio) hydroquinone during color development.
Silver bromide iodide emulsion and contained about 1S

0.09 m ^{2 of} the layer 160 mg gelatin, 112 mg silver 40 cement OK

and 45 mg of compound 1. The layer consisted of a blue-sensitive,

The hydroquinone compound of this layer and the hydroquinone compound I, 2- {4- [3- (4-tert-amy-x layers 15 and 18 oxidized in the Beiich-sulfophenoxy) -benzamido] -phenäthyl} -. V- (1-phenylation range with oxidized color developer, whereby 5-tetrazolylthio) hydroquinone containing gelatin

the tetrazolylthio residue was released, which prevented the development of silver bromide iodide emulsion and contained 100 mg of gelatin and 75 mg of silver silver salt of layers 11, 14 and 17 ^{on approximately the adjacent 0.09 m 2 of the layer containing the zinc sulfide nuclei.} and 30 mg of the hydroquinone compound I.

The film thus obtained was exposed to a colored image layer 13 and covered with a receiving sheet

The layer consisted of a non-diffuse paper, which had a gelatin layer containing a mordant such as cetyltrimethyldating magenta-colored filter dye 1-oxyammonium bromide on-4 '_ (4-tert-butylphenoxy) -4-phenylazo-2-naphthamide , immersed in a color developing solution of the following, as well as 2-octadecyl-5-sulfohydroquinone, potassium salt, composition:
containing gelatin-silver iodide emulsion and contained 80 mg gelatin, 55 ascorbic acid 200 mg ^{on about 0.09 m 2 of the layer}

50 mg silver, 22.5 mg filter dye and 30 mg of 4-amino-N-ethyl-N - /? - oxyäthyl-

Hydroquinones. The silver iodide of this layer and anihnsulfat 5 g

that of the layer 16 served to provide a diffusion of Na ₂ CO ₃ · H ₂ O 40 g

of the mercaptan from layers 12 and 15 to N, N-diethyl-1,3-propanediamine ImI

to prevent above. 60 sodium thiosulfate (pentahydrate) 100 mg

Layer 14 Μ ' ¹ ^ O filled up ^{to the liter,}

pH adjusted to 11.0,

The layer consisted of a zinc sulfide seed

(ZnS), the coupler l-phenyl-3- (3,5-disulfobenzamido) - and at about 30 ^c C for 5 minutes with the Papierauf-

Leave 4- (2-oxy-4-n-pentadecylazo) -5-pyrazolon, dipotassium-65 recording sheet in effective contact. Included

salt, as well as 2-octadecyr-5-sulfohydroquinone, potassium, the exposed halogen silver developed in the

salt, containing gelatin-silver thiocyanate emulsion layers 12, 15 and 18, and those present therein

and contained 100 mg of the hydroquinone compound on about 0.09 m ^{2 of the layer, oxidized with the}

49 50

the oxidized dye-green dye-forming coupler 2- (3,5-disulfodeveloping agent, which caused the oxybenzamido) -5-methyl-4- (4-octadecyloxyphenylazo) -dated hydroquinone compound to form the developmental phenol, dipotassium salt , was released in place of the inhibiting mercaptan used there, which kept the purple-red dye-forming coupler from developing on the adjoining surfaces of the silver 5. In doing so, 87 mg of the coupler were applied to about thiocyanate emulsion layers 11, 14 and 17 respectively, 0.09 m ^{2 of} the layer,
prevented. The rest of the positive areas of the “,. ,
Layers 11, 14 and 17 migrated developer solution Layer 25
developed the silver thiocyanate present there.This layer was essentially the same as physically to silver and the formed oxidized layer 22, but this time instead of the green color developer, one of these layers produced diffusible cyan, magenta-red sensitive silver halide emulsion in the development areas Gelatin-silver chlorobromide emulsion and yellow dyes, which was applied imagewise by diffusion,
the stained receiver sheet was transferred and layer 26
then a positive multicolor reproduction of the 15th

original subject matter. This layer was essentially the same as

. shift 23, except that so much Carey

B ei game 3 Lea silver was added to the emulsion that

A color film essentially similar to that shown in FIG. 2 4.6 mg of this came to about 0.09 m ^{2 of} the layer,

corresponded to the structure shown in the drawing, was 20

produced by a ^{c 1C}

Cellulose acetate film supports sequentially with the fol- This layer was essentially the same as

The lowering layers that correspond to the numbered layers of layer 21, with the exception, however, that the

F i g. 2 corresponded, was coated. fogged silver halide emulsion in place of the

25, a magenta image dye forming coupler

Layer 21 this time the yellow dye-forming coupler. The layer consisted of a fogged gel-oxy-4- (2,4-dinitrophenylthio) -N - [<5- (2,4-di-terttine-silver chlorobromideiodide emulsion, the 1 mole of amylphenoxy) butyl] -2-naphthamide.
Silver halide, 8400 ml l% strength aqueous solution of ^e ". , - "
a purple dye-forming coupler 1-phenyl-30 bcnicnt 28
3- (3,5-disulfobenzamido) -4- (4-octadecyloxyphenylazo) - This layer was essentially the same as 5-pyrazolone, disodium salt, further 740 ml of 7.5 ⁰ / _O strength layer 22, except that this time to Instead of the green-aqueous, saponin solution, 134 ml of 2.7% aqueous sensitized halosilver emulsion contained a blue-emulsion-mucochloric acid solution and as much water as the sensitive gelatin-silver chlorobromide emulsion that the total weight was 22.1 kg, and which 35 was used,
was applied to the carrier in such a way that on about layer 29
0.09 m ^{2 of} the layer 184 mg gelatin, 30 mg silver

and 30 mg of the coupler came. The layer consisted of a protective gelatin layer

with 50 mg gelatin to about 0.09 m ² .

bchicht II ^ ₀ j-jj _e veiled halogen silver emulsions were The layer consisted of a green sensitized prepared by applying the relevant emulsions gelatin silver chlorobromide iodide emulsion, 1 mol 30 seconds with a 40 watt silver halide about 1.5 m away, the hydroquinone compound V, Lamp were exposed.

2- [4- (3,5-Disulfobenzamido) -phenäthyl] -x- (l-phenyl- The film obtained was (in a camera) a

5-tetrazolylthio) -hydroquinone, disodium salt (Di- 45 colored picture object exposed and the exposed

hydrate), dispersed in aqueous gelatin solution, film and a paper receiving sheet, which is a

400 ml 7.5% saponin, 37 ml 2.7% muco pickling agents such as dimethyl / 3-oxyethyl - «- (octadecyl-

chloric acid and so much water that the amido) propylammonium dihydrogen phosphate contained

Total weight of the emulsion was 12 kg, and had the gelatin layer, in a color developing

which was applied to the layer 21 in such a way that 50 ler solution of the following composition was immersed: on about 0.09 m ^{2 of} the layer 214 mg of gelatin,

62 mg of silver and 91 mg of the hydroquinone compound V sodium carbonate 20 g

came. Sodium hexametaphosphate 20 g

. Benzyl alcohol ...... 10 ml

layer 23 ^ a-acetamido ^ amino-N.N-diethylaniline .. 2 g

The layer consisted of a gelatin-silver- filled up to the liter with water,

chloride emulsion, the 1 mole of halogen silver, 2.6 ml pjj _au f \\ set.
7.5 ° / oig ^it saponin, 43 ml of 2.7% strength mucochloric

and contained water enough to make the total weight of The film and the receiving paper sheet

the emulsion was 6480 g, and which was ^{squeezed together for about 5 minutes at about 29 °} C. in this way,

the layer 22 was applied so that on about 0.09 m ² developed the exposed halogen silver in the

of the layer 200 mg of gelatin and 100 mg of silver layers 22, 25 and 28 of silver, and the hydro

came. quinone compound V in the development area of this

Layer 24 layers oxidized with the

65 reaction formed oxidized color developing

This layer was essentially the same as the medium, causing one in the adjoining areas of the

the layer 21, with the exception that the layers 21, 24 and 27 diffusing mercaptan

layered halogen silver emulsion was made blue-free for some, the development of the

51 52

layered halogen silver in the relevant areas, layer 13
inhibited, while the unexposed developable,

veiled halogen silver in the positive areas The layer consisted of an antioxidant

of layers 21, 24 and 27 by the immigrated 2-octadecyl-5-sulfohydroquinone, potassium salt, contained

remaining color developer solution with simultaneous BiI- 5 trending gelatin-silver iodide emulsion, which in such a way

manure of diffusible purple-red, blue-green or the layer 12 was applied that on about 0.09 m ²

Yellow dyes physically developed into silver 100 mg gelatine, 50 mg silver and 30 mg of the hydro

became. The image dyes formed came from diffused quinones. The silver iodide of this layer and

essentially simultaneously image-wise on which the layer 16 served to prevent a diffusion of mer-

pickled receiving layer of the paper receiving sheet »o captan from layers 12 and 15 towards the top

and created a multicolored positive image on it,

of the original item. Layer 14

Those described in Examples 1, 2 and 3

Color films were produced in a manner similar to that in the The layer consisted of a zinc sulfide seed (ZnS),

relevant examples described, also with the 15 the coupler l- (2,5-dichlorophenyl) -3- [3- (4-tert.-amyl-

developed the following developer: phenoxy) -benzamido] -5-pyrazolon and the compound 2-octadecyl-5-sulfohydroquinone, potassium salt,

Gelatin-chlorosilver emulsion containing 200 mg ascorbic acid and

4-Amino-N-ethyl-N - ^ - oxyäthyl- held on about 0.09 m ² 100 mg gelatin, 40 mg silver,

aniline sulfate .... '5 g ₂₀ 5.5 x 10 ~ ^β g ZnS, 70 mg coupler and 15 mg der

Sodium carbonate, monohydrate 40 g hydroquinone compound. This pyrazolone coupler

Sodium at 5 g produced a non-diffuse

N, N-Diethyl-1,3-propanediamine 1 ml of the dierent purple-red azomethine dye image.

Sodium thiosulfate (pentahydrate) 100 mg

Made up to the liter with water, ² 5 layer 15

pH adjusted to 11.0. _ ,,. ,

The layer consisted of a green sensitive,

The hydroquinone compound I, 2- {4- [3- (4-tert-amyl-

obtained similar test results. x-sulfophenoxy) -benzamido] -phenäthyl} -x- (l-phenyl-

. 30 5-tetrazolylthio) hydroquinone, sodium salt, contains

Example 4 gelatin silver bromide iodide emulsion and

A color film essentially similar to that shown in FIG. 1 held 100 mg of gelatin on about 0.09 m ^{2 of the layer,}

The structure shown was prepared by adding 75 mg of silver and 60 mg of the hydroquinone compound I.

on a cellulose,.

acetate film carrier successively the following layers, 35 layer Io

corresponding to the numbered layers in FIG. 1 corresponded, the layer consisted of a Carey Lea silver and

were applied. the antioxidant 2-octadecyl-5-sulfohydroquinone, Ka-

Layer 11 lium salt, containing gelatin silver iodide emulsion,

which was applied to the layer 15 that on

The layer consisted of a zinc sulfide seed (ZnS), 40 about 0.09 m ^{2 of} the layer, 100 mg of gelatin, 50 mg of the Couplerl-Oxy-N - [(5- (4-tert-amyl-2-butylphenoxy) - silver in Form of the iodide, 10 mg Carey Lea silver butyl] -2-naphthamide and the antioxidant, 2-octa- and 30 mg of the hydroquinone compound came in. The decyl 5-sulfohydroquinone, potassium salt, contained yellow Carey Lea silver of this layer served as light gelatin chlorosilver emulsion ■ and contained on about filter to limit the blue image exposure on layer 18 0.09 m ^z of layer 100 mg gelatin, 40 mg silver, 45.
2.7 · ΙΟ- ⁷ g ZnS, 60 mg coupler and 15 mg of the hydro-layer 17
chinons. The phenolic coupler of this layer

gave in the reaction with oxidized paint The layer consisted of a zinc sulfide seed (ZnS), developing agent in the non-developmentally inhibited coupler «- {4 - [« - (2,4-di-tert-amylphenoxy) -acet surfaces of the layer 11 a non-diffusing 50 amido] benzoyl} -2-methoxyacetanilide and the anti-blue green Indoaniline dye image. oxydans 2-octadecyl-5-sulfohydroquinone, potassium salt,

containing gelatin-chlorosilver emulsion and

layer 12 _ωβ11 . _{on about} Q _{09 m} a of _{the layer 100mg} gelatin, '

The layer consisted of a red-sensitive containing 50 mg of silver, 1.1 x 10 ~ ^e g of ZnS, and 100 mg of coupler

Hydroquinone Compound I, i.e. H. 2- {4- [3- (4-tert-amyl- 55 15 mg of the hydroquinone. The coupler of this layer

x-sulfophenoxy) -benzamido] -phenäthyl} -x- (l-phenyl- gave a non-diffusing one during color development

5-tetrazolylthio) hydroquinone, sodium salt, contains yellow azomethine dye image.
gelatin silver bromide iodide emulsion and

held 100 mg gelatin, layer 18, on about 0.09 m ^{2 of layer}
75 mg of silver and 60 mg of the hydroquinone compound I. 60 The layer consisted of a blue-sensitive layer which was The hydroquinone compound of this layer and hydroquinone compound I 2- {4- [3- (4-tert-AmyI-x-suld that of layers 15 and 18) oxidized with fophenoxy) -benzamido] -phenäthyl} -Ä :-( l-phenyl-5-teoxidized color developer in the area of the trazolylthio) hydroquinone, sodium salt, containing exposure to form a quinone, from the gelatin silver bromide iodide emulsion and contained on below Cleavage of the tetrazolylthio residue ^{, which resulted in approximately 0.09 m 2 of} the layer, 100 mg gelatin, 175 mg speaking mercaptan, which contained the desilver and 30 mg of the hydroquinone compound I.
winding in the adjacent surfaces of the halogen. The film obtained was inhibited from colored image silver layers 11, 14 and 17, respectively. object exposed and the exposed material

7 minutes at 24 ° C in a color developer
treated with the following composition:

Ascorbic acid 200.0 mg

4-Amino-N-ethyl-N - /? - oxyäthylaniline-

. sulfate 4.0 g

4-amino-N-ethyl-N - /? - methylsulfone-

amidoethyl 2-methylaniline sulfate 1.0 g

H ₂ O 40.0 g

Na ₂ SO ₃ 15.0 g

Aminoethanol 2.2 ml

Potassium bromide 500.0 mg

Sodium thiosulfate (pentahydrate) 200.0 mg

6-nitrobenzimidazole nitrate 5.0 mg

Filled up to the liter with water,
pH adjusted to 11.0.

Na ₂ CO _:

After the treatment, the material was washed thoroughly with water and placed in a clarifier and Treated fixer of the following composition: so

Sodium thiosulfate 150.0 g

Sodium bisulfite 20.0 g

Filled up to the liter with water.

The material was then treated in a bleach bath of the following composition:

Potassium dichromate 5.0 g

Potassium ferricyanide 70.0 g

Potassium bromide 20.0 g

Filled up to the liter with water.

The material was washed again and again with the clarifying and fixing bath specified above treated, whereupon washed again and in a stabilizing bath 'of the following composition was post-treated:

the positive reproduction of the original subject matter.

Claims (13)

Patent claims: 1. Color photographic material, consisting of a support and at least two thereon arranged color-forming units, which are opposite to different spectral ranges of the visible Sensitive to the spectrum and by a barrier layer consisting of a hydrophilic colloid are separated from each other, characterized in that the color-forming Units consist of 1. a photosensitive emulsion, consisting of a hydrophilic colloid and a Silver halide, 2. one in contact with the silver halide of the photosensitive emulsion non-diffusible hydroquinone compound represented by the following formula Formaldehyde, 37 percent by weight ... 7.0 ml
Dispersants, e.g. B. Octylphenoxypolyäthoxyäthanol 0.5 g Filled up to the liter with water. 40 45 During the color development, the exposed halogen silver developed in layers 12, 15 and 18 to silver, and the hydroquinone compound according to the invention present in these layers was from the oxidized color developer formed in the development reaction is oxidized. From the so educated Quinone, the development-inhibiting mercaptan in question was split off, which in the adjacent Areas of the emulsion layers 11, 14 and 17 containing the zinc sulfide, the development by the in This prevented residual color developing solution from migrating into these layers while in the positive Image areas of the exposed layers 12, 15 and 18 correspond to areas of the layers 11, 14 and 17, respectively the spontaneously developable silver halide physically with essentially simultaneous formation of non diffusing blue-green, magenta and yellow dyes in the corresponding layers to form silver was developed, which as well as the silver of the exposed layers and possibly still undeveloped silver halide present merely in the known manner by fixing and bleaching Had to be removed to make a durable, multi-colored, L-B -S-R ' 3. in which: R and R ₁ denote hydrogen atoms or radicals which block the phenolic groups and can be split off by the action of alkali, - S - a connecting monothio radical, R 'a diffusible heterocyclic radical which can form a mercaptan with the monothio radical connected to it, L a Hydrogen atom or an acidic, solubilizing group, B an inert, diffusion-preventing organic group,
an unexposed developable emulsion consisting of a hydrophilic colloid and a water-insoluble metal salt which is reduced to metal without exposure to a color developing solution, and
4. a non-diffusible coupler in contact with the water-insoluble metal salt, represented by the following formulas I. FY- (Kp-B) ,,
or
II. BY- (Kp-L) _n in which: F is a dye radical which selectively absorbs certain wavelengths from the spectrum of visible light and has a solubilizing acid radical, Y a connecting azo, mercury, oxy, alkylidene, monothio, dithio or azoxy radical, K _p a coupler radical of a 5-pyrazolone, a phenolic coupler or a coupler with an open ketomethylene group, the coupler radical in the coupling positions with the connecting The radical Y is connected, η the number 1 or 2 if Y is an alkylidene radical, or the number 1 if Y is an azo, mercury, oxy, monothio, dithio or azoxy radical, and in which B and L have the meaning given, and that the barrier layer contains a water-insoluble compound that interferes with a mercaptan is able to form water-insoluble salt. 2. Photographic material according to claim 1, xo characterized in that the unexposed developable Emulsion contains a silver halide as a metal salt, which is so veiled, that it is with a photographic alkaline developing solution, which is one of a primary contains aromatic amine existing developer compound without exposure to metal is reduced. 3. Photographic material according to claim 1, characterized in that the developable Emulsion as a metal salt, a silver halide and additional seeds for physical development contains. 4. Photographic material according to claim 1, characterized in that there are three color-forming Units with red-, green- and blue-sensitive layers have that the blue-sensitive Layer contains a coupler that releases a diffusible yellow, acidic dye is capable of the green-sensitive layer containing a coupler which is diffusible Is able to set magenta dye in freedom, and that the red-sensitive layer one Contains coupler capable of releasing a diffusible cyan dye. 5. Photographic material according to claim 1, characterized in that the barrier layer or Barrier layers contain a silver halide as a salt-forming compound. 6. Photographic material according to claim 4, characterized in that the coupler for the yellow image dye from "-Benzoyl -" - (3-octadecylcarbamylphenylthio) -3,5-dicarboxyacetanilide, 2- (3, 5-disulfobenzamido) -5-methyl-4- (4-octadecyloxyphenylazo) phenol, Dipotassium salt, l-oxy-4- (2,4-dinitrophenylthio) -N - [<5- (2,4-di-tert-amylphenoxy) butyl] -2-naphthamide or l-oxy-4- {4- [4- (l-sulfophenyl-3-methylpyrazolyl) azo] -3-sulfophenylazo} -N - [<5- (2,4-di-tert-amylphenoxy) - butyl] - 2 - naphthamide, disodium salt, the coupler for the purple image dye from l-phenyl-3- (3,5-disulfobenzamido) - 4 - (2 - oxy - 4 - η - pentadecylphenylazo) -5-pyrazolone, dipotassium salt, or l-phenyl-3- (3,5-disulfobenzamido) - 4 - (4 - octadecyloxyphenylazo) -5-pyrazolone, disodium salt, and the coupler for the blue-green image dye from l-oxy-4- (3-octadecylcarbamylphenylthio) -N-ethyl-3 ', 5'-dicarboxy-2-naphthanilide or 2- (3,5-disulfobenzamido) -5-methyl-4- (4-octadecyloxyphenylazo) phenol, Dipotassium salt. 7. Photographic material according to claim 4, characterized in that the color-forming Unit containing the blue-sensitive layer, arranged farthest from the support is that the barrier layer separating this color-forming unit from the other color-forming units in addition to a silver halide, a yellow filter material, in particular a yellow dye contains that the silver halide of the barrier layer has a lower photosensitivity than that in the photosensitive layers of the other the color-forming units from each other separating barrier and a lower photosensitivity than that in the red and green-sensitive, light-sensitive layers and that the developable emulsions containing layers of the individual color-forming units each arranged closer to the carrier are than the corresponding photosensitive layers. 8. Photographic material according to claim 7, characterized in that the developable Emulsion as a metal salt silver thiocyanate or silver cyanide and additional seeds for a contains physical evolution. 9. Photographic material according to claim 7, characterized in that the developable Emulsion contains a silver halide containing zinc sulfide as a metal salt. 10. Material according to claims 1 to 9, characterized in that the hydroquinone compound the end a) 2- {4- [3- (4-tert-amyl-x-sulfophenoxy) -benzamido] -phenylethyl} -x- (l-phenyl-5-tetrazolylthio) -hydroquinone, Sodium salt, b) 5- [4- (3,5-Disulfobenzamido) phenethyl] -2-methyl-3- (1-phenyl-5-tetrazolylthio) hydroquinone, Disodium salt, c) 2- {4- [2- (2,4-di-tert-amylphenoxy) -5- (3,5-disuif obenzamido) benzamido] - phenylethyl} - x- (1-phenyl - 5 - tetrazolylthio ) - hydroquinone, disodium salt (dihydrate), d) 2- {4- [3- (4-tert-amyl-x-sulfophenoxy) -benzamido] -phenethyl} -; c- (l-phenyl-5-tetrazolylthio) -hydroquinone diacetate, Sodium salt (dihydrate), e) 2 - [4 - (3,5 - Disulfobenzamido) - phenethyl] - x- ( 1-phenyl - 5-tetrazolylthio) - hydroquinone, disodium salt (dihydrate), or f) 2 - [4 - (3,5 - Disulfobenzamido) phenethyl] - * - (2-benzoxazolylthio) hydroquinone, disodium salt (Dihydrate), consists. 11. Diffusion transfer color photographic process for making a positive Color image from an exposed photographic material according to Claims 1 to 11, characterized characterized in that the material has been treated with a photographic alkaline color developing solution which is a primary aromatic amine developing agent contains, and that the material is then in contact with a receiving layer containing a mordant for acidic dyes is brought. 12. The method according to claim 11, characterized in that the receiving layer has a Forms part of a special recording sheet separate from the photographic material and that the photographic material and the receiving sheet simultaneously with the developing solution be moistened. 13. A method of forming a positive color image by color development one image at a time exposed photographic material according to claim 1, characterized in that the individual layers of non-diffusing yellow, purple, and blue-green dyes in a manner known per se by treating with a photographic bleach of the in the development areas of these layers and the associated photosensitive layers developed silver and that the material containing the color images through Treating stabilized with a fixative, especially undeveloped material present Halogen silver is exempt. 1 sheet of drawings 609 728/362 11.66 © Bundesdruckerei Berlin