EP0007593A1 - Colour-photographic developing process - Google Patents

Abstract

With a color photographic material which contains several differently spectrally sensitized silver halide emulsion layers and associated couplers, a hydrophobic cyan coupler having been introduced into the respective layer using a hydrophobic coupler solvent and a hydrophilic yellow coupler without using a coupler solvent, color images with good tropical resistance of the cyan image and good Lightfastness of the yellow image is obtained when using a color developer mixture containing a hydrophilic and a hydrophobic color developer compound.

Description

The invention relates to a color photographic development process in which a color photographic material containing a hydrophobic cyan coupler and a hydrophilic yellow coupler is developed with a mixture of a hydrophobic and a hydrophilic color developer.

It is known to produce color photographic images by chromogenic development, i. H. by developing imagewise exposed silver halide emulsion layers in the presence of suitable color couplers by means of suitable color-forming developer substances - so-called color developers - the oxidation product of the developer substances which is formed in accordance with the silver image reacting with the color coupler to form a dye image. Aromatic compounds containing primary amino groups, especially those of the p-phenylenediamine type, are usually used as color developers.

In practice, a number of demands are placed on the color couplers and on the dyes obtained therefrom by chromogenic development. The coupling speed of the color couplers with the oxidation product of the color developer should be as high as possible. The color couplers and the dyes obtained from them must be sufficiently stable to light, elevated temperature and moisture.

This applies in particular to color photographic copying materials, such as photographic color papers, since the color images produced therefrom are often exposed to the end user for a longer period of time as a result of light and, if appropriate, increased temperature and room humidity.

It has been found that, as a rule, the blue-green dyes produced by chromogenic development show poor resistance to the action of light if the underlying blue-green couplers belong to the class of naphthol derivatives. In contrast, dyes from cyan couplers based on phenol are sufficiently lightfast. However, it has been found that the dyes formed from these couplers are generally particularly susceptible to tropical conditions if the couplers are water- or alkali-soluble and, consequently, without the use of hydrophobic coupler solvents, so-called oil formers, in the casting solutions for the red-sensitive silver halide emulsion layer or in adjacent, non-light-sensitive binder layer have been incorporated. One be then often observes a more or less sharp decrease in the original maximum cyan color density when stored under tropical conditions. In this respect, the cyan dyes behave somewhat more favorably if the hydrophobic oil formers mentioned are used to incorporate the underlying color couplers.

In particular, the hydrophobic couplers of organic solutions are incorporated with water does not or only to a small extent miscible solvents in the casting solution for the photographic layers _B ekannkanntlich advantageously in the presence of high-boiling. An emulsified fine droplet of a solution of the coupler in the oily coupler solvent is obtained in which the coupler is distributed in the hydrophilic binder, protected by an oily shell, as it were.

In order to achieve the highest possible color density from a hydrophobic cyan coupler emulsified in this way during development, it is essential to use a color developer compound which, at least in the oxidized form, can easily penetrate into the hydrophobic oil droplets. Hydrophobic color developer compounds are particularly suitable for this. However, in order to achieve sufficient color density in the other color coupler-containing layers when using hydrophobic color developer compounds, the corresponding color couplers should also be emulsified in hydrophobic form. The yellow couplers, which are hydrophobic or in a hydrophobically emulsified form, now often have the disadvantage that the development of dyes proceeds more slowly than in the case of a hydrophilic one Yellow coupler with a hydrophilic developer substance, especially when the yellow developing layer is at the bottom of the layer package. In this regard, hydrophilic yellow couplers are superior to them, but they do not give the desired high color density with the hydrophobic color developer substances and often form dyes whose light fastness is unsatisfactory.

The use of color couplers emulsified in hydrophobic form in addition to water- or alkali-soluble color couplers in the same material, possibly even in the same layer, is known per se (e.g. DE-OS 1 962 606, _DE - _AS 1 ₅ 47 816, GB Patent 1,107,453. U.S. Patent 3,515,557). This is used, for example, to adapt the reactivity of different color couplers to one another. As stated above, the color developer substance used for the development of such materials does not lead equally to the desired high maximum color density in hydrophobic and hydrophilic color couplers.

The invention is based on the object of specifying a method for the chromogenic development of a color photographic material with at least three silver halide emulsion layers of different spectral sensitivity and color couplers associated therewith, at least one color coupler being hydrophobic and at least one further color coupler being hydrophilic, in which both hydrophobic and hydrophilic color couplers are sufficiently high color densities can be achieved. In particular, the; chromogenic development both a blue-green partial color image with good tropical resistance and a yellow partial color image with good light fastness can be obtained simultaneously.

The solution to the problem is that a developer composition is used for the chromogenic development of the material described, which contains both a hydrophobic and a hydrophilic color developer compound. Sufficiently high color densities are achieved both from the hydrophobic color couplers and from the hydrophilic color couplers. It has also been found that this method can simultaneously obtain both a blue-green partial color image with good tropical resistance and a yellow partial color image with good lightfastness if the color photographic material is both a cyan coupler emulsified with a hydrophobic ulcer and a hydrophilic one without the use of an oil former contains incorporated yellow coupler. In the same way as a hydrophilic yellow coupler, a hydrophobic yellow coupler which is eumulsified using a comparatively hydrophilic oil former also acts.

The color developer preparation used for development accordingly contains at least two color developer compounds of different hydrophilicity. The difference in hydrophilicity results in a different distribution of the color developer oxidation products in the two-phase system consisting of hydrophilic binder and hydrophobic oil former. The hydrophobic color developer compound (in oxidized form) penetrates the oil droplets of the coupler solvent much more easily and therefore reacts preferentially with the hydrophobic coupler, while the hydrophilic color developer compound remaining mainly in the aqueous phase reacts predominantly with the hydrophilic coupler.

worin bedeuten

• R' Wasserstoff oder Methyl,
• R² Alkyl, vorzugsweise mit 1 bis 4 Kohlenstoffatomen,
• R³ Alkyl, vorzugsweise mit 1 bis 4 Kohlenstoffatomen, gegebenenfalls substituiert, beispielsweise durch Alkoxy, wie Methoxy, Ethoxy, Hydroxyl, Carbcxyl, Sulfo oder Methylsulfonylamido.

Hydrophobic and hydrophilic color developer verbi speak according to the invention of the general formula

in what mean

• R 'is hydrogen or methyl,
• R ² alkyl, preferably having 1 to 4 carbon atoms,
• R ^{3 is} alkyl, preferably having 1 to 4 carbon atoms, optionally substituted, for example by alkoxy, such as methoxy, ethoxy, hydroxyl, carboxyl, sulfo or methylsulfonylamido.

The properties "hydrophobic" and "hydrophilic" in the characterization of the color developer compounds are not to be understood in the absolute, but only in the relative sense, since there are naturally transitions flowing between the extremes.

For example, if the substituents R ^{3 are arranged} in the following row:

Sulfoalkyl, carboxyalkyl, hydroxyalkyl, alkoxyalkyl, alkyl, methylsulfonamidoalkyl, so the meaning of the corresponding color developer compounds in the oxidized state with hydrophilic couplers in the oxidized state decreases, with an unchanged meaning for R and _R ² , and the Ability to react with hydrophobically emulsified couplers, with sequential order. The hydrophilic couplers also include hydrophobic couplers per se, which are dissolved in hydrophilic oil formers and are thus dispersed in the layer. For the relation hydrophobic-hydrophilic in the characterization of the color developer compounds in the sense of the invention, it is therefore only important that two color developer compounds are used which lead to a different distribution of the developer oxidation products in the two-phase system. For example, a hydrophilic color developer compound in which R ^{3 is} a sulfoalkyl group can be combined with a hydrophobic color developer compound in which R ^{3 is} an alkoxyalkyl group. On the other hand, the combination R ³ = methylsulfonylamidoalkyl (hydrophobic) and R ³ = hydroxyalkyl (hydrophilic) is also conceivable. Naturally, the more hydrophilic the one and the more hydrophobic the other of the two color developer compounds, the more favorable a result can be achieved. The quantitative ratio between the hydrophilic and hydrophobic color developer compound can be varied within wide limits according to the respective requirements, for example between 1: 6 and 6: 1 (parts by weight). Depending on the layer arrangement, the reactivity difference of the couplers and the difference in the hydrophilicity of the color developer compounds, the person skilled in the art can determine the most favorable quantity ratio by means of a simple routine test.

Oil formers for the purposes of the present invention are the known coupler solvents which are insoluble or only slightly soluble in water, which are sometimes referred to in the literature as crystalloid solvents and have been described, for example, in US Pat. Nos. 2,304,940 and 2,322,027. The oil formers can be hydrophobic or hydrophilic; at least in the neutral or acidic medium, they form their own second phase in addition to the hydrophilic binder phase. Hydrophilic oil formers are known from US Pat. Nos. 3,689,271, 3,764,336 and 3,765,897. These are high-boiling organic low-molecular compounds which can penetrate semipermeable membranes and which generally boil above 175 ^° C. At room temperature, ie at 20 ° C, they are generally liquid or they melt at relatively low temperatures, ie at temperatures below 100 ° C. They are referred to as oil formers because they generally form oily or liquid solutions when mixed with couplers.

Coupler solvents are e.g.

those compounds which have one or more polar groups or atoms, for example hydroxyl, carboxylic acid, amide or keto groups or halogen atoms. The dissolving effect on the couplers should be as high as possible, and of course the solvents should be inert towards the silver halide emulsion in which they are incorporated. Of course, they should also be colorless if possible. heat and moisture stable and also be inert towards the various development and treatment baths in which the color photographic material is developed. In addition, their volatility should be as low as possible. Occasionally it proves to be advantageous to use a mixture of two or more different oil formers to produce the coupler emulsate. This is particularly the case if the compounds are of higher melting point, since the mutual melting point depression promotes the formation of oily droplets.

• Ethylbenzylmalonat, Phthalsäuredialkylester, wie z. B. Dimethylphthalat, Diethylphthalat, Dipropylphthalat, Dibutylphthalat, Di-n-amylphthalat und Diisoamylphthalat, Dibenzylphthalat, Butyl-o-methoxybenzoat, n-Hexylbenzoat, 1,3-Diacetoxybenzol, Phosphorsäuretriarylester, wie z. B. Triphenylphosphat, Trikresylphosphat, Tri-p-tert.-butylphosphat und Tri-o-phenylphenylphosphat, N-Butylacetanilid, Acetylmethyl-p-toluidin, Benzoylpiperidin, N-n-Amylphthalimid, N-n-Amylsuccinimid, Ethyl-N-phenylcarbamat, N,N-Dimethyl-p-toluolsulfonamid, N,N-Dibutyl-p-toluolsulfonamid, N,N-Di-n-butylharn- stoff, N,N'-Diethyl-N,N'-diphenylharnstoff, Benzophenon, 2,4-Dichlorbenzophenon, Acetophenon, Cyclohexanon, p-sek.-Amylbenzophenon, Methylisobutylketon, 1-Phenyl-1-hydroxy-n-heptan, Dibenzylessigsäure, Phenylethylessigsäure, ß-Phenylpropionsäure, Undecylensäure, Octadecenylbernsteinsäure, Monobenzylsuccinat, p-sek.-Amylbenzoesäure, Mono-n-amylphthalat.

The high-boiling crystalloid solvents listed below have proven to be particularly suitable high-boiling coupler solvents, ie oil formers:

• Ethylbenzylmalonat, dialkyl phthalate, such as. B. dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, di-n-amyl phthalate and diisoamyl phthalate, dibenzyl phthalate, butyl o-methoxybenzoate, n-hexyl benzoate, 1,3-diacetoxybenzene, phosphoric acid triaryl esters, such as, for. B. triphenyl phosphate, tricresyl phosphate, tri-p-tert-butyl phosphate and tri-o-phenylphenyl phosphate, N-butylacetanilide, acetylmethyl-p-toluidine, benzoylpiperidine, Nn-amylphthalimide, Nn-amylsuccinimate, ethyl-N, phenyl -Dimethyl-p-toluenesulfonamide, N, N-dibutyl-p-toluenesulfonamide, N, N-di-n-butylurea, N, N'-diethyl-N, N'-diphenylurea, benzophenone, 2,4-dichlorobenzophenone , Acetophenone, cyclohexanone, p-sec.-amylbenzophenone, methyl isobutyl ketone, 1-phenyl-1-hydroxy-n-heptane, dibenzylacetic acid, phenylethyl acetic acid acid, ß-phenylpropionic acid, undecylenic acid, octadecenylsuccinic acid, monobenzyl succinate, p-sec.-amylbenzoic acid, mono-n-amylphthalate.

Oil formers which are used particularly frequently and which have also proven to be outstandingly suitable in the context of the present invention are, for example, phosphoric acid triaryl esters, in particular tricresyl phosphate, and phthalic acid dialkyl esters, such as di-n-butyl phthalate. In addition, the list contains a whole series of compounds which, owing to the different functional groups, behave differently in terms of their affinity for the couplers to be dissolved and for the reagents of the various photographic treatment baths, in particular the developer oxidation product.

• A Trikresylphosphat,
• B Dibutylphthalat,
  
  
  

As already mentioned, hydrophilic oil formers are in principle also suitable for the storage of hydrophobic color couplers. According to the invention makes you this though possibly at _P urpur- and yellow couplers use; Only hydrophobic oil formers are used for the storage of cyan couplers. An example of a number of oil formers of increasing hydrophilicity is given below:

• A tricresyl phosphate,
• B dibutyl phthalate,
  
  
  

Since the distribution equilibrium of the color developer oxidation products also depends on the hydrophilicity of the ul former used, it is also possible to influence the coupling ability of the color couplers dissolved therein.

The photographic material to be developed according to the method of the invention contains at least three silver halide emulsion layers with different spectral sensitivity on a conventional substrate which can be transparent but is preferably opaque. A non-diffusing color coupler is assigned to each of these three layers in order to produce a partial color image, the color of which is generally complementary to the color of the light, for which the assigned silver halide emulsion layer is predominantly sensitive. A yellow coupler is assigned to the blue-sensitive silver halide emulsion layer, a purple coupler to the green-sensitive silver halide emulsion layer and a cyan coupler to the red-sensitive silver halide emulsion layer.

“Associated” is understood to mean that the mutual arrangement of the silver halide emulsion layer and color coupler is of such a type that an interaction between them is possible which permits an imagewise match between the silver image formed and the imagewise distribution of the image dye produced in the chromogenic development. The color coupler is usually embedded in the light-sensitive silver halide emulsion layer itself; however, it can also be contained in a non-light-sensitive neighboring layer for this purpose. Since the developer oxidation products generated during color development should only react with the assigned color coupler and if possible not in unassigned colors coupler-containing layers are to be diffused, expediently there are still separating layers between the light-sensitive silver halide emulsion layers, which may consist of pure binder or may contain substances distributed in a binder which are capable of reacting with color developer oxidation products to form colorless substances. In a known manner, these can be white coupler compounds or non-diffusing hydroquinone derivatives.

The preferred hydrophilic binder in the process of the present invention is gelatin, but it can also be replaced in whole or in part by other natural or synthetic binders. In the two-phase system mentioned, the hydrophilic binder represents the hydrophilic phase.

The usual known color couplers come into question as color couplers. Cyan coupler, for example, derivatives of phenol are capable in the 4-position with oxidized developer _F ARB to cyan Indochinonfarbstoffen to react. As a purple coupler

Pyrazolone derivatives should be mentioned in particular, and derivatives of benzoylacetanilide or pivaloylacetanilide are generally used as yellow couplers. In this context, reference should be made to the publication "Farbkuppler" by W. Pelz in "Mitteilungen aus die Forschungslaboratorien der Agfa", Leverkusen / Munich, Vol. III, p. 111 (1961) and to the article by K. Verkataramon in " _Th e _C hemistry of Synthetic Dyes "Vol 4, p 341 -. 387 (1971).

Hydrophobic color couplers are those that can generally not be incorporated into the casting solutions for the photographic layers from aqueous alkaline solutions. Groups which render water or alkali soluble, in particular sulfo or carboxyl groups, are generally absent from the hydrophobic color couplers. Conversely, the hydrophilic color couplers normally contain at least one sulfo or carboxyl group which makes them soluble in aqueous alkali. Because of this latter property, the hydrophilic color couplers are sometimes referred to as "soluble" couplers, in contrast to the "insoluble" or hydrophobic couplers.

According to the invention in its broadest aspect, the color photographic material to be developed contains at least one hydrophobic color coupler emulsified in droplets of a more or less hydrophobic oil former and at least one hydrophilic color coupler, which may have been added to the layer in the form of an aqueous alkaline solution or in the form of a Emulsions in a hydrophilic oil former. Hydrophobic and hydrophilic color couplers can be contained in the same layer or in different layers. In the first case, both couplers can contribute to the generation of the same partial color image.

In a preferred embodiment of the invention, the cyan coupler is hydrophobic and the yellow coupler is hydrophilic. The magenta coupler can be either hydrophobic or hydrophilic, or even as a combination of a hydrophilic magenta coupler with a magenta coupler emulsified in hydrophobic form.

example 1

A color photographic material with three gelatin-silver halide emulsion layers applied to an opaque support contains the coupler 1 for the generation of the yellow image in the blue-sensitive underlayer, the coupler 2 for the generation of the purple image in the green-sensitized middle layer and the coupler 3 for the generation of the in the red-sensitized top layer teal image. Coupler 2 and coupler 3 are emulsified using the hydrophilic oil former E. The formulas of the couplers are given at the end of the examples.

• Entwickler, 35°C, 2 min.

The material is exposed behind a silver gray wedge and processed as follows:

• Developer, 35 ° C, 2 min.

• 3 g Hydroxylammoniumsulfat,
• 3 g Natriumsulfit,
• 5 g Farbentwicklersubstanz mit R¹ = H, R² = Butyl, _R ³ _{= S}ulfobutyl,
• 0,7 g Kaliumbromid,
• 60 g Kaliumcarbonat,
• 2 g Natriumnitrilotriacetat.

1 liter contains:

• 3 g of hydroxylammonium sulfate,
• 3 g sodium sulfite,
• 5 g of color developer substance with R ¹ = H, R ² = butyl, _R ³ ₌ sulfobutyl,
• 0.7 g potassium bromide,
• 60 g potassium carbonate,
• 2 g sodium nitrilotriacetate.

It is then treated with a bleach-fixing bath of a known type, washed and dried.

Example 2

• In 1 Liter sind enthalten:
• 15 ml Benzylalkohol,
• 3 g Hydroxylammoniumsulfat,
• 3 g Natriumsulfit,
• 5 g Farbentwicklersubstanz mit R¹ = Methyl, R² = Ethyl, _R ³ = Methylsulfamidoethyl,
• 0,7 g Kaliumbromid,
• 35 g Kaliumcarbonat,
• 2 g Natriumnitrilotriacetat.

The material of Example 1 is in the following developer at 35 ⁰ C and 2 min. processed:

• 1 liter contains:
• 15 ml benzyl alcohol,
• 3 g of hydroxylammonium sulfate,
• 3 g sodium sulfite,
• 5 g of color developer substance with R ¹ = methyl, R ² = ethyl, _R ³ = methylsulfamidoethyl,
• 0.7 g potassium bromide,
• 35 g potassium carbonate,
• 2 g sodium nitrilotriacetate.

Example 3

The material is as described in Example 1. In contrast to this, coupler 3 is dissolved in dibutyl phthalate (hydrophobic) and this solution is dispersed in the top layer. The same applies to coupler 4 (instead of coupler 1) in the lower layer. The development is carried out as in Example 1.

Example 4

The material of Example 3 is processed as indicated in Example 2.

Example 5

The material is as described in Example 1. In contrast to this, coupler 3 is dissolved in dibutyl phthalate and this solution is dispersed in the top layer. Otherwise, the material has the structure described in Example 1. Development takes place with the following developer at 35 ^° C. and 2 minutes:

• 5 ml Benzylalkohol,
• 3 g Hydroxylammoniumsulfat,
• 3 g Natriumsulfit,
• 2 g Farbentwicklersubstanz mit R = H, R² = Butyl, _R ³ ₌ Sulfobutyl,
• 3 g Farbentwicklersubstanz mit R ¹ = Methyl, R² = Ethyl, R³ = Methylsulfonamidoethyl,
• 0,7 g Kaliumbromid,
• 35 g Kaliumcarbonat,
• 2 g Nitrilotriacetat.

1 liter contains:

• 5 ml of benzyl alcohol,
• 3 g of hydroxylammonium sulfate,
• 3 g sodium sulfite,
• 2 g of color developer substance with R = H, R ² = butyl, _R ³ ₌ sulfobutyl,
• 3 g of color developer substance with R ¹ = methyl, R ² = ethyl, R ³ = methylsulfonamidoethyl,
• 0.7 g potassium bromide,
• 35 g potassium carbonate,
• 2 g nitrilotriacetate.

Further processing as indicated in Example 1.

The wedge images obtained according to Examples 1 to 5 are evaluated as follows:

The maximum densities of the individual colors are determined. In addition, samples are kept for 7 days at 60 ° C. and 80% relative atmospheric humidity, after which the loss of color density at the initial density 1 is determined. Finally, samples are exposed to daylight for 5 · 10 ° Lux · h, after which the loss of color density at the initial density 1 is determined.

The result of these measurements is summarized in Table 1. It shows that the combination of a layer package with hydrophilically and hydrophobically incorporated couplers with a developer composition which contains two developer substances, one of which preferably couples with hydrophilically incorporated and the other preferably with hydrophobically incorporated couplers, leads to an optimal solution.

Example 6

• In 1 Liter sind enthalten:
• 15 ml Benzylalkohol,
• 3 g Hydroxylammoniumsulfat,
• 3 g Natriumsulfit,
• 5 g Farbentwicklersubstanz mit R¹ = Methyl, _R ² = Ethyl, R³ = Methylsulfamidoethyl,
• 0,7 g Kaliumbromid,
• 35 g Kaliumcarbonat,
• 2 g Natriumnitriloacetat.

A color photographic material with coupler 1 for producing the yellow image in the lower layer, with coupler 2 dissolved in dibutyl phthalate and dispersed in the middle layer and with coupler 3 dissolved in dibutyl phthalate and dispersed in the top layer is in the following developer 2 min. developed at 35 ° C:

• 1 liter contains:
• 15 ml benzyl alcohol,
• 3 g of hydroxylammonium sulfate,
• 3 g sodium sulfite,
• 5 g of color developer substance with R ¹ = methyl, _R ² = ethyl, R ³ = methylsulfamidoethyl,
• 0.7 g potassium bromide,
• 35 g potassium carbonate,
• 2 g sodium nitriloacetate.

Thereafter, a bleach-fix bath of known type is used delt, watered and dried.

Example 7

• In 1 Liter sind enthalten:
• 15 ml Benzylalkohol,
• 3 g Hydroxylammoniumsulfat,
• g Natriumsulfit,
• 5 g Farbentwickler mit R¹ = Methyl, R² = Isopropyl, _R ³ ₌ Sulfobutyl,
• 0,7 g Kaliumbromid,
• 35 g Kaliumcarbonat,
• 2 g Nitrilotriacetat.

Weitere Verarbeitung wie unter Beispiel 6 angegeben.The material of Example 6 is developed in the following developer:

• 1 liter contains:
• 15 ml benzyl alcohol,
• 3 g of hydroxylammonium sulfate,
• g sodium sulfite,
• 5 g of color developer with R ¹ = methyl, R ² = isopropyl, _R ³ ₌ sulfobutyl,
• 0.7 g potassium bromide,
• 35 g potassium carbonate,
• 2 g nitrilotriacetate.

Further processing as indicated in Example 6.

Example 8

• 1 Liter enthält:
• 15 ml Benzylalkohol,
• 3 g Hydroxylammoniumsulfat,
• 3 g Natriumsulfit,
• 1,5 g Farbentwickler mit R¹ = Methyl, R² = Ethyl, R³ = _Methylsulfonamidoethyl,
• 3 g Farbentwickler mit R¹ = Methyl, R² = Isopropyl, R³ = Sulfobutyl,
• 0,7 g Kaliumbromid,
• 35 g Kaliumcarbonat,
• 2 g Nitrilotriacetat.

Weitere Verarbeitung wie in Beispiel 6 angegeben.The material of Example 6 is developed in the following developer:

• 1 liter contains:
• 15 ml benzyl alcohol,
• 3 g of hydroxylammonium sulfate,
• 3 g sodium sulfite,
• 1.5 g of color developer with R ¹ = methyl, R ² = ethyl, R ³ = _M ethylsulfonamidoethyl,
• 3 g of color developer with R ¹ = methyl, R ² = isopropyl, R ³ = sulfobutyl,
• 0.7 g potassium bromide,
• 35 g potassium carbonate,
• 2 g nitrilotriacetate.

Further processing as indicated in Example 6.

The wedge images obtained according to Examples 6 to 8 are evaluated in the same way as the wedge images of Examples 1 to 5. The result of these measurements is summarized in Table 2. The table shows that an optimal result is obtained if a color photographic material with both hydrophilically and hydrophobically incorporated couplers is processed with a developer composition which contains two developer substances, one of which preferably reacts with hydrophilically incorporated couplers and the other preferably with hydrophobically incorporated couplers responds.

Examples of the individual types of couplers are:

Claims (6)

1. A method for the chromogenic development of a color photographic material with at least three silver halide emulsion layers of different spectral sensitivity and associated non-diffusing color couplers, of which at least one is hydrophobic and was incorporated into the respective layer containing a hydrophilic binder using a hydrophobic oil former, and of which at least one is further hydrophilic and has been incorporated into the layer containing a hydrophilic binder without using an oil former or is hydrophobic and has been incorporated into the layer containing a hydrophilic binder using a comparatively hydrophilic oil former, characterized in that a developer composition is used for the chromogenic development which contains a first and a second color developer compound, the first and the second color developer compound oxidation products with different Ve division in the two-phase system consisting of the hydrophobic oil former and the hydrophilic binder. 2. The method according to claim 1, characterized in that at least one cyan coupler is hydrophobic and was incorporated into the layer using a comparatively hydrophobic oil former and that at least one yellow coupler is hydrophilic and was incorporated into the layer without using an oil former. 3. The method according to claim 1, characterized in that at least one cyan coupler is hydrophobic and was incorporated into the layer using a comparatively hydrophobic oil former and that at least one Yellow coupler is hydrophobic and was incorporated into the layer using a comparatively hydrophilic oil former. 4. The method according to claim 2 or 3, characterized in that a hydrophobic cyan coupler based on phenol is used. 5. The method according to claim 1, characterized in that the developer composition contains a first and a second color developer compound, both of the formula

correspond to what R ^{1 is} hydrogen or methyl _R ² alkyl
and _R ^{3 is} sulfoalkyl, carboxyalkyl or hydroxyalkyl in the case of the first color developer compound and alkoxyalkyl, alkyl or methylsulfonamidoalkyl in the case of the second color developer compound. 6. The method according to claim 5, characterized in that as the first color developer compound N-butyl- _N - ω-sulfobutylp-phenylenediamine or 2-amino-5- (N-isogropyl-N-ω-sulfobutylamino) toluene and as the second Color developer compound 2-amino-5- (N-ethyl-N-methylsulfonamido-ethylamino) toluene is used.