DE2159903C3 - Process for making color photographic images - Google Patents

Description

R ₁ -N- (CH ₂ ) "- OR ₂

NH ₂

where mean:

Ri and R2 each represent an alkyl radical with 1 to 4 carbon atoms, R3 an alkyl or alkoxy radical with 1 to 4 carbon atoms and η = 2.3 or

2. The method according to claim 1, characterized in that there is a color developer with a Color developing agent of the given formula used, in which Ri is an ethyl radical.

3. The method according to claim 1, characterized in that one has a recording material a red, a green and a blue sensitive silver halide emulsion layer are used.

4. The method according to claim 1, characterized in that one is a recording material used, the silver halide emulsion layers of which consist of silver bromide iodide emulsion layers.

5. The method according to claim 1, characterized in that one for color development of the silver halide emulsion layers Color developing baths containing diffusing color couplers are used, one of which is used for developing the roller-sensitive Silver halide emulsion layer a cyan dye-providing color coupler; one for developing the blue-sensitive silver halide emulsion layer a color coupler providing a yellow dye and one for developing the green-sensitive silver halide emulsion layer contains a magenta dye-providing color coupler with the proviso that at least one of the color developing baths used as a color developing agent

3-alkyl-N-alkyl-N-alkoxyalkyl-p-phenylenediamine and / or at least one 3-alkoxy-N-alkyl-N-alkoxyalkyl-p-phenylenediamine the given formula contains.

6. The method according to claim 5, characterized in that at least that for generating the yellow image dye used at least one color developing agent as the color developing agent

3-alkyl-N-alkyl-N-alkoxyalkyl-p-phenylenediamine
and / or contains at least one 3-alkoxy-N-alkyl-N-alkoxyalkyl-p-phenylenediamine of the formula given.

7. Process according to Claims 1 to 6, characterized in that one is used as the color developer compound used:

N-ethyl-N-methoxyethyl-3-methyl-

p-phenylenediamine,

N-ethyl-N-methoxybutyl-3-methyl-

p-phenylenediamine,

N-ethyl-N-ethoxyethyl-3-methyl-

p-phenylenediamine,

N-ethyl-N-methoxyethyl-3-n-propyl-

p-phenylenediamine,

N-ethyl-N-methoxyethyl-3-methoxy-

p-phenylenediamine and / or

N-ethyl-N-butoxyethyl-3-methyl-

p-phenylenediamine.

8. The method according to claim 4, characterized in that one is a recording material used in which the silver halide of the silver bromide iodide emulsion layers consists of 1 to 20 mol% of iodide.

9. The method according to claim 8, characterized in that one has a recording material a silver bromide iodide emulsion layer containing at least 1 mol% more iodide than contains at least one of the other silver bromide iodide emulsion layers.

10. The method according to claim 1, characterized in that the black and white development in The presence of a diffusing 4-thiazolin-2-thione.

The invention relates to a method for producing color photographic images, in which a color photographic Recording material consisting of a transparent substrate and at least two silver halide emulsion layers applied thereon, which are sensitive to different regions of the spectrum, after the image-appropriate exposure initially subjected to a black-and-white development and thereafter color developed in the presence of non-diffusing image dyes providing color couplers will.

It is known that color photographic images are used to produce multicolored photographic images Recording materials with differently sensitized emulsion layers, the non-diffusing color couplers may contain, in which case the color development can be carried out in a color development step in which a color negative is produced, provided that the color development step is the first development step is. On the other hand, it is also possible to first generate a color reversal image, in which case first a negative black and white development is carried out, which is followed by a process step

adjoins, in which the still existing non-expo ned and undeveloped silver halide is made developable, followed by color development connects. In the case of reversal color photographic materials which do not contain color couplers brought diffusing color couplers in aqueous alkaline color developer solutions to the application selectively color-develop one silver halide emulsion layer at a time. The color development of a multilayer multicolored recording material without color coupler after the color reversal process thus requires initially a negative black and white development, which is not the case in a subsequent process stage exposed and undeveloped silver halide in one of the emulsion layers made selectively developable will. This layer is then applied using a color developer solution with a diffusing color coupler, which forms a non-diffusing dye that is sensitive to light in its color this layer is complementary, color-developed. Then the unexposed and undeveloped Silver halide made the second emulsion layer selectively developable, whereupon this layer with a second color developing solution is color developed. This second color developing solution contains in turn a diffusing color coupler capable of forming a non-diffusing dye, its The hue of the photosensitivity of this layer is complementary. Eventually that becomes unexposed and undeveloped silver halide made the third emulsion layer selectively developable, whereupon this Layer using another color developing solution that has a diffusing color coupler contains, which is able to form a non-diffusing dye, the color of which is complementary Photosensitivity of this third layer, which is developed in color. Following the color winding will be the silver and any silver halide still present are removed by a silver bleaching process, whereupon the photographic Material can be fixed.

It is also known e.g. B. from "Photographic Science and Engineering", Vol. 13, No. 3, 1969, cables 141-143, that in the black and white development of a multilayer, multicolored recording material with silver bromide iodide emulsion layers, of which at least one layer is at least 1 mol% contains more iodide than at least one of the other silver halide emulsion layers, special effects occur which have become known as "interimage effects" or neighboring effects. These effects are evidently caused by the fact that the imagewise distributed iodide ions, which have been set free by the development of the layer with the higher molar percentage of iodide, diffuse into the emulsion layer or emulsion layers which have the lower molar percentage of iodide , whereby an imagewise inhibition of the development of the latent image takes place, which leads to an increase in the amount of silver halide in the layer or layers containing less iodide corresponding to the image development in the layer containing more iodide. During the subsequent color development, the increase in the silver halide concentration in the layer or layers containing less iodide leads to a correspondingly increased dye formation ^{after negative development, ie after black (15 white development).}

It is also known e.g. B. from Journal of the Optical Society of America, 42, No. 9, pages 663-669 (1952), such neighboring effects in the subtractive Exploit color process to improve color rendering. So it is from the quoted Known literature reference, Neighboring Effects for Correcting Undesired Absorption of Photographic Dyes to use.

It is also known that the presence of certain additives such. B. diffusing 4-Thiazolin-2-thione, in emulsion layers of multilayer color photographic recording materials Allow neighboring effects to be produced during the development of the silver image.

Finally, it is also known that in the context of color photographic development processes in which color developing agents composed of active primary aromatic amines are used Not all of the silver halide grains that have latent image centers become silver and dye to be developed. These so-called "dead grains" are of course an undesirable ballast of the color photographic development process.

On the other hand, it is also known, e.g. B. from the FR-PS 9 83 022 and the journal "Journal of the American Chemical Society", 73 (1951), pages 3100-3125, for Development of color photographic recording materials, p-phenylenediamines, especially their asymmetrical ones To use dialkyl derivatives.

From US Pat. No. 2,163,166 it is also known to use p-phenylenediamine compounds as color developer compounds for developing color photographic recording materials with an amino group represented by a radical of the formula

- (- CH ₂ CH ₂ O- ^ CH ₂ CH ₂ -OH

where η is an integer, e.g. B. 3 to 5, substituted to be used.

The object of the invention is to provide a method for producing color photographic images, in which intensified neighbor effects are generated and an improved color rendering is effected. Included should at the same time make effective use of the latent, imagewise exposed silver halide grains can be achieved by increasing the ratio of dye generated to exposed silver halide. Furthermore, the color haze, i.e. the color development in the non-image areas, should be reduced will.

The invention was based on the knowledge that the task at hand can be achieved by using very specific ones Can dissolve color developer compounds.

The invention is a method for producing color photographic images, in which a color photographic recording material, consisting of a transparent support and a at least two applied to it, sensitive to different areas of the spectrum Silver halide emulsion layers, after the imagewise exposure, initially a black-and-white development and then in the presence of non-diffusing image dyes providing color couplers is color developed, which is characterized in that a color developing bath is used for color development used, which as color developer compound at least one, optionally present in salt form, 3-alkyl-N-alkyl-N-alkoxy-alkyl-p-phenylenediamine

and / or at least one 3-alkoxy-N-alkyl-N-alkoxy-alkyl-p-phenylenediamine contains the following formula:

where mean:

Ri and R2 each represent an alkyl radical with 1 to 4 carbon atoms, R3 an alkyl or alkoxy radical with 1 to 4 carbon atoms and η = 2, 3 or 4.

The method of the invention enables the production of color photographic images in the context of subtractive color process with improved color rendering as a result of increased neighbor effects as well the production of color photographic images with reduced color fog in the unexposed Districts and higher color densities in the exposed districts, a color development process is also used created that is less pH sensitive. Eventually, there will be improved color rendering achieved by developing practically all silver halide grains with latent images, practically no dead silver halide grains remain.

Conventional known imagewise exposed ones are suitable for carrying out the process of the invention multi-colored multi-layer color photographic recording materials made of a transparent Substrate with silver halide emulsion layers applied thereon, which are sensitive to at least two of the red, green and blue areas of the visible spectrum. These are preferably silver bromide iodide emulsion layers of Camera sensitivity.

In the process of the invention, the silver halide emulsion layers are used of the recording materials used in the exposed areas initially developed into black and white silver images, with neighboring effects be evoked. These neighboring effects are increased according to the invention in that the Color development takes place in the presence of certain color developing agents of the specified structure, which provide non-diffusing dyes, the color of which corresponds to the photosensitivity of the corresponding Silver halide emulsion layers are practically complementary.

The use of color developing agents as follows has been found to be particularly advantageous Proven formula:

CH ₃ CH ₂ -N- (CH ₂ ) "- O-R ₂

where π has the meaning given, R2 is a methyl-ethyl, propyl or butyl radical and R _{3 is} a methyl-ethyl, propyl or butyl radical or a methoxy-ethoxy, propoxy or butoxy radical.

The color couplers required to carry out the process of the invention can either be in the in correspondingly sensitized silver halide emulsion layers in the form of non-diffusing color couplers, in which case the Color development of all emulsion layers, e.g. B. all three emulsion layers, advantageously in one single development stage is carried out using a color developing solution containing at least one 3-alkyl-N-alkyl-N-alkoxyalkyl-p-phenylenediamine developer compound and / or at least one 3-alkoxy-N-alkyl-N-alkoxyalkyl-p-phenylenediamine color developing agent the given formula contains. On the other hand, however, it is also possible to use diffusing To use color couplers and to apply them in developer solutions. For example a diffusing cyan dye image forming coupler in a cyan color developer bath applied, which causes the color development of the red-sensitive layer, while a diffusing, yellow dye image-forming color coupler in a yellow developer bath is applied, which develops the blue-sensitive silver halide emulsion layer in color and finally a diffusing magenta dye image forming color coupler in a purple developer bath is used, which is used for color development of the green-sensitive silver halide emulsion layer of a recording material without non-diffusing Color coupler is intended. It applies here that at least one of the color developer baths used is a 3-alkyl-N-alkyl-N-alkoxyalkyl-p-phenylenediamine and / or a 3-alkoxy-N-alkyl-N-alkoxyalkyl-p-phenylenediamine given formula as a color developing agent.

A customary aqueous alkaline developer solution is advantageously used for black-and-white development used with at least one non-dye forming silver halide developing agent, preferably with at least one hydroquinone, p-methylaminophenol, l-phenyl-3-pyrazolidone and / or 4,4-dimethyl-3-pyrazolidone.

After black and white development, the undeveloped silver halide can be processed using various measures, for example by exposure to light or by treatment with a chemical fogging agents, e.g. B. an alkali metal borohydride or an aminoborane, developable before or during color development.

In the development of color photographic recording materials, which the use of diffusing color couplers in separate color developer solutions require, the emulsion layers are selectively treated one after the other after the black-and-white development, with the aim of making the remaining silver halide developable in an emulsion layer make, whereupon this layer is color-developed, whereupon the silver halide of another Emulsion layer is made developable, etc.

The development of a color photographic recording material, consisting of a transparent substrate and a red-sensitive emulsion layer applied to it, one applied to it green-sensitive emulsion layer, a bleachable yellow-colored filter layer and one thereon applied blue-sensitive emulsion layer

follows, for example, in such a way that after the black-and-white development there is a selective re-exposure the lower red-sensitive emulsion layer takes place with red light through the support, whereupon the Blaugrijn development follows. Then will washed the material, whereupon the blue-sensitive emulsion layer selectively re-exposed to blue light will. This is followed by yellow development, after which the material is washed again. Finally, the middle green-sensitive layer is re-exposed to white light. on the other hand this layer can also be used, for example, by means of a chemical concealment agent in front of or made developable during the crimson development.

When the three emulsion layers have finished developing their color, the recording material becomes washed, whereupon any silver and any remaining silver halide by means of a silver bleaching bath removed, whereupon the material is fixed in a fixer. For bleaching and fixing the For example, conventionally known alkali metal ferricyanide bleach baths are suitable for color-developed recording materials and conventionally known alkali metal thiosulfate fixing baths.

Color developing agents suitable for carrying out the process of the invention are, for example:

1. N-ethyl-N-methoxyethyl-3-methylp-phenylenediamine;

2. N-ethyl-N-methoxybutyl-3-methyl-p-phenylenediamine;

3. N-ethyl-N-ethoxyethyl-3-methylp-phenylenediamine;

4. N-ethyl-N-methoxyethyl-3-n-propylp-phenylenediamine;

5. N-ethyl-N-methoxyethyl-3-methoxyp-phenylenediamine and

6. N-ethyl-N-butoxyethyl-3-methyl-p-phenylenediamine.

The developer compounds used according to the invention can be used as free bases or in the form of Salts with organic or inorganic acids can be used. For example, they can be used in Form of their hydrochloric acid salts, their sulfuric acid salts, their phosphoric acid salts, their oxalic acid salts, their p-toluenesulfonic acid salts, their benzenedisulfonic acid salts and their naphthalene disulfonic acid salts can be used.

The color developer compounds used in accordance with the invention can advantageously be used in aqueous alkaline color developer solutions within a broad concentration range, preferably in concentrations of about 0.5 to about 15 g / l, in particular in concentrations of about 1.0 to about 12.0 g / l.

The developer solutions or developer baths can be used for typical color developers ^ - sungcn or baths have known composition. This means that the developing solutions or Ao Developer baths can be built up using conventional additives, for example using

Alkali metal chlorides, alkali metal bromides. Alkali metal iodides, alkali metal sulfites ^ Alkali Metal Sulphates ^ Alkali metal carbonates,

Alkali metal hydroxide,

Alkali metal metaborates,

Alkali metal phosphates, ethylenediamine,

Citrazinic acid, antifoggants ^ e.g. B.

5-nitrobenzimidazole, furthermore

Auxiliary developer associations, e.g. B.

1-phenyl-3-pyrazolidones,

Stabilizers for developer compounds,

z. B. diethylhydroxylamine, dihydroxyacetone,

Glycolaldehyde, glyceraldehyde,

Dihydroxymaleic acid, furthermore

Sodium hexametaphosphate and the like.
A typical color developing bath for color development of a recording material which contains incorporated color couplers has, for example, the following composition:

Color developer Benzyl alcohol 0-12ml Alkali metal hexameta phosphate 0-3g Alkali metal sulfite 2-20g Trialkali metal phosphate · 12H ₂ O 10-6Og Alkali metal bromide 0-5g Alkali metal iodide (0.1% solution) 0-15ml Color developing agent according to formula 0.5-15 g Ethylene diamine sulfate 0-20g Citrazinic acid 0-5g Dithiooctanediol 0-5g Topped up with water 1 liter

The color developer also contains so much alkali, for example alkali metal hydroxide or alkali metal carbonate, that a pH of about 10.0 to gives about 14.0. The alkali metal ions consist, for example, of sodium, potassium or lithium ions.

Typical color developing baths which are used for developing color photographic recording materials without color couplers are suitable, for example, have the following composition:

Blue-green and yellow color developer baths

Alkali metal hexameta 0-3g phosphate 3.0-2Og Alkali metal sulfite 0.2-5 g Alkali metal bromide Trialkalimetnll- 20.0-6Og phosphate · I2H2O Alkali metal iodide 2.0-5OmI (0.1% solution) Furbene winder connection 0.5-1Og according to formula Antifoggants 1.0-4OmI (1% igc solution) 0-7Og Alknlimetallsulfut 0.5-8 g Diffusing color coupler 0-2OmI Hexylene glycol Diethylhydroxylttinine 0.3-10 ml (85%) Auxiliary coupler 0-8g (e.g. citric acid) Auxiliary developer 0.1-2 g (e.g. l-phenyl-3-pyrnzolldon) Alkuli for attitude 10-14 a pH of I liter Topped up with water uiif

709 627/1.

WBß

ir · .-:

In the case of a cyan color developer bath, in advantageously a conventional phenolic or naphtholic blue-green dye-forming agent Color couplers are used, whereas in the case of yellow color developing baths, a conventional one is preferably used known open chain acylacetamide color coupler is used.

As the antifoggant, conventionally known antifoggants such as 5-nitrobenzimidazole can be used or 5-nitrobenzimidazole-6-nitrate can be used. Furthermore, the most diverse alkaline substances, which are commonly used for the production of color developer baths, for Preparation of the color developer baths used according to the invention, for example alkali metal hydroxides. Alkali metal carbonates and borax, the alkali metal ions used in the preparation of color developing baths Alkali metal compounds used can in a conventionally known manner, for example from Sodium, potassium and / or lithium ions exist.

The magenta color developer baths can have the same composition as the cyan and yellow dye developer baths described, with the exception that they contain no auxiliary developing agent or any antifoggant, but in addition to the specified compounds per liter: 0.3-5 g of an alkali metal thiocyanate 1.0-8 ml Ethylenediamine and
0-2 g of a chemical fogging agent for silver halide.

Typical chemical fogging agents are, for example, those from US Pat. No. 3,246,987 known nucleating agents

z. B. amine boranes, e.g. B. trimethylamine borane, diethylamine borane, triethylamine borane, tert-butylamine borane, pyridine borane, 2,6-lutidine borane and the like,
also polyamine boranes, z. B.
Ethylenediaminediborane, hydrazinediborane, also phosphine boranes, e.g. B.
Dimethylphosphine borane,
also arsine boranes, z. B. Dimethylarsine borane, also stilbene borane,
z. B. Dimethylstilbenboran, Borazine, / .. 13. Borazine, Ν, Ν ', Ν'-trimethylborazine, Ν, Ν', Ν "-trimethylborazine and the like. If no chemical concealment agent is used in the magenta color developing unit, a chemical concealment bath can advantageously be used shortly before the magenta color development. On the other hand, the unexposed green-sensitive silver halide emulsion layer can also be made developable by exposure to light. A typical chemical wear band has the following composition:

0.6 g of an Alknlimoinllhcxumciuphosphuics, 2.1b g of an Alktilimetallhydroxydes, 0.10 g of a chemical wear agent for silver halide,
Filled up with water to the ΓI liter.

To prepare the directory, the common known chemical masking agents, as indicated above can be used.

In the color photographic cr Recording materials which do not contain color couplers can use color developing solutions the usual known diffusing color couplers can be used. Such color couplers are for example known from the following USA patents:

22 66 452; 22 95 009; 23 13 586; 23 62 598;

23 69 929; 27 72 162; 30 02 836; 23 11 082;
23 53 205; 23 69 489; 26 00 788; 23 43 703;

ίο 28 99 306: 21 15 394; 21 08 602; 21 13 330;
22 71 238; 22 89 805 and 24 39 352.
The transparent support of the photographic recording materials suitable for carrying out the process of the invention can consist of one of the customary, known transparent film supports, for example cellulose nitrate, a cellulose ester, polyvinyl acetate, polystyrene, a polycarbonate or a polyester, for example polyethylene terephthalate, but also of glass. The differently sensitive silver halide emulsion layers, for example the red-, green- and blue-sensitive silver halide emulsion layers, can be arranged in different orders on the support. Advantageously, the red-sensitized silver halide emulsion layer is closest to the support, followed by and finally the green-sensitized silver halide emulsion layer

the blue-sensitized silver halide emulsion layer

The method of the invention enables, for example

wise to develop a type of color photographic recording material which has a non-diffusing, a cyan dye forming coupler in the red sensitized silver halide emulsion layer further contains a non-diffusing, magenta dye-forming color coupler in the green sensitized emulsion layer and a non-diffusing yellow dye forming agent Color couplers in the blue sensitized silver halide emulsion layer. Furthermore, it makes this possible

Process of the invention such color photographic

To develop recording materials which do not have non-diffusing color couplers in the emulsion layers contain.

Sensitization may not occur between two or more of the light-sensitized layers hydrophilic colloid interlayers may be arranged. It has proven to be particularly advantageous between the blue-sensitized and the green-sensitized silver hulogcnide emulsion layers have a bleachable yellow filter layer to arrange.

To prepare the individual layers of the recording materials farbpholographischen the usual known hydrophilic colloids can, as photographic usually for making up

The hydrophilic colloids can be used alone or together with other binders and can consist of naturally occurring substances, e.g. B. proteins, e.g. gelati

(10 nc and gelatin derivatives, cellulose derivatives, polysaccharides, for example dextrose, gum arabicut ™ u, like. As well as zen from synthetic polymeric substances. for example water-soluble Poiyvinylverbin fertilize. /. B. polyvinyl pyrrolidone and acrylamide poly

kidneys.

For the production of Aufzeiehnungsmaierialien can now the usual known from development silver hulogenide emulsions can be used

their silver halide, for example, from silver chloride, silver chloride bromide, silver chloride bromide iodide, silver bromide and silver bromide iodide may exist. Particularly beneficial results are mixed with Obtained silver halide emulsions which contain an iodide, for example silver bromide iodide, silver chlorobromide iodide or silver chloride iodide, and which contain mixed silver halide crystals in which the Iodide makes up about 1 to about 20 mole percent of the halide.

It has proven to be particularly advantageous for achieving neighbor effects if at least one Silver halide emulsion layer is present with colored crystals which contain at least 1 mol% more iodide contained than other silver halide crystals in at least one of the other silver halide emulsion layers. However, any silver halide emulsion can be used provided that the emulsion is differs in at least one layer from the emulsion of at least one other layer, and with regard to the rate of development and / or the excess halide in the silver halide.

In addition to or instead of the described differences in the individual silver halide emulsion layers can advantageously determine one or more of the silver halide emulsion layers Additions are incorporated, which inter-layer or intra-layer neighboring effects evoke during black and white development. Typical such additives are diffusing, in 3-position substituted 4-thiazoline-2-thiones, for example those of the structural formula given below:

-N
H

in which: X denotes an alkyl radical, in particular one short-chain alkyl radical, for example a Mcthylodcr Ethyl radical or an alkyl radical which is substituted by at least one hydroxyl radical, for example a hydroxy methyl or / I-hydroxyethyl residue, or a glucose or arabinose residue, or a Alkyl radical with at least one Gurbonylgtuppc, /.B. a formyl, carboxyl, ethoxycurbonyl or acetoxymethyl radical and Z is a radical as defined for X or, preferably, a Wusscrstoffatom.

Such compounds are from the UK Patent 12 20 136 known.

Particularly advantageous 4-thiuzoline-2-thiones have proven to be those which are able to enolize to corresponding mercaptions, for example at a point in time at which the 4-thiuzolin-2-thione reveals the light-sensitive silver halide of a hydrophilic colloid layer , is added.
Typical 4-thiazolin-2-thlono are for example:

4-thiuzoline-4-carboxalclehyd-2-lhione;

S "carbaihoxy-4-methyl-4-thlu / .olin-2-thione;

4-curboxy-4-lhiazolin-2-thlone:

4-carboxy-5-methyl-4-ihUizolln-2-ihione;

4- (D-arubino-octruucetoxybutyl) -

4-thiuzolin-2-thione;

4- (D-Arubino-1,2,3,4-ieiruhyclroxybuivl)

4-thiu / .olin-2-thione;

4-hydroxymethyl-4-thiazolin-2-thione and
4-methyl-4-thiazolin-2-thione.
In solution, these compounds diffuse through hydrophilic colloid layers of a photographic material into which they have been incorporated or to which they are added in a working solution prior to silver image development or in the silver image development itself.
The links form with the silver halogenic

ίο the emulsion layers an immobile complex unc are set free by the silver halide grains when they are developed into silver.

It is assumed that the picture-wise in-freedom set These compounds contain the latent image silver in a layer during development prior to silver halide Inhibits the development of halogenide in an adjacent layer, creating so-called "undercut" neighboring effects be evoked. Such neighboring effects are characterized by the suppression of ai certain gamut of colors produced by neutral exposure and the lack of such suppression for this color gamut for a single color exposure. Such neighbor effects lead to saturated ones ren and stronger dye images. They can advantageously be determined by measuring methods, you for example by Hanson and Horton in the Journal of the Optical Society of America, 42, No. 9 Pages 663-669 of September 1952 and by Pinney ir the magazine "The SPSE Reporter", from November 1960 under the name "Interimage Effects anc Color Reproduction «.

The 4-thiazolin-2-thione substituted in the 3-position « Silver halide emulsion layers are advantageously used in concentrations from about 5.0 to about 5.0 500 mg per mole of silver, in particular in concentrations of about 100 to 200 mg per mole of silver, are added.

If the 4-thiazoline-2-substituted in the 3-position

thione introduced into an emulsion from a solution, for example from a black and white developer solution solution during the photographic development process, in this case it is preferred Concentrations from about 0.1 mg to about 1.0 g per liter of solution, preferably from about 1.0 mg to 50 mg applied per liter.

The method of the invention thus does not result in the manner in which the neighbor effects caused by, but rather only on the fact that such neighbor effects exist. It fell showed that regardless of the way in which these neighboring effects occurred during the black and white development winding are increased or increased during the color winding process of the invention can be increased.

The individual Silberhalogenlclemulsionsschichten dei for performing the method used färb photogruphischcn Aufzeichnungsmatcrialien It can advantageously be sensi bill Siert spectrally in a conventional manner, for example by chen Ubii bekunnten cyanine, merocyanine, complex cyanine ·. complex morocyanin ·, styryl · and / oclei hemicyuninfurbslopen. These dyestuffs are normally characterized by so-called basic nuclei, for example thiuzol, ben / oihiu / ol, naphthothiazole, naphthoxazole, benzoselenazole, nuphihosclenuzol or quinol nuclei, and also so-called FnIIc vuinfnr. 1. B. hydantoin, 2-thlohyduntoin, oxuzolidoiv or pyru / olonkcrnc. Such dyes are

for example from USA patents 21 85 182; 22 41 237; 26 35 961; 26 52 330; 26 66 761; 27 04 715; 25 26 632; 25 03 776; 24 93 748 and 33 84 486 known.

Those for making a color photographic suitable for practicing the method of the invention Silver halide emulsions used in the recording material may further include conventionally known ones Additives, e.g. chemical sensitizers, e.g. B. sulfur sensitizers, for example AHyI-thiocarbamide Thiourea, allyl isothiocyanate, cystine and the like, as well as various gold compounds, z. B. potassium chloroaurate and auritrichloride (see. USA. Patent 25 40 085; 25 97 856 and 25 97 915), as well as a wide variety of palladium compounds, for example Palladium chloride (cf. USA. Patent 25 40 096), potassium chloropalladate (cf. USA. Patent 25 98 079), as well as mixtures of such sensitizers, finally antifoggants, e.g. B. Ammonium chloroplatinate (cf. USA. Patent 25 66 245), ammonium chloroplatinite (cf. USA. Patent 25 66 263), benzotriazole, nitrobenzimidazole, 5-nitroindazole, benzidine and mercaptans (see the book von M e s "The Theory of the Photographic Process", Verlag Macmillan, 1942, page 460) or mixtures of these, furthermore hardeners, for example formaldehyde or chromium aluminum sulfate (cf. USA patent specification 17 63 533), also glyoxal (cf. USA patent 18 70 354), dibromacrolein (cf. British patent 4 06 750), aziridine hardeners (see USA patents 29 64 404, 29 50 197 and 30 17 280), oxazolium hardeners (See USA patents 33 16 095 and 33 21 313) and also vinyl sulfone curing agents (see Belgian patent specification 6 86 440) included.

If photographic recording materials with color couplers contained therein are used to carry out the process of the invention, these color couplers can consist of the customary known color couplers as used for the production of such recording materials. Typical couplers which form so-called phenolic or naphtholic blue-green dyes and which are suitable for the production of such recording materials are described, for example, in U.S. Patents 24 23 730, 24 74 293, 25 21 908, 27 25 291, 28 01171 and 32 53 294 . Typical ketomethylene yellow couplers that may be included in the color photographic material used to practice the method of the invention are disclosed, for example, in U.S. Patents 2,298,443, 2,778,658, 28,01171, 2,875,057, 3,253,924, and 32,77 155 known. Typical 5-pyrazoion magenta couplers which may have been used to produce a corresponding color photographic material are described, for example, in U.S. Patents 2,600,788, 2,800,171 and 3,252,924.

Conventional, known dispersion processes can be used to incorporate the color couplers are unier the use of customary known dispersants, such as those known for example from the USA-Ptuent documents 23 22 027, 23 04 940 and 28 01171 are.

Production of the used according to the invention Color developer blends

The color developer compounds used according to the invention can be prepared, for example, by reacting a corresponding ω-alkoxyalkyl chloride or oj-alkoxynylkyl bromide with a corresponding 3-alkylaniline or 3-alkoxyaniline, for example N-ethyl-3-alkylaniline or N-ethyl-3-alkoxyaniline. The tertiary anilines obtained in this reaction can then either be nitrosated or azo-coupled, which is followed by a catalytic hydrogenation to produce the corresponding p-phenylenediamine. Some of the developer compounds which can be used according to the invention can advantageously be isolated in the form of their acid salts.

ίο A) The di-p-toluenesulfonic acid salt of the color developing agent No. 3 (N-ethyl-N-ethoxyethyl-3-methylp-phenylenediamine) can be produced in an advantageous manner as follows:

1. N- (j3-Ethoxyethyl) -N-ethyl-3-methylaniline

A mixture of 135 g of N-ethyl-3-methylaniline, 153 g of 2-bromoethyl ethyl ether (purified by treatment with sodium bicarbonate and distillation), 88.2 g of sodium bicarbonate, 1100 ml of ethanol and 290 ml of water was refluxed for a total of 64 hours. The ethanol was made by distillation removed and the oily layer was extracted with ether. The ether extracts were dried and concentrated and the residue was distilled under reduced pressure. After removing the low-boiling Pre-fractions were a fraction with a boiling range of 92 to 95 ° C at a pressure of 1 mm (which is slightly overheated). The yield of the reaction product was about 70% Theory.

I1.4- (2,5-dichlorophenylazo) -N- (0-ethoxyethyl) -N-ethyl-3-methylaniline

44 g of 2,5-dichloroaniline was dissolved in a mixture of 240 ml of concentrated hydrochloric acid and 700 ml of water by heating with stirring on a steam bath. After the solution had taken place, the reaction mixture was ^{cooled to 5 °} C. with stirring, the hydrochloride salt separating out.

A solution of 19 g of sodium nitrite in 75 ml of water was added dropwise with stirring, the Temperature was maintained at about 5 ° C. When the addition was complete, it was continued for another 20 minutes stirred, whereupon the excess nitrous acid

was destroyed by the addition of sulfamic acid. The cold diazonium solution was filtered and in a Times to a cold solution of 56 g of compound 1) in dilute hydrochloric acid. Now there was considerably more water

so added, whereupon a total of 250 g of sodium succtate were added with stirring to effect the coupling . The reaction mixture was then left to stand for a few hours, whereupon the precipitated azo dye was nitrated off and in one time from about

1000 ml of ethanol was recrystallized. The recrystallized dye was then recrystallized again from 900 ml of ethanol. The yield of the reaction product was about 77%. The melting point of the reaction product was 74.5 to 75.5 ⁰ C.

4-Amino-N- (0-etho> iyathyl) -N-ethyl 3-methylane, di-P-toluenesulfonic acid salt

3 g of the azo dyes »II were reduced in a Parr shaker, namely below Use of 300 ml of absolute alcohol and Runey nickel as a catalyst. After the reduction was complete, the catalyst was filtered off and on a Funnel washed with ethanol. Now became one

Solution of 3 g of p-ToltiolsuHonsiiurc (hydrate) in 50 ml of ethanol was added, whereupon the solution was evaporated to dryness under reduced pressure. The semi-solid mass thus obtained was then thoroughly slurried in 35 ml of hot isopropyl alcohol, whereby a gradually crystalline product was obtained. The mixture was then cooled to about 25 ° C and allowed to stand overnight. The developer salt was then filtered off and washed on a funnel with small amounts of isopropyl alcohol. The yield of developing agent having a melting point 214-216 ^C. C was about 70%.

B) The di-p-toluenesulfonic acid salt of the color developer compound No. 5 (N-ethyl-N-methoxyethyl-3-methoxy-p-phenylenediamine) was prepared in a similar manner to developer compound 3, however using N-ethyl-3-methoxyaniline and 2-Bromoälhylmethyläther as starting compounds.

20th

III. N-Athyi-3-methoxy-N - (/} - methoxyethyl) aniline

A mixture of 100 g of N-ethyl-3-methoxyaniline, 92 g of 2-bromoethyl methyl ether, 55.8 g of sodium bicarbonate, 1000 ml of ethanol and 280 ml of water were refluxed for a total of 68 hours heated. The alcohol was then removed under reduced pressure, followed by the remaining oily layer Ether was extracted. The combined ether extracts were then dried and concentrated. The remaining oil was then distilled under reduced pressure. Compound IH was found in one yield of 35% of theory in the form of a fraction with a boiling range of 149 to 151 ° C at a pressure of 8 mm received.

35

IV.4- (2,5-dichlorophenylazo) -N-ethyl-3-methoxy-N- (j9-methoxyethyl) aniline

The azo dye was obtained from the compound III in Made exactly the same way as it was used to make the azo dye used to make it developer compound 3 was used. The yield of compound IV with a melting point of 94 to 96 ° C (from ethanol) was about 73%.

Di-p-toluenesulfonic acid salt of

4-amino-N-ethyl-3-methoxy-

N-fj3-methoxyethyl) aniline

Exactly 4.86 g of the azo dye IV was mixed in a shaker according to Par using 300 ml of absolute alcohol and Raney nickel as a catalyst reduced. After the reduction is finished the catalyst was filtered off and washed on a funnel with alcohol. The solution of the reduced Azo dye was a total of 4.84 g of p-toluenesulfonic acid (Hydrate) added in 50 ml of ethanol. There was no precipitation. The solution was at reduced Pressure evaporated to dryness. The resulting gummy residue was then in a small Dissolved amount of absolute alcohol, whereupon a large volume of ethyl ether was added. The developer salt was again eliminated as a rubbery product. The solution was thoroughly in a refrigerator cooled to precipitate the suspension. The ether-alcohol layer was decanted. This way of treatmentc was repeated twice to remove any regenerated 2,5-dichloroaniline. Finally d ^ s Developer salt thoroughly slurried with ether alone, whereby it gradually became crystalline. It was dried in a vacuum oven. The yield of developer compound 5, which had a melting point of 160 to 162 "C, was 62%.

The di-p-toluenesulfonic acid salt of Developer Compound 1 was prepared in a manner similar to that of Acid salt of color developing agent 5 prepared, with the exception, however, that instead of N-ethyl-3-methoxyaniline an equimolar amount of N-ethyl-3-methylaniline was used.

The di-p-loluenesulfonic acid salt of the color developing agent 2 was prepared in the same way as the acid salt of color developing agent 5, with the exception, however, that instead of 2-bromoethyl methyl ether, an equimolar amount of co-bromobutyl methyl ether has been used.

The di-p-toluenesulfonic acid salt of color developing agent 4 was prepared in the same manner as for the acid salt the color developer compound 3 indicated, with the exception, however, that instead of N-ethyl-3-methylaniline an equimolar amount of N-ethyl-3-propylaniline was used.

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

example 1

Two sections of multilayer color photographic film recording material were included a cellulose acetate film support and the layers applied thereon in the following order, namely a red sensitized gelatin-silver bromide iodide emulsion layer, a green sensitized gelatin-silver bromide iodide emulsion layer, a gelatin layer with bleachable yellow Carey Lea silver and a blue sensitized gelatin silver bromide iodide emulsion layer exposed sensitometrically to a step tablet, whereupon the exposed test specimens were subjected to the development process given below at 27 ° C were subjected to:

Stages of the development process Duration Pre-hardening 2 min. Water 30 sec. Develop with Negative developer 3 min. 40 sec. Water 1 min. Exposing to red light through the substrate Bluish green development 4 min. 30 sec. Water 2 min. Exposing with blue Light through the Emulsion layers Yellow development 4 min. Water 2 min. Borohydride bath 1 min. Water 30 sec. Purple t winding 5 min. 30 sec. Water 4 min. Ferricyanide bath 2 min. Hypo-fixing bath 2 min. Water 4 min. dry

17th

The solutions or baths used to carry out the development process were owned by the the following composition:

Vanguard 0.5 g Sodium hexametaphosphate 1.7 ml sulfuric acid 15.0 g Sodium tetraborate · 5H2O 2.0 g Sodium bromide 200.0 g Sodium sulfate 20.0 ml Formalin (37.5%) 1.0 g Sodium bisulfite 1.0 litei Topped up with water Negative developer 0.6 g Sodium hexametaphosphate 79.0 g Sodium sulfite Monomethyl-p-aminophenol- 5.0 g sulfate 1.0 g Sodium hydroxide 2.0 g Hydroquinone 35.0 g sodium 12.5 ml Potassium iodide (0.1% solution) 3.0 g Sodium bromide 1.7 g Sodium thiocyanate 4.0 g Hydroquinone monosulfate 1.0 liter Topped up with water Blue-green developer bath 0.6 g Sodium hexametaphosphate 2.5 g Sodium bromide 5-nitrobenzimidazole nitrate 3.0 ml (1% in 0.1% NaOH solution) 11.0 ml Potassium iodide (0.1% solution) 10.0 g Sodium sulfite 60.0 g Sodium sulfate 3.8 g Sodium hydroxide 1.0 g Sodium thiocyanate 0.65 g Hydroxylamine sulfate 4-amino-N-ethyl-N-jS-hydroxy- 2.05 g ethyl 3-methylaniline sulfate l-hydroxy-N- (2-acetamido- 1.65 g phen-ethyl) -2-naphthamide 5.0 ml Hexylene glycol Polyoxyethylene 1.0 g (Molar weight 1540) 0.45 g N-benzyl-p-aminophenol 2.0 ml Methanol 0.16 g p-aminophenol 1.0 liter Topped up with water Yellow developer bath 0.6 g Sodium hexametaphosphate 10.0 g Sodium sulfite 0.55 g Sodium bromide 1.00 g Polyoxyethylene (mol.wt. 4000) 26.0 ml Potassium iodide (0.1% solution) Color developer compound *) 5-nitrobenzimidazole 10.0 ml (10% solution) 2.1g Sodium hydroxide 64.0 g Sodium sulfate 10.0 ml Hexylene glycol 2.0 g Λ-pivalyl acetanilide Forming yellow dye Color coupler: 1.38 ml Diethyl hydroxylamine 0.5 g 1-phenyl-5-pyrazolidone

Made up to 1 liter with water

pH value at 27 ^° C = 12.0

Section 1 was developed yellow in a (developer bath, the 1.06 g of the color developer compound N-Ethyl-N- (j3-hyroxyäihyl) -3-methyl-p-phenylcndiumin contained. In contrast, section II was developed in the yellow developer bath itself, and 2.0 g / l of the color developer compound No. l.d. H. of N-ethyl-N-nielhoxyäthyl-3-methyl-p-phenylene contained diamine.

Borohydride bath 0.6 g Sodium hexametaphosphal 2.16 g Sodium hydroxide 0.10 g Potassium boron hydride 1.0 liter Topped up with water Purple developer bath 4.0 g Sodium hexametaphosphate 2.1 ml sulfuric acid 40.0 g Sodium phosphate ■ 12H ₂ O 5.0 g Sodium sulfite 1.0 g Sodium thiocyanate 7.5 ml Potassium iodide (0.1% solution) 0.5 g Sodium bromide 60.0 g Sodium sulfate 4-amino-N-ethyl-N-jS-hydroxy- 2.9 g ethyl 3-methylaniline sulfate 0.72 g Citrazinic acid 3.0 ml Ethylenediamine 1.0 g Polyoxyethylene (mol.wt. 4000) 10.0 ml Hexylene glycol 5-pyrazolone coupler des U.S. Patent 3,152,896 1.67 g known type 0.32 g Sodium hydroxide 1 liter Topped up with water

The bleach bath used consisted of a conventional one, an alkali metal bromide and an alkali metal ferricyanide containing bleach bath. The Hypo-Fixierbart consisted of a common alkali metal thiosulphate fixer.

A comparison of the developed sections indicated that the developed according to the method of the invention Section II versus Film Section I which had been developed in accordance with the prior art showed significantly better color rendering of the step tablet used as a template than that after the State of the art developed section. Furthermore, the developed according to the method of the invention showed Section on considerably stronger shades of blue.

Example 2

The procedure described in Example 1 was repeated, but this time using the color developing agents 2, 3, 4, 5 and 6 were tested in place of Color Developing Compound 1. The color developing agents 2, 3, 4, 5 and 6 were used in equimolar amounts in place of color developing agent 1 im Yellow developer bath used. In each case, color reproductions were made using the method of the invention obtained which was superior to the reproduction according to the method of the prior art described was obtained. In particular, the sections developed by the method of the invention had considerably stronger shades of blue.

Example 3

21

Two sections 1 and II of a multilayer, multicolor photographic recording material, consisting of a cellulose acetate film layer with layers applied thereon in the following order, namely a red-sensitized gelatin-silver bromide emulsion layer (with 6 mol% iodide), containing a mixture of non-diffusing, cyan dye-forming _couplings! learning _0, ie a Naphlhamidkuppler of the known type from the USA. PateiHschrift-24 74 293, and a phenolic coupler of the prior art from the USA. Patentschri'i-28 95 826 type, a green sensitized silver bromoiodide gelatin mt

6 mol% iodide containing a non-diffusing, a magenta dye-forming coupler of the 5-pyrazolone type (see. US Pat. No. 29 08 573) and a blue-sensitized gelatin silver bromide iodic emulsion layer with 6 mol% iodide containing a non- diffusing, a delivering yellow dye! Couplers of the <* - pivalyl - «- phenoxyacetanilide type known from US Pat.

Section I was prepared at 38 ° C. according to that known from Example 2 of U.S. Pat. No. 2,984,567 Process developed, but instead of the color developer solution specified in Example 2 of the patent a developer solution of the following composition was used:

59

Sodium sulfite 2.9 g Trisodium phosphate · 12H ₂ O 36.0 g N-ethyl-N- (| S-methanesulfonamido- ethyl) -3-methyl-p-phenylene- diamine 10.5 g Citrazinic acid 135 g Dithiooctanediol 1.00 g Topped up with water 1.0 liter pH = 11.25

35

40

Section II was developed after exposure by the method of the invention, the same procedure as was used for the development of Section I, with the exception However, that the 10.5 g / l N-ethyl-N- (j3-methyIsulfonamido-ethyl) -3-methyl-p-phenylenediamine by 14 g / l N-ethyl-N-methoxy-ethyl-3-methyl-p-phenylenediamine have been replaced.

_{The D m} »r values determined for the developed sections are compiled in the following table:

table

proceedings Blue- Yellow Purple- green- color Red- color drinking picture color fabric image fabric image

55

60

According to the prior art 2.9
According to invention 3.3

Example 4

2.4 2.7

3.2 3.6

Two sections, III and IV, of the multilayer, multicolor recording material described in Example 3 were each subjected to a gradual exposure as required for the verification of Neighbor effects is used. The gradual exposure consisted of exposure to red light, a subsequent exposure to blue light and a flash exposure to green light.

The exposed section II was made according to the procedure described in Example 3 for section I. while Section IV was developed according to the method of the invention as in Example 3 for the Section II, was developed.

Density-exposure curves were plotted. A comparison of these curves showed that the undesired green light absorption of the cyan and yellow dye images in the case of Section IV, d. H. of the section developed by the method of the invention had been corrected, whereas the undesired light absorption in the case of section III, which is carried out according to the method of the invention had been developed, had been considerably undercorrected.

Example 5

First, a multilayer, multicolor color photographic recording material of the in Example 3 prepared type described. However, the recording material produced was different of the recording material described in Example 3 as follows:

In the red sensitive layer, a non-diffusing phenolic, a blue-green image became supplying color coupler of the type known from US Pat. No. 24 23 730. Further became a yellow image dye forming coupler of α-acylacetamide type in the blue-sensitive layer housed. The newly produced recording material thus differed from that in Example 3 described recording material only through the use of other color couplers.

Sections I and II of this recording material were then exposed as described in Example 4. Sections I and II were then made according to the prior art method and the other developed according to the method of the invention as described in Example 3.

Density-exposure curves were prepared from the processed recording materials. This Curves showed that the undesirable green light absorption in the cyan and yellow dye images in the Case of applying the method of the invention was corrected by amplifying the Neighboring effect, whereas the undesired light absorption in the case of the application of the traverser of the prior art have been significantly undercorrected.

Example 6

Four sections, namely Sections V, VI and VII and VIII, of the multilayer described in Example 3 Multicolored recording material was exposed sensitometrically to a step tablet and developed.

Sections V and VI were prepared using the prior art procedure as described in Example 3 has been described, developed using a color developing solution whose pH value in the case of section V was adjusted to 10.4 and in the case of section VI to 11.6.

Sections VI and VIII were made according to the method of the invention described in Example 3 developed using a color developing solution, the pH of which in the case of the section VII to 10.4 and in the case of section VIII to 11.6 had been set.

In each case, the change was developed Cyan dye density determined, which was brought about by increasing the pH of the color developer solution from 10.4 to 11.6 for an exposure level that contributes to a cyan density between 1 and 2 resulted in a pH of 10.4.

Similarly, in the case of the developed yellow dye images and magenta dye images proceedings. The results obtained are summarized in the following table:

table

Dye image

Change in dye density
by increasing the pH
of the color developer bath from 10.4 to 11.6

Procedure of the
State of
technology

Procedure of
invention

Blue green

Purple

+ 0.30
-0.25
+ 0.43

+ 0.12
-0.12
+ 0.14

22nd

Color developer compound (Λ) versus one of us US-PS 21 63 166 known, structurally very similar color developer compound (B) can be achieved.

The color developing agent used in the present invention (A) consisted of:

N-ethyl-N - (/? - methoxyethyl) -3-methyl-p-phenylenediamine, Di-p-toluenesulfonate of the following formula:

H ₅ QN-CH ₂ CH ₂ -O-CH ₃

Compound (B) according to Example 4 of US Pat. No. 2,163,166, tested for comparison purposes, consisted of:

N-Ethyl-N [^ - (/ 3-hydroxyethoxy) ethy!] - 3-methyl-pphenylenediamine, Di-p-toluenesulfonate of the following formula:

H ₅ C ₂ -N-CH ₂ CH ₂ -O-CH ₂ CH ₂ OH

NH ₂

SO ₃ H

35

From the results obtained, it can be seen that when the method of the invention is carried out, a there is less change in dye density at a given level of exposure than in the case of Prior art processes which make the process of the invention less pH sensitive is as the prior art method.

Example 7
(Comparative example)

This example illustrates the beneficial results that can be obtained with one used in accordance with the invention Test series I

40 Two sections A and B of a multilayer, multicolor photographic material as described in Example 3 were exposed and developed in the manner indicated in Example 3.

The only difference in development was that a Color developing solution was used which contained 14.0 g of color developing agent (A) per liter of solution, and that a color developing solution per liter was used to develop the B section Solution 14.7g (i.e. an equimolar amount) of the Color developing agent (B) contained. The following results were obtained:

Dmin green blue Dmin green blue IOt 0.20 0.24 Red 4.02 4.14 Test item A (procedure according to 0.20 3.50 Invention) 0.19 0.19 3.02 3.16 Test item B (procedure with 0.16 3.04 well-known color developer connection)

From the results obtained it is found that when the color developing agent (A) is used, sharper, higher contrast and denser images are obtained than in the case of the use of the color developing agent (B).

Test series II
Test series Ila

Two sections A and B of a multilayer, multicolor recording material as in Example 1 were exposed and developed in the manner described in Example 1. The only difference in developing sections A and B, the development of section A a yellow image dye-forming color development was used, the 2.52 g of the color developer

containing compound (A) per liter of solution, while a yellow one for the development of the section B Image dye forming color developing solution containing 2.64 g of the color developing agent was used (B), d. H. an equimolarc amount per liter of solution.

The same color developer solutions were used to develop the cyan and magenta color partial images used.

ίο The ones listed in the following table were found Get results:

Dmin

rol

green

Dmax
Red

green

blue

Test A (method according to 0.04 0.15

Invention)

Test item B (method with 0.04 0.15

known color developer compound)

From the results obtained, it is found that in the case of using the color developing agent (A) the density of the yellow image dye was considerably higher than when using the Color developing agent (B).

Test series Hb

Two further sections A 'and B' of the same recording material were made in the same way exposed sensitometrically and then developed as follows:

Pre-hardening,

Water,

0.16
0.16

4.49
4.46

3.86 3.80

4.24 3.80

MQ development,

Water,

Red light exposure,

Development of the blue-green partial image *), watering,

Blue light exposure,

Development of the yellow partial image, watering,

Ferricyanide bleach,

Hypo-Fixing Bath,

Water,

Dry.

In the case of this test series Ub too, the development process of sections A 'and B' only differed in the use of various color developing agents in the development of the yellow partial image. The results compiled in the following table were obtained:

Dmin green blue Dmax green blue Red + + 0.10 Red + 4.28 + + + 0.10 + ₊ 3.80 ₊

Test item A '(procedure
according to the invention)
Test item B '(procedure with
known color developer compound)

+ Dye was washed out.
+ + No purple dye was developed.

Correspondingly more favorable results were obtained as in the case of test series IIIa.

*) In the color developer solution used to develop the cyan partial image , the color coupler used in Example 1 was replaced by the soluble dye- forming color coupler 3,6-disulfo-8-amino-1-naphthol (H-SUure) of the formula

H, N OH

HOjS

SO ₃ H SS replaced. The color coupler reacted with the oxidized color developer compound to produce a dye which completely diffused In dl <developer solution from the recording material. In this way, no blue-green image dye was produced in the rat-sensitive silver halide emulsions. The removal of this dye! and not developing a crimson! The aim of the partial image was to generate only a yellow partial image in the blue-sensitive silver halide demulsions layer.

60 709Θ27 / 14Β

Claims (1)

Patent claims: 1. Process for producing color photographic Images in which a color photographic recording material consisting of a transparent Layer support and at least two applied to it, opposite different areas of the spectrum sensitive silver halide emulsion layers, after imagewise exposure initially subjected to black and white development and then in the presence of not color couplers producing diffusing image dyes, characterized in that that a color developing bath is used for color development, which acts as a color developing agent at least one 3-alkyl-N-alkyL-N-alkoxy-alkyl-p-phenylenediamine, optionally present in salt form and / or at least one 3-alkoxy-N-alkyI-N-alkoxy-alkyl-p-phenylenediamine the following formula contains: