EP0415056A2 - Colour photographic recording material with a coupler liberating a photographically useful compound - Google Patents

Abstract

When using DIR couplers of the formula I in color photographic silver halide materials, high edge effects and interimage effects are achieved. <IMAGE> In formula I are: R¹ is alkyl, for example -C4H9-t, aryl, for example p-alkoxyphenyl -NH-aryl or -NH-NH-R³; R² H, halogen, e.g. Chlorine, alkoxy, alkylthio or -NH-R <4>; R³, R <4> acyl; X is the residue of a photographically active compound with a monocyclic 1,2,3- or 1,2,4-triazole ring; TIME a link; n 0 or 1.

Description

The invention relates to a color photographic recording material having at least one light-sensitive silver halide emulsion layer which contains a coupler which, during color development, contains a photographically active group, e.g. releases a development inhibitor.

It is known to carry out the chromogenic development in the presence of compounds which, during development, release imagewise diffusible substances which have a certain effect, for example are able to influence the development of silver halide. If this effect consists in inhibiting further development, such compounds are referred to as so-called DIR compounds (DIR = development inhibitor releasing). The DIR compounds can be those which release an inhibitor residue with the oxide tion product of a color developer to form a dye (DIR coupler), or those that release the inhibitor without simultaneously forming a dye. The latter are also referred to as DIR connections in the narrower sense.

DIR couplers are known, for example, from US-A-3 148 062, US-A-3 227 554, US-A-3 615 506, US-A-3 617 291 and DE-A-24 14 006.

However, the diffusible, photographically active compounds that are released during development can also be, for example, a dye, a coupler, a hardening agent, a silver halide solvent, a fogging agent, a development accelerator, a developer compound, a bleaching inhibitor, a bleaching accelerator Trade mordants or a sensitizer.

Development inhibitors released are usually heterocyclic mercapto compounds or triazoles or benzotriazoles. With regard to the essentially colorless coupling of DIR compounds, reference is made, for example, to US Pat. No. 3,632,345, DE-A-23 59 295 and DE-A-25 40 959. By using DIR compounds, a large number of photographic, the Effects influencing image quality are brought about. Such effects are, for example, the lowering of the gradation, the achievement of a finer grain of color, the improvement of the sharpness by the so-called edge effect and the improvement of the color purity and Color brilliance through so-called interimage effects. Reference is made, for example, to the publication "Development-Inhibitor-Releasing (DIR) Couplers in Color Photography" by CR Barr, JR Thirtle and PW Vittum, Photographic Science and Engineering 13 , 74 (1969).

The colorless coupling DIR compounds have the advantage over the color coupling DIR couplers that they can be used universally, so that the same connection can be used in all light-sensitive layers of a color photographic recording material regardless of the color to be produced. DIR couplers, on the other hand, can usually only be used in part of the light-sensitive layers because of the color they produce, unless the color secondary density attributable to them is tolerable in the other layers. This advantage of the DIR compounds is offset by the disadvantage that they are generally less reactive than the DIR couplers. In practice, it has therefore mostly been limited to using DIR couplers and, if necessary, two or more different ones in the same recording material, different DIR couplers being assigned to the differently spectrally sensitized layers in accordance with the color produced from the latter.

It is usually important that the photographically active compound be released rapidly from the coupler upon development, especially when the photographically active compound is to influence the further course of development. It is therefore very desirable if the couplers in question are very active are. In addition to the group of the photographically active compound bound to the coupling point of the coupler as a so-called escape group, the structure of the coupler is also of particular importance. DIR couplers derived from α-heterocyclically substituted acetamides are known from JP-A-52 082 423. EP-AO 287 833 describes quinazolone acetanilide DIR couplers which have extremely advantageous properties.

The aim of the invention is to achieve improvements in general solubility and in alkali solubility while maintaining the good properties of the quinazolone acetanilides (good level of action, high stability, good accessibility). Surprisingly, it was found that by replacing the carbonyl group of the quinazolone ring with a sulfone group (benzosulfondiazine ring) while maintaining the other structural elements, DIR couplers are obtained whose pK values are 2.5 to 3 units lower than those of the comparable quinazolone acetanilides.

worin bedeuten:
R¹ Alkyl, beispielsweise -C₄H₉-t, Aryl, beispielsweise p-Alkoxyphenyl -NH-Aryl oder -NH-NH-R³;
R² H, Halogen, z.B. Chlor, Alkoxy, Alkylthio oder -NH-R⁴;
R³, R⁴ Acyl;
X den Rest einer fotografisch wirksamen Verbindung mit einem monocyclischen 1,2,3- oder 1,2,4-Triazol­ring;
TIME ein Bindeglied, das bei Reaktion des Kupplers mit dem Oxidationsprodukt eines Farbentwicklers zusam­men mit dem daran gebundenen Rest X freigesetzt wird und seinerseits unter den Entwicklungsbedin­gungen den Rest X als fotografisch wirksame Verbin­dung freisetzt;
n 0 oder 1.The invention relates to a color photographic recording material having at least one light-sensitive silver halide emulsion layer and a coupler associated therewith which is capable of releasing a photographically active compound, characterized in that the coupler corresponds to the following formula I.

in which mean:
R¹ is alkyl, for example -C₄H₉-t, aryl, for example p-alkoxyphenyl -NH-aryl or -NH-NH-R³;
R² H, halogen, for example chlorine, alkoxy, alkylthio or -NH-R⁴;
R³, R⁴ acyl;
X is the residue of a photographically active compound with a monocyclic 1,2,3- or 1,2,4-triazole ring;
TIME is a link which, when the coupler reacts with the oxidation product of a color developer, is released together with the radical X attached to it and in turn releases the radical X as a photographically active compound under the development conditions;
n 0 or 1.

An alkyl radical represented by R 1 in formula I is straight-chain or branched, substituted or unsubstituted and contains 1-20 C atoms; Methyl, ethyl, butyl, hexyl, dodecyl and especially -C₄H₉-t are examples of this.

An aryl group represented by Formula 1 or contained in R1 is in particular phenyl or a for example phenyl group substituted by halogen, alkyl, alkoxy, acylamino or sulfamoyl, for example p-alkoxyphenyl, o-alkoxyphenyl, 2-chloro-5-acylaminophenyl, 2-hexadecyloxy-5- (N-methyl) sulfamoyl.

An acyl radical represented by R³ or R⁴ in formula I can be derived from an aliphatic or aromatic carboxylic acid or sulfonic acid, from a carbamic acid or sulfamic acid or from a carbonic acid semiester. Acyl radicals derived from aliphatic carboxylic acids, e.g. Alkylcarbonyl.

H-, wobei das O-Atom an die Kupplungsstelle des Kupplers und das C-Atom an ein N-Atom einer fotografisch wirksamen Verbindung gebunden ist (z.B. DE-A-27 03 145), eine Gruppe, die nach Abspaltung vom Kuppler einer intramo­lekularen nukleophilen Verdrängungsreaktion unterliegt und hierbei die fotografisch wirksame Verbindung frei­setzt (z.B. DE-A-28 55 697), eine Gruppe, in der nach Abspaltung vom Kuppler eine Elektronenübertragung ent­lang eines konjugierten Systems stattfinden kann, wo­durch die fotografisch wirksame Verbindung freigesetzt wird (z.B. DE-A-31 05 026), oder eine Gruppe

-X-

, worin X (z.B. -O-) an die Kupplungsstelle des Kupplers und das C-Atom an ein Atom der fotografisch wirksamen Verbindung gebunden ist und worin R beispiels­weise für Aryl steht (z.B. EP-A-O 127 063). Die Gruppe TIME kann auch eine Gruppe sein, die nach Abspaltung aus der Kupplungsstelle des Kupplers selbst eine Kupplungs­reaktion oder eine Redoxreaktion eingehen kann und als Folge einer solchen Reaktion die an sie gebundene Gruppe X freisetzt.A link represented by Formula I by TIME is a group which, after being split off from the coupling point of the coupler when it is coupled with the oxidation product of the silver halide developing agent, is capable of releasing a photographically active residue bound to it, in the present case a triazole of the formula II, in a subsequent reaction . The group TIME is also referred to as a time control element because, in the presence of such a group, the photographically active residue attached to it is released in many cases in a delayed manner and can take effect. Known timing elements are, for example, a group

-O-

H-, the O atom being bound to the coupling point of the coupler and the C atom being bound to an N atom of a photographically active compound (for example DE-A-27 03 145), a group which, after being split off from the coupler, is an intramolecular compound nucleophilic displacement reaction and thereby releases the photographically active compound (eg DE-A-28 55 697), a group in which, after separation from the coupler, electron transfer can take place along a conjugate system, whereby the photographically active compound is released (eg DE-A-31 05 026), or a group

-X-

, in which X (for example -O-) is bonded to the coupling point of the coupler and the C atom to an atom of the photographically active compound and in which R is, for example, aryl (for example EP-AO 127 063). The group TIME can also be a group which, after being split off from the coupling point of the coupler, can itself undergo a coupling reaction or a redox reaction and, as a result of such a reaction, releases the group X bound to it.

worin bedeuten:
Z den Rest zur Vervollständigung eines 1,2,3- oder 1,2,4-Triazolringes;
R⁵ und R⁶ H, Alkyl, Aryl, eine heterocyclische Gruppe, Alkoxy, -S-R⁷, Amino, Acylamino, eine Carbon­säureestergrupe oder -CO-NR⁸R⁹,
wobei gilt, daß wenigstens einer der Reste R⁵ und R⁶ eine Gruppe mit fotografischer Wirksamkeit darstellt oder daß die Verbindung der Formel II

nach Freisetzung als Ganzes eine fotografisch wirksame Verbindung ist, insbesondere ein Silber­halogenidentwicklungsinhibitor ist;
R⁷ Alkyl, Cycloalkyl, Aralkyl, Alkenyl, Alkinyl oder Aryl;
R⁸ Alkyl, Aralkyl oder Aryl;
R⁹ H, einen Rest wie R⁸ oder R⁸ und R⁹ zusammen den Rest zur Vervollständi­gung einer cyclischen Aminogruppe.The cleavable group X is the remainder of a photographically active compound which is bonded to the coupling point of the coupler or to the timing element TIME via a nitrogen atom of a 1,2,3- or 1,2,4-triazole ring. Such a group X corresponds, for example, to the formula

in which mean:
Z is the balance to complete a 1,2,3- or 1,2,4-triazole ring;
R⁵ and R⁶ H, alkyl, aryl, a heterocyclic group, alkoxy, -S-R⁷, amino, acylamino, a carboxylic acid ester group or -CO-NR⁸R⁹,
with the proviso that at least one of the radicals R⁵ and R⁶ represents a group with photographic activity or that the compound of the formula II

after release as a whole is a photographically active compound, especially a silver halide development inhibitor;
R⁷ alkyl, cycloalkyl, aralkyl, alkenyl, alkynyl or aryl;
R⁸ alkyl, aralkyl or aryl;
R⁹ H, a radical such as R⁸ or R⁸ and R⁹ together the radical to complete a cyclic amino group.

An alkyl radical represented by R⁵, R⁶, R⁷, R⁸ or R⁹ in formula II can be straight-chain or branched and can contain up to 10 carbon atoms; Examples are methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, pentyl, hexyl, octyl. The alkyl radicals can be substituted, for example by hydroxyl, alkoxy, alkylthio, acylamino or a cyclic imide group.

A cycloalkyl radical represented by R⁷ is, for example, cyclohexyl; an aralkyl radical (R⁷, R⁸) is, for example, benzyl; an alkenyl radical is, for example, allyl or 2-butenyl; an alkynyl radical is, for example, propynyl.

A cyclic amino group (R⁸, R⁹) is for example a piperidino or morpholino group.

worin
Y den zur Vervollständigung eines carbocyclischen oder heterocyclischen, gegebenenfalls substitu­ierten Ringes erforderlichen Rest bedeutet.A cyclic imido group is, for example, a succinimido group, maleimido group, phthalimido group, hexahydrophthalimido group or a group of the formula

wherein
Y represents the radical required to complete a carbocyclic or heterocyclic, optionally substituted ring.

A heterocyclic group represented by R⁵ or R⁶ is, for example, a furyl, thiazolyl or 1,2,4-triazolyl group. Such a heterocyclic group can carry further substituents, e.g. Alkyl, alkoxy, alkylthio (-S-R⁷).

In particularly preferred couplers of the present invention, R⁵ is alkylthio and R⁶ is H, alkyl, alkylthio, aryl or a heterocyclic group, with the measure gave that at least one of the radicals R⁵ and R⁶ at a distance of 2 to 4 atoms from the triazole ring contains a group saponifiable in aqueous alkali, cf. German patent application P 39 18 394.7.

The DIR couplers according to the invention from the series of benzo-1,2,4-sulfondiazine-3-acetic anilides are excellently soluble in esters and alcohols, so that their incorporation into photographic layers presents no difficulties and means no restrictions in the choice of the coupler solvent.

The same also applies to the other DIR coupler types according to the general formula I, in which the function (-CO-R¹) corresponds to a ketone or a diacylhydrazine.

The new DIR couplers couple above pH = 8.5 largely independently of the pH of the developer. A material built with them is less susceptible to fluctuations in the alkali content of the developer in terms of its sensitometric properties than a material built with conventional DIR couplers.

The coupling color of the chromogenic dyes formed from the new DIR couplers is in the range from orange to scarlet red, so it contributes comparatively little to the image information of the negative.

The advantageous properties of the couplers according to the invention are presumably not least also toward this to be attributed to the fact that the triazole ring is apparently not only a good leaving group (leaving group), so that the couplers are very reactive, but apparently also has a certain tendency to adsorb on the silver halide grain and thereby influence the processes taking place during the development of the silver halide. The groups determining the effectiveness of the photographically active compound apparently come into particularly favorable contact with the surface of the silver halide grain. It is therefore preferred according to the invention if the photographically active compound is one which influences the development of the silver halide, for example a development accelerator, a fogging agent, a bleaching accelerator or particularly preferably a development inhibitor. In the latter case in particular, it is further preferred if at least one of the radicals R⁵ and R⁶ is -S-R⁷ and at least one contains a saponifiable group.

Since they are very active, the couplers according to the invention can be used in comparatively low concentrations. This also facilitates their use in layers of the color photographic recording material in which mainly purple or cyan dyes are produced without the respective color image being significantly impaired by an undesirable secondary density.

DIR couplers that are particularly useful in the context of the invention are, for example, the following:

The DIR couplers are synthesized in a substantially known manner by known processes.

The starting material is the 2-aminobenzenesulfonamides, which in turn are either 2-amino or 2-acylamino zolsulfochloride or by hydrogenation of 2-nitrobenzenesulfonamides are easily accessible. Substituents can either be present in the 2-aminobenzenesulfonamide from the outset or introduced by electrophilic substitution. For example, the alkylthio group of 2-amino-5-alkylthiobenzenesulfonamides can be introduced by the sequence rhodanation, alkaline hydrolysis, alkylation, an acylamino group by nitration, reduction and acylation.

The ketone, anilide or acylhydrazide function is introduced via the second building block, which is derived from an acylacetic ester or a malonic ester.

3-pivaloylmethyl-benzo-1,2,4-sulfonediazines are e.g. preferably produced by base-catalyzed condensation of pivaloyl acetate with 2-aminobenzenesulfonamides, benzo-1,2,4-sulfondiazine-3-acetanilides either by reacting a maloniminoether anilide with a 2-aminobenzenesulfonamide or in two stages by reacting a maloniminoetherester with a 2-aminobenzenesulfonamide and post-reaction formed benzo-1,2,4-sulfondiazine-3-ethyl acetate.

The 1,2,3-triazole, which acts as an inhibitor, is also preferably introduced in a conventional manner by halogenation, preferably bromination, and subsequent nucleophilic substitution, preferably under aprotic conditions. The corresponding synthesis steps run consistently over well-characterized and stable compounds and in good yields.

Synthesis examples 1. Benzo-1,2,4-thiadiazine-1,1-dioxide-3-acetic acid ethyl ester (3.1.)

20 g of diethyl malonate imide hydrochloride and 17 g of 2-aminobenzenesulfonamide in 150 ml of ethanol are heated under reflux for 45 min and discharged onto 300 g of ice. After suctioning off and crystallizing from ethanol, 12 g of white needles with a melting point of 130-135 ° C. are obtained.

2. Benzo-1,2,4-thiadiazine-1,1-dioxide-3-acetic acid- [2-tetradecyloxy) anilide (3.2.)

10 g of the heated under 3.1. Compound obtained and 11 g of 2-tetradecyloxyaniline in 50 ml of ortho-dichlorobenzene for 2 h at 180 ° C, cools to 70 ° C and discharges onto 100 ml of methanol. After suctioning off and drying in air, 13 g of pale yellowish powder with a melting point of 117-119 ° C. are obtained.

3. Benzo-1,2,4-thiadiazine-1,1-dioxide-3-bromoacetic acid- (2-tetradecyloxy) anilide (3.3.)

It is added dropwise to a suspension of 10 g of 3.2. Compound obtained in 100 ml of acetic acid at room temperature 3.4 g of bromine in 10 ml of acetic acid. After 30 minutes, 3 g of sodium acetate are added and 100 g of ice are added. It is decanted from the precipitated product and stirred with 30 ml of methanol.

After drying in air, almost white powder with a decomposition melting point of 138-140 ° C. is obtained. Yield: 9.5 g.

4. Connection DIR-4

6 g of the under 3.3. Brominated coupler obtained and 2.6 g of 4- (2-benzoyloxy) ethylthio-1,2,3-triazole, prepared by reacting Na-4-mercapto-1,2,3-triazole with 2-chloroethylbenzoate, are in 30 ml of dimethylacetamide were stirred at room temperature with the addition of 4 g of potassium carbonate for 2 h. It is then poured onto 100 g of ice and 5 ml of acetic acid, waited about 3 hours until crystallization has started, decanted, washed twice with 100 ml of water and digested with 10 ml of isopropanol.

3.8 g of compound 3 with a melting point of 150 ° C. (decomp.) Are obtained.

Thin-layer chromatography (silica gel, eluent: toluene-ethyl acetate) shows 2 orange-coupling isomers after spraying with color developer CD3 and alkaline persulfate solution.

The compounds of the present invention are suitable for use as DIR couplers in color photographic, in particular multilayer, recording materials. Since they are essentially yellow couplers, they are preferably used in or associated with a light-sensitive silver halide emulsion layer with a predominant sensitivity to the blue spectral range of visible light. The particular advantage of the couplers according to the invention, namely a comparatively low development inhibition in the layer to which such a compound is assigned, in addition to a comparatively high development inhibition in adjacent unassigned layers, naturally comes into play particularly when it is a multi-layer color photographic recording material which, in addition to a predominantly blue-sensitive silver halide emulsion layer, contains further light-sensitive silver halide emulsion layers with predominant sensitivity for the green or red spectral range of the visible light. Couplers which give only a little color during development can be assigned to a blue-sensitive, a green-sensitive or a red-sensitive layer or also several of these layers without fear of color falsification.

In the preparation of the light-sensitive color photographic recording material, the diffusion-resistant DIR couplers of the present invention, if appropriate together with other couplers, can be introduced into the casting solution of the silver halide in a known manner emulsion layers or other colloid layers can be incorporated. For example, oil-soluble or hydrophobic couplers can be added to a hydrophilic colloid solution, preferably from a solution in a suitable coupler solvent (oil former), optionally in the presence of a wetting or dispersing agent. The hydrophilic casting solution can of course contain other conventional additives in addition to the binder. The solution of the coupler need not be directly dispersed in the casting solution for the silver halide emulsion layer or other water permeable layer; Rather, it can also be advantageously first dispersed in an aqueous, non-photosensitive solution of a hydrophilic colloid, whereupon the mixture obtained, after removal of the low-boiling organic solvents used, may be mixed with the coating solution for the photosensitive silver halide emulsion layer or another water-permeable layer before application.

Suitable light-sensitive silver halide emulsions are emulsions of silver chloride, silver bromide or mixtures thereof, possibly with a low silver iodide content of up to 15 mol% in one of the commonly used hydrophilic binders. Gelatin is preferably used as a binder for the photographic layers. However, this can be replaced in whole or in part by other natural or synthetic binders.

The emulsions can be chemically and spectrally sensitized in the usual way, and the emulsion layers Like other non-photosensitive layers, they can be cured in the usual way with known curing agents.

Color photographic recording materials usually contain at least one silver halide emulsion layer for the recording of light from the three spectral ranges red, green and blue. For this purpose, the light-sensitive layers are spectrally sensitized in a known manner by means of suitable sensitizing dyes. Blue-sensitive silver halide emulsion layers do not necessarily have to contain a spectral sensitizer, since in many cases the intrinsic sensitivity of the silver halide is sufficient for the recording of blue light.

Each of the light-sensitive layers mentioned can consist of a single layer or, in a known manner, for example in the case of the so-called double-layer arrangement, also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470). Usually, red-sensitive silver halide emulsion layers are arranged closer to the layer support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, a yellow filter layer which is not sensitive to light generally being located between green-sensitive layers and blue-sensitive layers. However, other arrangements are also conceivable. A non-light-sensitive intermediate layer is usually arranged between layers of different spectral sensitivity Preventing the incorrect diffusion of developer oxidation products. If there are several silver halide emulsion layers of the same spectral sensitivity, these can be directly adjacent to one another or be arranged such that there is a light-sensitive layer with a different spectral sensitivity between them (DE-A-1 958 709, DE-A-25 30 645, DE-A -26 22 922).

Color photographic recording materials for producing multicolored images usually contain, in spatial and spectral assignment to the silver halide emulsion layers of different spectral sensitivity, coloring compounds, here in particular color couplers, for producing the different partial color images cyan, purple and yellow.

Spatial assignment is understood to mean that the color coupler is in such a spatial relationship with the silver halide emulsion layer that an interaction between them is possible which allows an image-wise match between the silver image formed during development and the color image generated from the color coupler. This is usually achieved by the fact that the color coupler is contained in the silver halide emulsion layer itself or in a possibly non-light-sensitive binder layer adjacent to it.

Spectral assignment means that the spectral sensitivity of each of the photosensitive Silver halide emulsion layers and the color of the partial color image generated from the spatially assigned color coupler have a specific relationship to one another, with each of the spectral sensitivities (red, green, blue) being assigned a different color of the relevant partial color image (for example cyan, purple, yellow).

One or more color couplers can be assigned to each of the differently spectrally sensitized silver halide emulsion layers. If there are several silver halide emulsion layers of the same spectral sensitivity, each of them can contain a color coupler, which color couplers need not necessarily be identical. They should only result in at least approximately the same color during color development, normally a color that is complementary to the color of the light, for which the silver halide emulsion layers in question are predominantly sensitive.

In preferred embodiments, red-sensitive silver halide emulsion layers are at least one non-diffusing color coupler for producing the blue-green partial color image, green-sensitive silver halide emulsion layers at least one non-diffusing color coupler for producing the purple partial color image and blue-sensitive silver halide emulsion layers for generating the yellow partial color coupler for producing the partial color image. However, other assignments are also known.

Color couplers for producing the blue-green partial color image are usually couplers of the phenol or α-naphthol type; suitable examples are

Color couplers for generating the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; suitable examples are

Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the α-acylacetamide type; suitable examples of this are α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers of the formulas

The color couplers can be 4-equivalent couplers, but also 2-equivalent couplers. The latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site which is split off during the coupling. The 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products. The 2-equivalent couplers also include those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products, either directly or after one or more further groups have been cleaved from the primarily cleaved residue (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolds, for example as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.

Since in the DIR, DAR or FAR couplers the effectiveness of the residue released during the coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable which give essentially colorless products on coupling (DE-A-1 547 640).

The cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).

According to the invention, the color photographic recording material additionally contains at least one DIR coupler of the formula I, which coupler contains not only in the yellow layer but also in the purple layer and / or also in the blue-green layer and also in a non-light-sensitive layer adjacent to one of the layers mentioned can be.

In addition to the constituents mentioned, the color photographic recording material of the present invention can contain further additives, for example antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties. The adverse effects of UV light on the color images produced with the color photographic recording material according to the invention To reduce or avoid, it is advantageous to use UV-absorbing compounds in one or more of the layers contained in the recording material, preferably in one of the upper layers. Suitable UV absorbers are described for example in US-A-3 253 921, DE-C-2 036 719 and EP-A-0 057 160.

The usual layer supports can be used for the materials according to the invention, see Research Disclosure No. 17 643, Section XVII.

The usual hydrophilic film-forming agents are suitable as protective colloid or binder for the layers of the recording material, e.g. Proteins, especially gelatin. Casting aids and plasticizers can be used. Reference is made to the compounds specified in Research Disclosure No. 17,643 in Sections IX, XI and XII.

The layers of the photographic material can be hardened in the usual manner, for example with hardeners of the epoxy type, the heterocyclic ethylene imine and the acryloyl type. Furthermore, it is also possible to harden the layers according to the process of DE-A-22 18 009 in order to obtain color photographic materials which are suitable for high-temperature processing. It is also possible to harden the photographic layers with hardeners of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type.

Further suitable hardening agents are known from DE-A-24 39 551, DE-A-22 25 230, DE-A-23 17 672 and from Research Disclosure 17 643, Section XI given above.

Further suitable additives are given in Research Disclosure 17 643 and in "Product Licensing Index" from December 1971, pages 107-110.

In order to produce color photographic images, the color photographic recording material according to the invention is developed with a color developer compound. All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine dyes can be used as the color developer compound. Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines, such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl-3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.

Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3100 (1951) and in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, pages 545 ff.

After color development, the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together will. The usual compounds can be used as bleaching agents, for example Fe³⁺ salts and Fe³⁺ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes, etc. Particularly preferred are iron III complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediamine triacetic acid, alkyliminodicarboxylic acids and alkyliminodicarboxylic acids and Phosphonic acids. Persulphates are also suitable as bleaching agents.

example 1

A color photographic recording material for color negative color development was produced (layer structure 1A comparison) by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given. All silver halide emulsions were stabilized per 100 g of AgNO₃ with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

Layer structure 1 A (comparison)

• Layer 1 (antihalo layer)
  black colloidal silver sol with
  0.2 g Ag
  1.2 g gelatin
  0.1 g UV absorber UV-1
  0.2 g UV absorber UV-2
  0.02 g tricresyl phosphate (CPM)
  0.03 g dibutyl phthalate (DBP)
• Layer 2 (Mikrat intermediate layer)
  Mikrat-silver bromide iodide emulsion (0.5 mol% iodide;
  average grain diameter 0.07 µm) from 0.25 g AgNO₃, with
  1.0 g gelatin
• Layer 3 (red-sensitive layer, medium-sensitive)
  red-sensitized silver bromoiodide emulsion
  (4.0 mol% iodide;
  average grain diameter 0.45 µm) from 5.35 g AgNO₃, with
  3.75 g gelatin
  1.33 g cyan coupler C-19
  0.05 g RM-1 red mask
  0.118 g DIR coupler DIR-A
  1.33 g CPM
  0.236 g DBP
• Layer 4 (intermediate layer)
  from 1.43 g gelatin
  0.74 g scavenger
• Layer 5 (green-sensitive layer, medium-sensitive)
  green-sensitized silver bromoiodide emulsion
  (4.0 mol% iodide;
  average grain diameter 0.45 µm) from 3.10 g AgNO₃, with
  2.33 g gelatin
  0.775 g magenta coupler M-12
  0.050 g yellow mask YM-1
  0.068 g DSR coupler DIR-A
  0.775 g CPM
  0.136 g DBP
• Layer 6 (intermediate layer)
  like layer 4
• Layer 7 (yellow filter layer)
  yellow colloidal silver sol with 0.09 g Ag,
  0.34 g gelatin
• Layer 8 (blue sensitive layer, medium sensitive),
  blue-sensitized silver bromoiodide emulsion
  (4.0 mol% iodide;
  average grain diameter 0.45 µm) from 3.46 g AgNO₃, with
  1.73 g gelatin
  1.25 g yellow coupler Y-20
  0.076 g DIR coupler DIR-A
  1.25 g CPM
  0.152 g DBP
• Layer 9 (intermediate layer)
  like layer 4
• Layer 10 (protective and hardening layer) made of 0.68 g gelatin
  0.73 g hardener (CAS Reg.No. 65411-60-1)
  0.50 g formaldehyde scavenger FF

In Example 1 the following compounds are used in addition to the couplers already mentioned:

Na perfluorobutanesulfonate is used as a wetting agent in all layers. DIR coupler used in layer structure 1 A (comparison):

Further layer structures 1 B to 1 F were produced accordingly, which differ from layer structure 1 A only in the DIR coupler used in layers 3, 5 and 8.

Development was carried out after exposure of a gray wedge as described in "The British Journal of Photography", 1974 , pages 597 and 598.

The results after processing are shown in Table 1. The interimage effects IIE are calculated as follows:

Here means:
γ- _red gradation with selective exposure to red light
γ- _green gradation with selective exposure to green light
γ- _blue gradation with selective exposure with blue light
γ- _w gradation when exposed to white light
The edge effect KE given in Table 1 is the difference between micro and macro density with macro density = 1, as described in James, The Theory of the Photographic Process, 4th Edition, Macmillan Publishing Co., Inc 1977, page 611. Here:
KE _bg KE in the red-sensitized layer
KE _pp KE in the green-sensitized layer Table 1 Layer structure TO YOU IIE _gb IIE _pp IIE _bg KE _pp KE _bg 1 A A 3rd 44 35 0.39 0.44 1 B 1 17th 70 45 0.56 0.66 1 C. 4th 11 99 44 0.74 0.81 1 D 5 4th 58 34 0.38 0.52 1 E 8th 8th 64 37 0.47 0.61 1 F 9 28 74 46 0.55 0.70

Claims (6)

1. Color photographic recording material with at least one photosensitive silver halide emulsion layer and a coupler assigned to it which is capable of releasing a photographically active compound, characterized in that the coupler corresponds to the following general formula I.

in which mean:
R¹ is alkyl, for example -C₄H₉-t, aryl, for example p-alkoxyphenyl -NH-aryl or -NH-NH-R³;
R² H, halogen, for example chlorine, alkoxy, alkylthio or -NH-R⁴;
R³, R⁴ acyl;
X is the residue of a photographically active compound with a monocyclic 1,2,3- or 1,2,4-triazole ring;
TIME is a link which, when the coupler reacts with the oxidation product of a color developer, is released together with the radical X attached to it and in turn releases the radical X as a photographically active compound under the development conditions;
n 0 or 1. 2. Recording material according to claim 1, characterized in that the coupler is a DIR coupler (X is the rest of a development inhibitor). 3. Recording material according to one of claims 1 and 2, characterized in that X for a group of the following formula

stands in which mean:
Z is the balance to complete a 1,2,3- or 1,2,4-triazole ring;
R⁵ and R⁶ H, alkyl, aryl, a heterocyclic group, alkoxy, -S-R⁷, amino, acylamino, a carboxylic acid ester group or -CO-NR⁸R⁹;
R⁷ alkyl, cycloalkyl, aralkyl, alkenyl, alkynyl or aryl;
R⁸ alkyl, aralkyl or aryl;
R⁹ H, a remainder like R⁸
or R⁸ and R⁹ together the rest to complete a cyclic amino group. 4. Recording material according to claim 2, characterized in that the DIR coupler is contained in a predominantly blue-sensitive silver halide emulsion layer, and that the recording material contains at least one further predominantly green-sensitive or predominantly red-sensitive silver halide emulsion layer. 5. Recording material according to claim 2, characterized in that the DIR coupler is contained in a predominantly red-sensitive silver halide emulsion layer. 6. Color photographic recording material with at least one predominantly blue-sensitive silver halide emulsion layer unit, which is assigned to at least one yellow coupler, one predominantly green-sensitive silver halide emulsion layer unit, which is associated with at least one purple coupler, and one predominantly red-sensitive silver halide emulsion layer unit, which is associated with at least one cyan coupler, characterized in that at least one partial layer the predominantly green-sensitive silver halide emulsion layer unit or the predominantly red-sensitive silver halide emulsion layer unit contains a DIR coupler of the following formula I:

in which mean:
R¹ is alkyl, for example -C₄H₉-t, aryl, for example p-alkoxyphenyl -NH-aryl or -NH-NH-R³;
R² H, halogen, for example chlorine, alkoxy, alkylthio or -NH-R⁴;
R³, R⁴ acyl;
X is the residue of a photographically active compound with a monocyclic 1,2,3- or 1,2,4-triazole ring;
TIME is a link that is released when the coupler reacts with the oxidation product of a color developer together with the radical X attached to it, and in turn the radical X as a photo under the development conditions releases graphically effective connection;
n 0 or 1.