EP0369235B1 - Photographic-recording material - Google Patents

Description

The invention relates to a photographic recording material with a layer support and at least one photosensitive silver halide emulsion layer arranged thereon.

According to the invention, the material contains special triazoles as antifoggants.

Recording materials with light-sensitive silver halide emulsions, in particular chemically sensitized, are known to tend to form fog, caused by germs which can be developed without exposure.

It is known to add so-called antifoggants or stabilizers to photographic silver halide emulsions to reduce the formation of fog, e.g. B. heterocyclic compounds containing sulfur, for example in the form of a mercapto group.

For example, reference is made to the German interpretation documents 1 183 371 (GB 1 067 066), 1 189 380 (US 3 364 028 and 3 365 294), 1 597 503 (US 3 615 617), DE 1 979 027, to the German published documents 1 522 363 (GB 1 186 441), 2 042 533 (US 3 761 278), 2 130 031 and 2 308 530.

Some triazoles have also been proposed as antifoggants (US-A-2,353,754, US-A-3,157,509, US-A-4,049,458, JP-A-63,223,635).

Furthermore, these compounds are used to adapt the sensitivity of the emulsions to the specified standard in the event of production fluctuations.

When the conventional antifoggants cited above are used to lower the sensitivity, a flattening of the gradation curve of the respective silver halide emulsion occurs as an undesirable side effect.

The object of the invention was now to develop a photographic recording material in which the sensitivity of the silver halide emulsions in the event of production fluctuations can be regulated in accordance with the specified standard without a gradation flattening occurring at the same time.

enthält, worin

A

H, Kation eines Metallatoms oder eines Nichtmetallrestes, Gruppe mit kovalenter Bindung zu dem Stickstoffatom des Triazols, die erst bei der Verarbeitung des Materials unter Freisetzung des Triazols gespalten wird, ausgewählt aus der Gruppe bestehend aus

-CO-N(CH₃)₂, -CO-CH₃, -SO₂-N(CH₃)₂ und SO₂-CH₃,

R₁

gegebenenfalls substituiertes C₁-C₉-Alkyl, C₂-C₈-Alkenyl, C₆-C₁₀-Aryl, SR₃,

R₂

H, gegebenenfalls substituiertes C₁-C₉-Alkyl, C₂-C₈-Alkenyl, C₆-C₁₀-Aryl, C₅-C₁₀-Heteroaryl, Cl, Br, -COOR₃, -COR₃, -OCOR₃,

R₃

gegebenenfalls substituiertes C₁-C₉-Alkyl, C₂-C₈-Alkenyl, C₆-C₁₀-Aryl, C₅-C₁₀-Heteroaryl,

bedeuten und wobei die Summe der in den Resten R₁, R₂ und R₃ enthaltenen Kohlenstoffatome gleich oder größer 5 ist, falls R₂ eine Carbonestergruppe darstellt.The invention relates to a photographic recording material with a support and at least a photosensitive silver halide emulsion layer arranged thereon, characterized in that the at least one silver halide emulsion layer contains an antifoggant of the formula I

contains what

A

H, cation of a metal atom or a non-metal radical, group with covalent bond to the nitrogen atom of the triazole, which is only cleaved when the material is processed to release the triazole, selected from the group consisting of

-CO-N (CH₃) ₂, -CO-CH₃, -SO₂-N (CH₃) ₂ and SO₂-CH₃,

R₁

optionally substituted C₁-C₉-alkyl, C₂-C₈-alkenyl, C₆-C₁₀-aryl, SR₃,

R₂

H, optionally substituted C₁-C₉-alkyl, C₂-C₈-alkenyl, C₆-C₁₀-aryl, C₅-C₁₀-heteroaryl, Cl, Br, -COOR₃, -COR₃, -OCOR₃,

R₃

optionally substituted C₁-C₉ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, C₅-C₁₀ heteroaryl,

mean and wherein the sum of the carbon atoms contained in the radicals R₁, R₂ and R₃ is equal to or greater than 5 if R₂ represents a carboxylic ester group.

Examples of cations of a metal atom according to group A are Na ^⊕ , K ^⊕ , Mg ^2⊕ and Zn ^2⊕ ; a cation of a non-metal radical represents, for example, NH₄ ^⊕ .

Suitable heteroaryl radicals are, for example: thiophene, furan, 1,2,4-triazole and pyridine.

Suitable substituents of the radicals R₁, R₂ and R₃ are conventional substituents in the field of photographic antifoggants, such as halogen, in particular chlorine or bromine, C₁-C₄-alkoxy groups, C₁-C₄-alkoxycarbonyl, C₆-C₁₀-aryloxycarbonyl and C₁-C₄-alkylcarbonyloxy.

Aryl and heteroaryl can also be substituted with C₁-C₈ alkyl.

Suitable examples are the following compounds according to the invention, in which group A each represents hydrogen.

The antifoggants according to the invention are used in an amount of 10⁻⁵ to 10⁻², preferably 1 to 5 x 10 x³ mol per mol of silver halide.

The compounds are prepared by known methods, as described, for example, in the literature:
For R₁ = alkyl, aryl and R₂ = carboxylic acid ester group in Klein et al .; J. Heterocyclic Chem. 13 , 589 (1976). The alcohol component of the ester can be exchanged by transesterification with sodium alcoholate catalysis at 60 to 100 ° C.

For R₁ = alkylthio and R₂ = carboxylic acid ester group in Nemeryuk et al., Coll. Czech. Chem. Commun. 51: 215 (1981) and Goerdeler et al., Ber. 99 , 1618 (1966).

For R₁ = alkylthio and R₂ = alkanoyl or aroyl in RT Chakrasuli et al., Synthesis 1988 , 453.

5-Mercapto-1,2,3-triazole can be used, for example, to obtain alkylthio-1,2,3-triazoles by alkylation with alkyl bromides.

1,2,4-triazole-substituted 1,2,3-triazoles can be prepared in a conventional manner by ring-closing reaction of a 1,2,3-triazolecarboxylic acid ester with thiosemicarbazide.

Examples of photographic materials are black and white films, color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the silver color bleaching process.

Color photographic recording materials with a transparent layer support and at least three light-sensitive silver halide emulsion layers of different spectral sensitivity arranged thereon, to which a yellow coupler, a magenta coupler and a cyan coupler are each spectrally assigned, are preferred.

Suitable supports for the production of color photographic materials are, for example, films and foils of semisynthetic and synthetic polymers, such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate, and paper laminated with a baryta layer or α-olefin polymer layer (eg polyethylene). These carriers can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light. The surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.

The color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.

Binding agents, silver halide grains and color couplers are essential components of the photographic emulsion layers.

Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers. Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, starch or alginates. Semi-synthetic gelatin substitutes are usually modified natural products. Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives, which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers, are examples of this.

The binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents. Such functional Groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.

The gelatin which is preferably used can be obtained by acidic or alkaline digestion. Oxidized gelatin can also be used. The production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff. The gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.

The silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide. For example, the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide. In the case of color negative and color reversal films, silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions are usually used. It can be predominantly compact crystals, which are, for example, regularly cubic or octahedral or can have transitional forms. However, platelet-shaped crystals can preferably also be present, whose average ratio of diameter to thickness is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain. However, the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, for example 12: 1 to 30: 1.

The silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. Doping of the individual grain areas are different. The average grain size of the emulsions is preferably between 0.2 μm and 2.0 μm, the grain size distribution can be either homodisperse or heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ± 30%. In addition to the silver halide, the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.

Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.

The photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsions, The Focal Press, London (1966) from soluble silver salts and soluble halides.

The silver halide is preferably precipitated in the presence of the binder, for example the gelatin, and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used. The latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide. The water-soluble silver salts and the halides are combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded. The pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation. In addition to the preferred precipitation with an excess of halide, so-called inverse precipitation with an excess of silver ions is also possible. In addition to precipitation, the silver halide crystals can also grow by physical ripening (Ostwald ripening) in the presence of excess halide and / or silver halide complexing agent. The growth of the emulsion grains can even predominantly through Ostwald ripening take place, preferably a fine-grained, so-called Lippmann emulsion, mixed with a sparingly soluble emulsion and redissolved on the latter.

Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe may also be present during the precipitation and / or physical ripening of the silver halide grains.

The precipitation can also be carried out in the presence of sensitizing dyes. Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.

After crystal formation has been completed or at an earlier point in time, the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchangers.

The silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached. The procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).

The chemical sensitization with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII Periodic table (e.g. gold, platinum, palladium, iridium), thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described for example by F. Hamer "The Cyanine Dyes and Related Compounds") , 1964, or Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Vol. 18, pp. 431 ff. And Research Disclosure No. 17643, Section III). As an alternative or in addition, a reduction sensitization can be carried out with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid) using hydrogen, by means of low pAg (eg less than 5) and / or high pH (eg above 8) .

The photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.

In addition to the compounds according to the invention, azaindenes, preferably tetra- and penta-azaindenes, are suitable, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Furthermore, salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, Nitroindazole, optionally substituted benzotriazoles or benzthiazolium salts can be used. Heterocycles containing mercapto groups, for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group. Other suitable compounds are published in Research Disclosure No. 17643 (1978), Section VI.

The stabilizers can be added to the silver halide emulsions before, during or after their ripening. Of course, the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.

Mixtures of two or more of the compounds mentioned can also be used.

The photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics ( eg acceleration of development, high contrast, sensitization etc.). In addition to natural surface-active compounds, e.g. saponin, mainly synthetic surface-active compounds (surfactants) are used: non-ionic surfactants, e.g. alkylene oxide compounds, glycerol compounds or glycidol compounds, cationic surfactants, e.g. higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, containing anionic surfactants Acid group, for example carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, for example amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.

The photographic emulsions can be spectrally sensitized using methine dyes or other dyes. Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Research Disclosure 17643/1978 in Department IV contains an overview of the polymethine dyes suitable as spectral sensitizers, their suitable combinations and combinations with a super-sensitizing effect.

• 1. als Rotsensibilisatoren
  9-Ethylcarbocyanine mit Benzthiazol, Benzselenazol oder Naphthothiazol als basische Endgruppen, die in 5- und/oder 6-Stellung durch Halogen, Methyl, Methoxy, Carbalkoxy, Aryl substituiert sein können sowie 9-Ethyl-naphthoxathia- bzw. -selencarbocyanine und 9-Ethyl-naphthothiaoxa bzw. -benzimidazocarbocyanine, vorausgesetzt, daß die Farbstoffe mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff tragen.
• 2. als Grünsensibilisatoren
  9-Ethylcarbocyanine mit Benzoxazol, Naphthoxazol oder einem Benzoxazol und einem Benzthiazol als basische Endgruppen sowie Benzimidazocarbocyanine, die ebenfalls weiter substituiert sein können und ebenfalls mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff enthalten müssen.
• 3. als Blausensibilisatoren
  symmetrische oder asymmetrische Benzimidazo-, Oxa-, Thia- oder Selenacyanine mit mindestens einer Sulfoalkylgruppe am heterocyclischen Stickstoff und gegebenenfalls weiteren Substituenten am aromatischen Kern, sowie Apomerocyanine mit einer Rhodaningruppe.

The following dyes, sorted by spectral range, are particularly suitable:

• 1. as red sensitizers
  9-ethylcarbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups, the can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl and 9-ethyl-naphthoxathia or -selenecarbocyanine and 9-ethyl-naphthothiaoxa or -benzimidazocarbocyanine, provided that the dyes at least carry a sulfoalkyl group on the heterocyclic nitrogen.
• 2. as green sensitizers
  9-ethyl carbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzthiazole as basic end groups, and also benzimidazocarbocyanines, which may also be further substituted and must likewise contain at least one sulfoalkyl group on the heterocyclic nitrogen.
• 3. as blue sensitizers
  symmetrical or asymmetrical benzimidazo, oxa, thia or selenacyanines with at least one sulfoalkyl group on the heterocyclic nitrogen and optionally further substituents on the aromatic nucleus, and apomerocyanines with a rhodanine group.

RS 1:

R₁, R₃, R₇, R₉ = H; R₂, R₈ = Cl;

R₅ = C₂H₅; R₆ = SO₃^⊖; m, n = 3; X, Y = S;

RS 2:

R₁, R₃, R₉ = H; R₂ = Phenyl;

R₅ = C₂H₅; R₆ = SO₃^⊖; R₇, R₈ = -OCH₃; m = 2; n = 3; X = O; Y = S;

RS 3:

R₁, R₉ = H; R₂, R₃ zusammen -CH=CH-CH=CH-; R₄ = SO₃^⊖Na^⊕; R₅ = C₂H₅; R₆ = SO₃^⊖; R₇, R₈ = Cl; m, n = 3; X = S; Y = N-C₂H₅;

RS 4:

R₁ = OCH₃; R₂, R₈ = CH₃; R₃, R₄, R₇, R₉ = H; R₅ = C₂H₅; R₆ = SO₃^⊖; m = 2; n = 4; X = S; Y = Se;

RS 5:

R₁, R₇ = H; R₂, R₃ sowie R₈, R₉ zusammen -CH=CH-CH=CH-;

R₅ = C₂H₅; R₆ = SO₃^⊖; m = 2; n = 3; X, Y = S;

GS 1:

R₁, R₃, R₇, R₉ = H; R₂ = Phenyl;

R₅ = C₂H₅; R₆ = SO₃^⊖; R₈ = Cl; m = 2; n = 3; X, Y = O;

GS 2:

R₁, R₂, R₇, R₈ = Cl; R₃, R₅, R₆, R₉ = H;

m, n = 2; X, Y = N-C₂H₅;

GS 3:

R₁, R₇ = H; R₂, R₃ sowie R₈, R₉ zusammen -CH=CH-CH=CH-; R₄ = SO₃^⊖Na^⊕; R₅ = C₂H₅; R₆ = SO₃^⊖; m, n = 3; X, Y = O;

GS 4:

R₁, R₃, R₄, R₇, R₈, R₉ = H; R₂ = OCH₃; R₅ = C₂H₅; R₆ = SO₃^⊖; m = 2; n = 4; X = O; Y = S;

BS 1:

BS 2:

BS 3:

R₁₁ = -CH₂-COOH

BS 4:

R₁₁ = C₂H₅

BS 5:

R₁₁ = C₂H₅

Auf Sensibilisatoren kann verzichtet werden, wenn für einen bestimmten Spektralbereich die Eigenempfindlichkeit des Silberhalogenids ausreichend ist, beispielsweise die Blauempfindlichkeit von Silberbromiden.Examples, in particular for negative and reversal film, are the red sensitizers RS, green sensitizers GS and blue sensitizers BS, which can be used individually or in combination with each other, e.g. RS 1 and RS 2, and GS 1 and GS 2.

RS 1:

R₁, R₃, R₇, R₉ = H; R₂, R₈ = Cl;

R₅ = C₂H₅; R₆ = SO₃ ^⊖ ; m, n = 3; X, Y = S;

RS 2:

R₁, R₃, R₉ = H; R₂ = phenyl;

R₅ = C₂H₅; R₆ = SO₃ ^⊖ ; R₇, R₈ = -OCH₃; m = 2; n = 3; X = O; Y = S;

RS 3:

R₁, R₉ = H; R₂, R₃ together -CH = CH-CH = CH-; R₄ = SO₃ ^⊖ Na ^⊕ ; R₅ = C₂H₅; R₆ = SO₃ ^⊖ ; R₇, R₈ = Cl; m, n = 3; X = S; Y = N-C₂H₅;

RS 4:

R₁ = OCH₃; R₂, R₈ = CH₃; R₃, R₄, R₇, R₉ = H; R₅ = C₂H₅; R₆ = SO₃ ^⊖ ; m = 2; n = 4; X = S; Y = Se;

RS 5:

R₁, R₇ = H; R₂, R₃ and R₈, R₉ together -CH = CH-CH = CH-;

R₅ = C₂H₅; R₆ = SO₃ ^⊖ ; m = 2; n = 3; X, Y = S;

GS 1:

R₁, R₃, R₇, R₉ = H; R₂ = phenyl;

R₅ = C₂H₅; R₆ = SO₃ ^⊖ ; R₈ = Cl; m = 2; n = 3; X, Y = O;

GS 2:

R₁, R₂, R₇, R₈ = Cl; R₃, R₅, R₆, R₉ = H;

m, n = 2; X, Y = N-C₂H₅;

GS 3:

R₁, R₇ = H; R₂, R₃ and R₈, R₉ together -CH = CH-CH = CH-; R₄ = SO₃ ^⊖ Na ^⊕ ; R₅ = C₂H₅; R₆ = SO₃ ^⊖ ; m, n = 3; X, Y = O;

GS 4:

R₁, R₃, R₄, R₇, R₈, R₉ = H; R₂ = OCH₃; R₅ = C₂H₅; R₆ = SO₃ ^⊖ ; m = 2; n = 4; X = O; Y = S;

BS 1:

BS 2:

BS 3:

R₁₁ = -CH₂-COOH

BS 4:

R₁₁ = C₂H₅

BS 5:

R₁₁ = C₂H₅

Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromides.

The differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it. Usually, the red-sensitive layers become cyan couplers, assigned to the green-sensitive layers of purple couplers and the blue-sensitive layers of yellow couplers.

BG 1:

R₁ = H; R₂ = H;

BG 2:

R₁ = -NHCOOCH₂-CH(CH₃)₂; R₂ = H; R₃ = -(CH₂)₃-OC₁₂H₂₅

BG 3:

R₁ = H; R₂ = -OCH₂-CH₂-SO₂CH₃; R₃ = C₁₆H₃₃

BG 4:

R₁ = H; R₂ = -OCH₂-CONH-(CH₂)₂-OCH₃;

BG 5:

R₁ = H; R₂ = H;

BG 6:

R₁ = H; R₂ = H;

BG 7:

R₁ = H; R₂ = Cl; R₃ = -C (C₂H₅)₂-(CH₂)₂₀-CH₃

BG 8:

R₁ = H; R₂ = -O-CH₂-CH₂-S-CH(COOH)-C₁₂H₂₅ R₃ = Cyclohexyl

BG 9:

R₁ = -C₄H₉; R₂ = H; R₃ = -CN; R₄ = Cl

BG 10:

R₁ = -C₄H₉; R₂ = H; R₃ = H; R₄ = -SO₂CHF₂

BG 11:

R₁ = -C₄H₉;

R₃ = H; R₄ = -CN

BG 12:

R₁ = C₂H₅; R₂ = H; R₃ = H; R₄ = -SO₂CH₃

BG 13:

R₁ = -C₄H₉; R₂ = H; R₃ = H; R₄ = -SO₂-C₄H₉

BG 14:

R₁ = -C₄H₉; R₂ = H; R₃ = -CN; R₄ = -CN

BG 15:

R₁ = -C₄H₉; R₂ = H; R₃ = H; R₄ = -SO₂-CH₂-CHF₂

BG 16:

R₁ = -C₂H₅; R₂ = H; R₃ = H; R₄ = -SO₂CH₂-CHF-C₃H₇

BG 17:

R₁ = -C₄H₉; R₂ = H; R₃ = H; R₄ = F

BG 18:

R₁ = -C₄H₉; R₂ = H; R₃ =H; R₄ = -SO₂CH₃

BG 19:

R₁ = -C₄H₉; R₂ = H; R₃ =H; R₄ = -CN

BG 20:

R₁ = -CH₃; R₂ = -C₂H₅; R₃, R₄ = -t-C₅H₁₁

BG 21:

R₁ = -CH₃; R₂ = H; R₃, R₄ = -t-C₅H₁₁

BG 22:

R₁ = -C₂H₅; R₂ = -C₂H₅; R₃, R₄ = -t-C₅H₁₁

BG 23:

R₁ = -C₂H₅; R₂ = -C₄H₉; R₃, R₄ = -t-C₅H₁₁

BG 24:

R₁ = -C₂H₅; R₂ = -C₄H₉; R₃, R₄ = -t-C₄H₉

BG 25:

R₁, R₂ = -t-C₅H₁₁; R₃ = -C₄H₉; R₄ = H; R₅ = -C₃F₇

BG 26:

R₁ = -NHSO₂-C₄H₉; R₂ = H; R₃ = -C₁₂H₂₅; R₄ = Cl; R₅ = Phenyl

BG 27:

R₁, R₂ = -t-C₅H₁₁; R₂ = Cl, R₃ = -CH(CH₃)₂; R₄ = Cl; R₅ = Pentafluorphenyl

BG 28:

R₁ = -t-C₅H₁₁; R₂ = Cl; R₃ = -C₆H₁₃; R₄ = Cl; R₅ = -2-Chlorphenyl

Farbkuppler zur Erzeugung des purpurnen Teilfarbenbildes sind in der Regel Kuppler vom Typ des 5-Pyrazolons, des Indazolons oder der Pyrazoloazole; geeignete Beispiele hierfür sind

PP 1:

PP 2:

R₂ = H

PP 3:

R₁ = -C₁₃H₂₇; R₂ = H

PP 4:

R₁ = -O-C₁₆H₃₃; R₂ = H

PP 5:

R₁ = -C₁₃H₂₇;

PP 6:

PP 7:

R₁ = -C₉H₁₉;

PP 8:

PP 9:

PP 10:

PP 11:

R₂ = H

PP 12:

R₂ = H

PP 13:

R₂ = H

PP 14:

PP 15:

PP 16:

PP 17:

PP 18:

R₂ = -CH₃

PP 19:

R₂ = -CH₃

PP 20:

R₂ = -t-C₄H₉

PP 21:

R₂ = -CH₃

PP 22:

Farbkuppler zur Erzeugung das gelben Teilfarbenbildes sind in der Regel Kuppler mit einer offenkettigen Ketomethylengruppierung, insbesondere Kuppler vom Typ des α-Acylacetamids; geeignete Beispiele hierfür sind α-Benzoylacetanilidkuppler und α-Pivaloylacetanilidkuppler der Formeln

GB 1:  

R₂ = Cl;

GB 2:  

R₂ = -OC₁₆H₃₃; R₃ = -SO₂NHCH₃
GB 3:  

R₂ = Cl R₃ = -NHSO₂-C₁₆H₃₃
GB 4:  

R₂ = Cl; R₃ = -COOC₁₂H₂₅
GB 5:  

R₂ = Cl

GB 6:  

R₂ = Cl;

GB 7:  

R₂ = Cl; R₃ = -NHSO₂C₁₆H₃₃
GB 8:  

R₂ = Cl;

GB 9:  

R₂ = OC₁₆H₃₃; R₃ = -SO₂NHCOC₂H₅
GB 10:  

R₂ = Cl;

GB 11  :

R₂ = Cl;

GB 12:  

R₂ = Cl;

GB 13:  

R₂ = -OC₁₆H₃₃; R₃ = -SO₂NHCH₃
GB 14:  

R₂ = Cl

GB 15:  R₁, R₃, R₅, R₆ = H; R₄ = -OCH₃;

GB 16:  R₂, R₆ = H; R₁ = -OC₁₆H₃₃; R₄, R₅ = -OCH₃;

GB 17:  R₂, R₆ = H; R₁ = -OCH₃, R₄ = Cl; R₅ = -COOC₁₂H₂₅;

GB 18:  R₂ = H; R₁ = -OC₁₆H₃₃; R₄ = Cl; R₅, R₆ = -OCH₃;

GB 19:  R₂, R₅ = H; R₁ = -OC₁₆H₃₃; R₄ = -OCH₃;

R₆ = -SO₂N(CH₃)₂
GB 20:  R₂, R₆ = H; R₁, R₄ = -OCH₃;

GB 21:

  
Bei den Farbkupplern kann es sich um 4-Äquivalentkuppler, aber auch um 2-Äquivalentkuppler handeln. Letztere leiten sich von den 4-Äquivalentkupplern dadurch ab, daß sie in der Kupplungsstelle einen Substituenten enthalten, der bei der Kupplung abgespalten wird. Zu den 2-Äquivalentkupplern sind solche zu rechnen, die farblos sind, als auch solche, die eine intensive Eigenfarbe aufweisen, die bei der Farbkupplung verschwindet bzw. durch die Farbe des erzeugten Bildfarbstoffes ersetzt wird (Maskenkuppler), und die Weißkuppler, die bei Reaktion mit Farbentwickleroxidationsprodukten im wesentlichen farblose Produkte ergeben. Zu den 2-Äquivalentkupplern sind ferner solche Kuppler zu rechnen, die in der Kupplungsstelle einen abspaltbaren Rest enthalten, der bei Reaktion mit Farbentwickleroxidationsprodukten in Freiheit gesetzt wird und dabei entweder direkt oder nachdem aus dem primär abgespaltenen Rest eine oder mehrere weitere Gruppen abgespalten worden sind (z.B. DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), eine bestimmte erwünschte fotografische Wirksamkeit entfaltet, z.B. als Entwicklungsinhibitor oder -accelerator. Beispiele für solche 2-Äquivalentkuppler sind die bekannten DIR-Kuppler wie auch DAR- bzw. FAR-Kuppler.Color couplers for producing the blue-green partial color image are usually couplers of the phenol or α-naphthol type; suitable examples are

BG 1:

R₁ = H; R₂ = H;

BG 2:

R₁ = -NHCOOCH₂-CH (CH₃) ₂; R₂ = H; R₃ = - (CH₂) ₃-OC₁₂H₂₅

BG 3:

R₁ = H; R₂ = -OCH₂-CH₂-SO₂CH₃; R₃ = C₁₆H₃₃

BG 4:

R₁ = H; R₂ = -OCH₂-CONH- (CH₂) ₂-OCH₃;

BG 5:

R₁ = H; R₂ = H;

BG 6:

R₁ = H; R₂ = H;

BG 7:

R₁ = H; R₂ = Cl; R₃ = -C (C₂H₅) ₂- (CH₂) ₂₀-CH₃

BG 8:

R₁ = H; R₂ = -O-CH₂-CH₂-S-CH (COOH) -C₁₂H₂₅ R₃ = cyclohexyl

BG 9:

R₁ = -C₄H₉; R₂ = H; R₃ = -CN; R₄ = Cl

BG 10:

R₁ = -C₄H₉; R₂ = H; R₃ = H; R₄ = -SO₂CHF₂

BG 11:

R₁ = -C₄H₉;

R₃ = H; R₄ = -CN

BG 12:

R₁ = C₂H₅; R₂ = H; R₃ = H; R₄ = -SO₂CH₃

BG 13:

R₁ = -C₄H₉; R₂ = H; R₃ = H; R₄ = -SO₂-C₄H₉

BG 14:

R₁ = -C₄H₉; R₂ = H; R₃ = -CN; R₄ = -CN

BG 15:

R₁ = -C₄H₉; R₂ = H; R₃ = H; R₄ = -SO₂-CH₂-CHF₂

BG 16:

R₁ = -C₂H₅; R₂ = H; R₃ = H; R₄ = -SO₂CH₂-CHF-C₃H₇

BG 17:

R₁ = -C₄H₉; R₂ = H; R₃ = H; R₄ = F

BG 18:

R₁ = -C₄H₉; R₂ = H; R₃ = H; R₄ = -SO₂CH₃

BG 19:

R₁ = -C₄H₉; R₂ = H; R₃ = H; R₄ = -CN

BG 20:

R₁ = -CH₃; R₂ = -C₂H₅; R₃, R₄ = -t-C₅H₁₁

BG 21:

R₁ = -CH₃; R₂ = H; R₃, R₄ = -t-C₅H₁₁

BG 22:

R₁ = -C₂H₅; R₂ = -C₂H₅; R₃, R₄ = -t-C₅H₁₁

BG 23:

R₁ = -C₂H₅; R₂ = -C₄H₉; R₃, R₄ = -t-C₅H₁₁

BG 24:

R₁ = -C₂H₅; R₂ = -C₄H₉; R₃, R₄ = -t-C₄H₉

BG 25:

R₁, R₂ = -t-C₅H₁₁; R₃ = -C₄H₉; R₄ = H; R₅ = -C₃F₇

BG 26:

R₁ = -NHSO₂-C₄H₉; R₂ = H; R₃ = -C₁₂H₂₅; R₄ = Cl; R₅ = phenyl

BG 27:

R₁, R₂ = -t-C₅H₁₁; R₂ = Cl, R₃ = -CH (CH₃) ₂; R₄ = Cl; R₅ = pentafluorophenyl

BG 28:

R₁ = -t-C₅H₁₁; R₂ = Cl; R₃ = -C₆H₁₃; R₄ = Cl; R₅ = -2-chlorophenyl

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

PP 1:

PP 2:

R₂ = H

PP 3:

R₁ = -C₁₃H₂₇; R₂ = H

PP 4:

R₁ = -O-C₁₆H₃₃; R₂ = H

PP 5:

R₁ = -C₁₃H₂₇;

PP 6:

PP 7:

R₁ = -C₉H₁₉;

PP 8:

PP 9:

PP 10:

PP 11:

R₂ = H

PP 12:

R₂ = H

PP 13:

R₂ = H

PP 14:

PP 15:

PP 16:

PP 17:

PP 18:

R₂ = -CH₃

PP 19:

R₂ = -CH₃

PP 20:

R₂ = -t-C₄H₉

PP 21:

R₂ = -CH₃

PP 22:

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

GB 1:

R₂ = Cl;

GB 2:

R₂ = -OC₁₆H₃₃; R₃ = -SO₂NHCH₃
GB 3:

R₂ = Cl R₃ = -NHSO₂-C₁₆H₃₃
GB 4:

R₂ = Cl; R₃ = -COOC₁₂H₂₅
GB 5:

R₂ = Cl

GB 6:

R₂ = Cl;

GB 7:

R₂ = Cl; R₃ = -NHSO₂C₁₆H₃₃
GB 8:

R₂ = Cl;

GB 9:

R₂ = OC₁₆H₃₃; R₃ = -SO₂NHCOC₂H₅
GB 10:

R₂ = Cl;

GB 11:

R₂ = Cl;

GB 12:

R₂ = Cl;

GB 13:

R₂ = -OC₁₆H₃₃; R₃ = -SO₂NHCH₃
GB 14:

R₂ = Cl

GB 15: R₁, R₃, R₅, R₆ = H; R₄ = -OCH₃;

GB 16: R₂, R₆ = H; R₁ = -OC₁₆H₃₃; R₄, R₅ = -OCH₃;

GB 17: R₂, R₆ = H; R₁ = -OCH₃, R₄ = Cl; R₅ = -COOC₁₂H₂₅;

GB 18: R₂ = H; R₁ = -OC₁₆H₃₃; R₄ = Cl; R₅, R₆ = -OCH₃;

GB 19: R₂, R₅ = H; R₁ = -OC₁₆H₃₃; R₄ = -OCH₃;

R₆ = -SO₂N (CH₃) ₂
GB 20: R₂, R₆ = H; R₁, R₄ = -OCH₃;

GB 21:

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 point, 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 that contain a cleavable residue in the coupling point, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue ( eg DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic activity unfolds, for example as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR and FAR couplers.

Beispiele für Maskenkuppler sind

DIR-Kuppler, die Entwicklungsinhibitoren vom Azoltyp, z.B. Triazole und Benzotriazole freisetzen, sind in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 27 26 180, 36 26 219, 36 30 564, 36 36 824, 36 44 416 und 28 42 063 beschrieben. Weitere Vorteile für die Farbwiedergabe, d.h., Farbtrennung und Farbreinheit, und für die Detailwiedergabe, d.h., Schärfe und Körnigkeit, sind mit solchen DIR-Kupplern zu erzielen, die z.B. den Entwicklungsinhibitor nicht unmittelbar als Folge der Kupplung mit einem oxidierten Farbentwickler abspalten, sondern erst nach einer weiteren Folgereaktion, die beispielsweise mit einer Zeitsteuergruppe erreicht wird. Beispiele dafür sind in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-157 146 und 204 175, in US-A-4 146 396 und 4 438 393 sowie in GB-A-2 072 363 beschrieben.Examples of white couplers are:

Examples of mask couplers are

DIR couplers which release development inhibitors of the azole type, for example triazoles and benzotriazoles, are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 27 26 180, 36 26 219, 36 30 564, 36 36 824, 36 44 416 and 28 42 063. Further advantages for color reproduction, ie, color separation and color purity, and for detail reproduction, ie, sharpness and granularity, can be achieved with those DIR couplers which, for example, do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after a further follow-up reaction, which is achieved, for example, with a timing group. Examples of these are in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-157 146 and 204 175, in US-A-4 146 396 and 4 438 393 and in GB -A-2 072 363.

DIR couplers which release a development inhibitor which is decomposed into essentially photographically ineffective products in the developer bath are described, for example, in DE-A-32 09 486 and in EP-A-167 168 and 219 713. This measure ensures trouble-free development and processing consistency.

When using DIR couplers, in particular those which release a well-diffusible development inhibitor, improvements in color rendering, for example more differentiated color rendering, can be achieved by suitable measures in optical sensitization, for example in EP-A-115 304, 167 173 , GB-A-2 165 058, DE-A-37 00 419 and US-A-4 707 436.

The DIR couplers can be added to a wide variety of layers in a multilayer photographic material, for example also light-insensitive or intermediate layers. However, they are preferably added to the light-sensitive silver halide emulsion layers, the characteristic properties of the silver halide emulsion, for example its iodide content, the structure of the silver halide grains or their grain size distribution having an influence on the photographic properties achieved. The influence of the inhibitors released can be limited, for example, by incorporating an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it may be advantageous to use a DIR coupler which forms in the respective layer in which it is introduced a color which is different from the color to be produced in this layer in the coupling.

To increase the sensitivity, the contrast and the maximum density, DAR or FAR couplers can be used, which release a development accelerator or an fogger. Compounds of this type are, for example, in DE-A-25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-89 834, 110 511, 118 087, 147 765 and described in US-A-4,618,572 and 4,656,123.

As an example of the use of BAR couplers (Bleach Accelerator Releasing Coupler), reference is made to EP-A-193 389.

It can be advantageous to modify the effect of a photographically active group which is split off from a coupler in that an intermolecular reaction of this group occurs after its release with another group according to DE-A-35 06 805.

Beispiele für DAR-Kuppler

Da bei den DIR-, DAR- bzw. FAR-Kupplern hauptsächlich die Wirksamkeit des bei der Kupplung freigesetzten Restes erwünscht ist und es weniger auf die farbbildenden Eigenschaften dieser Kuppler ankommt, sind auch solche DIR-, DAR- bzw. FAR-Kuppler geeignet, die bei der Kupplung im wesentlichen farblose Produkte ergeben (DE-A-15 47 640).Examples of DIR couplers are:

Examples of DAR couplers

Since with DIR, DAR or FAR couplers mainly the effectiveness of the residue released during coupling is 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-15 47 640).

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).

The material may further contain compounds other than couplers, which can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR-hydroquinones and other compounds, as described for example in US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.

High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211. The high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.

The couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it to the casting solution for the layer in question. Choosing the right one Solvents or dispersants depend on the solubility of the compound.

Methods for introducing compounds which are essentially insoluble in water by grinding processes are described, for example, in DE-A-26 09 741 and DE-A-26 09 742.

Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-0 043 037.

Instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.

The compounds can also be introduced into the casting solution in the form of loaded latices. Reference is made, for example, to DE-A-25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-A-0 014 921, EP-A-0 069 671, EP-A-0 130 115, U.S.-A-4,291,113.

The diffusion-resistant incorporation of anionic water-soluble compounds (for example of dyes) can also be carried out with the aid of cationic polymers, so-called pickling polymers.

Suitable oil formers are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.

Examples of suitable oil formers are dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert.-amylphenol, dioctylacelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-doxy-5-butyl-2-butyl -octylaniline, paraffin, dodecylbenzene and diisopropylnaphthalene.

Each of the differently sensitized, light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470). In this case, red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.

If the green or red-sensitive layers are suitably low in their own sensitivity, other layer arrangements can be selected without the yellow filter layer, in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.

The non-light-sensitive intermediate layers, which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.

Suitable agents, which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), Chapter VII, 17 842/1979, pages 94-97 and 18.716 / 1979, page 650 and in EP-A- 69,070, 98,072, 124,877, 125,522 and in US-A-463,226.

R₁, R₂ =

-t-C₈H₁₇
-s-C₁₂H₂₅
-t-C₆H₁₃

-s-C₈H₁₇
-C₁₅H₃₁

Liegen mehrere Teilschichten gleicher spektraler Sensibilisierung vor, so können sich diese hinsichtlich ihrer Zusammensetzung, insbesondere was Art und Menge der Silberhalogenidkörnchen betrifft, unterscheiden. Im allgemeinen wird die Teilschicht mit höherer Empfindlichkeit von Träger entfernter angeordnet sein als die Teilschicht mit geringerer Empfindlichkeit. Teilschichten gleicher spektraler Sensibilisierung können zueinander benachbart oder durch andere Schichten, z.B. durch Schichten anderer spektraler Sensibilisierung getrennt sein. So können z.B. alle hochempfindlichen und alle niedrigempfindlichen Schichten jeweils zu einem Schichtpaket zusammengefaßt sein (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).Examples of particularly suitable compounds are:

R₁, R₂ =

-t-C₈H₁₇
-s-C₁₂H₂₅
-t-C₆H₁₃

-s-C₈H₁₇
-C₁₅H₃₁

If there are several sub-layers of the same spectral sensitization, these can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains. In general, the sublayer with higher sensitivity will be located further away from the support than the sublayer with lower sensitivity. Partial layers of the same spectral sensitization can be adjacent to one another or through other layers, for example through Layers of other spectral sensitization must be separated. For example, all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).

The photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides and others.

Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film. Connections of different structures are usually used for the two tasks. Examples are aryl-substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3,707,375), butadiene compounds (US-A-4,045,229) or benzoxazole compounds (US-A-3,700,455).

R, R₁ = H; R₂ = t-C₄H₉
R = H; R₁, R₂ = t-C₄H₉
R = H; R₁, R₂ = t-C₅H₁₁
R = H; R₁ = s-C₄H₉; R₂ = t-C₄H₉
R = Cl; R₁ = t-C₄H₉; R₂ = s-C₄H₉
R = Cl; R₁, R₂ = t-C₄H₉
R = Cl; R₁ = t-C₄H₉; R₂ = -CH₂-CH₂-COOC₈H₁₇
R = H; R = i-C₁₂H₂₅; R₂ = CH₃
R, R₁, R₂ = t-C₄H₉

R₁, R₂ = n-C₆H₁₃; R₃, R₄ = CN
R₁, R₂ = C₂H₅;

R₄ = COOC₈H₁₇
R₁, R = C₂H₅;

R₄ = COOC₁₂H₂₅
R₁, R₂ = CH₂=CH-CH₂; R₃, R₄ = CN

R₁, R₂ = H; R₃ = CN; R₄ = CO-NHC₁₂H₂₅
R₁, R₂ = CH₃; R₃ = CN; R₄ = CO-NHC₁₂H₂₅

Es können auch ultraviolettabsorbierende Kuppler (wie Blaugrünkuppler des α-Naphtholtyps) und ultraviolettabsorbierende Polymere verwendet werden. Diese Ultraviolettabsorbentien können durch Beizen in einer speziellen Schicht fixiert sein.Examples of particularly suitable compounds are

R, R₁ = H; R₂ = t-C₄H₉
R = H; R₁, R₂ = t-C₄H₉
R = H; R₁, R₂ = t-C₅H₁₁
R = H; R₁ = s-C₄H₉; R₂ = t-C₄H₉
R = Cl; R₁ = t-C₄H₉; R₂ = s-C₄H₉
R = Cl; R₁, R₂ = t-C₄H₉
R = Cl; R₁ = t-C₄H₉; R₂ = -CH₂-CH₂-COOC₈H₁₇
R = H; R = i-C₁₂H₂₅; R₂ = CH₃
R, R₁, R₂ = t-C₄H₉

R₁, R₂ = n-C₆H₁₃; R₃, R₄ = CN
R₁, R₂ = C₂H₅;

R₄ = COOC₈H₁₇
R₁, R = C₂H₅;

R₄ = COOC₁₂H₂₅
R₁, R₂ = CH₂ = CH-CH₂; R₃, R₄ = CN

R₁, R₂ = H; R₃ = CN; R₄ = CO-NHC₁₂H₂₅
R₁, R₂ = CH₃; R₃ = CN; R₄ = CO-NHC₁₂H₂₅

Ultraviolet absorbing couplers (such as α-naphthol type cyan couplers) and ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.

Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.

Suitable whiteners are described, for example, in Research Disclosure 17,643 (Dec. 1978), Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.

Certain binder layers, in particular the most distant layer from the support, but also occasionally intermediate layers, especially if they are the most distant layer from the support during manufacture, may contain photographically inert particles of inorganic or organic nature, e.g. as a matting agent or as a spacer (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).

The average particle diameter of the spacers is in particular in the range from 0.2 to 10 μm. The spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath. Examples of suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.

Zusätze zur Verbesserung der Farbstoff-, Kuppler- und Weißenstabilität sowie zur Verringerung des Farbschleiers (Research Disclosure 17 643/1978, Kapitel VII) können den folgenden chemischen Stoffklasen angehören: Hydrochinone, 6-Hydroxychromane, 5-Hydroxycumarane, Spirochromane, Spiroindane, p-Alkoxyphenole, sterische gehinderte Phenole; Gallussäurederivate, Methylendioxybenzole, Aminophenole, sterisch gehinderte Amine, Derivate mit veresterten oder verätherten phenolischen Hydroxylgruppen, Metallkomplexe.Suitable formalin scavengers include
H₂N-CONH- (CH₂) ₂-NH-CONH₂,

Additives to improve dye, coupler and whiteness stability and to reduce the color fog (Research Disclosure 17 643/1978, Chapter VII) can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, spiroindanes, p- Alkoxyphenols, steric hindered phenols; Gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.

Compounds that have both a hindered amine partial structure and a hindered phenol partial structure in one molecule (US-A-4,268,593) are particularly effective in preventing the degradation (degradation) of yellow color images as a result the development of heat, moisture and light. In order to prevent the deterioration (deterioration or degradation) of crimson color images, in particular their impairment (deterioration or degradation) as a result of exposure to light, Spiroindane (JP-A-159 644/81) and chromanes are caused by Hydroquinone diethers or monoethers are particularly effective (JP-A-89 835/80).

sowie die als EOP-Fänger aufgeführten Verbindungen.Examples of particularly suitable compounds are:

as well as the compounds listed as EOP catchers.

The layers of the photographic material can be hardened with the usual hardening agents. Suitable curing agents include formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen contain (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207) divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5 triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 732 316 and US-A-2 586 168); Isocyanates (US-A-3 103 437); Aziridine compounds (US-A-3 017 280 and US-A-2 983 611); Acid derivatives (US-A-2 725 294 and US-A-2 725 295); Carbodiimide type compounds (US-A-3 100 704); Carbamoylpyridinium salts (DE-A-22 25 230 and DE-A-24 39 551); Carbamoyloxypyridinium compounds (DE-A-24 08 814); Compounds with a phosphorus-halogen bond (JP-A-113 929/83); N-carbonyloximide compounds (JP-A-43353/81); N-sulfonyloximido compounds (US-A-4 111 926), dihydroquinoline compounds (US-A-4 013 468), 2-sulfonyloxypyridinium salts (JP-A-110 762/81), formamidinium salts (EP-A-0 162 308) , Compounds having two or more N-acyloximino groups (US-A-4 052 373), epoxy compounds (US-A-3 091 537), isoxazole-type compounds (US-A-3 321 313 and US-A-3 543 292); Halocarboxyaldehydes such as mucochloric acid; Dioxane derivatives such as dihydroxydioxane and di-chlorodioxane; and inorganic hardeners such as chrome alum and zirconium sulfate.

The hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened, or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.

There are slow-acting and fast-acting hardeners and so-called instant hardeners, which are particularly advantageous, in the classes listed. Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry and the swelling of the layer structure occurs as a result of the crosslinking reaction . Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).

These hardening agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin with the formation of peptide bonds and crosslinking of the gelatin.

• (a)
  
  worin

  R₁

  Alkyl, Aryl oder Aralkyl bedeutet,

  R₂

  die gleiche Bedeutung wie R₁ hat oder Alkylen, Arylen, Aralkylen oder Alkaralkylen bedeutet, wobei die zweite Bindung mit einer Gruppe der Formel

  

  verknüpft ist, oder

  R₁ und R₂

  zusammen die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes erforderlichen Atome bedeuten, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,

  R₃

  für Wasserstoff, Alkyl, Aryl, Alkoxy, -NR₄-COR₅, -(CH₂)_m-NR₈R₉, -(CH₂)_n-CONR₁₃R₁₄ oder

  

  oder ein Brückenglied oder eine direkte Bindung an eine Polymerkette steht, wobei

  R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈, und R₁₉

  Wasserstoff oder C₁-C₄-Alkyl,

  R₅

  Wasserstoff, C₁-C₄-Alkyl oder NR₆R₇,

  R₈

  -COR₁₀

  R₁₀

  NR₁₁R₁₂

  R₁₁

  C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

  R₁₂

  Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

  R₁₃

  Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

  R₁₆

  Wasserstoff, C₁-C₄-Alkyl, COR₁₈ oder CONHR₁₉,

  m

  eine Zahl 1 bis 3

  n

  eine Zahl 0 bis 3

  p

  eine Zahl 2 bis 3 und

  Y

  O oder NR₁₇ bedeuten oder

  R₁₃ und R₁₄

  gemeinsam die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes erforderlichen Atome darstellen, wobei der Ring z.B durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,

  Z

  die zur Vervollständigung eines 5- oder 6-gliedrigen aromatischen heterocyclischen Ringes, gegebenenfalls mit anelliertem Benzolring, erforderlichen C-Atome und

  X^⊖

  ein Anion bedeuten, das entfällt, wenn bereits eine anionische Gruppe mit dem übrigen Molekül verknüpft ist;

• (b)
  
  worin

  R₁, R₂, R₃ und X^⊖

  die für Formel (a) angegebene Bedeutung besitzen.

Suitable examples of instant hardeners are, for example, compounds of the general formulas

• (a)
  
  wherein

  R₁

  Means alkyl, aryl or aralkyl,

  R₂

  has the same meaning as R₁ or means alkylene, arylene, aralkylene or alkaralkylene, the second bond having a group of the formula

  

  is linked, or

  R₁ and R₂

  together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, the ring being able to be substituted, for example, by C₁-C₃alkyl or halogen,

  R₃

  for hydrogen, alkyl, aryl, alkoxy, -NR₄-COR₅, - (CH₂) _m -NR₈R₉, - (CH₂) _n -CONR₁₃R₁₄ or

  

  or a bridge link or a direct bond to a polymer chain, wherein

  R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈, and R₁₉

  Hydrogen or C₁-C₄ alkyl,

  R₅

  Hydrogen, C₁-C₄-alkyl or NR₆R₇,

  R₈

  -COR₁₀

  R₁₀

  NR₁₁R₁₂

  R₁₁

  C₁-C₄ alkyl or aryl, especially phenyl,

  R₁₂

  Hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,

  R₁₃

  Hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,

  R₁₆

  Hydrogen, C₁-C₄-alkyl, COR₁₈ or CONHR₁₉,

  m

  a number 1 to 3

  n

  a number 0 to 3

  p

  a number 2 to 3 and

  Y

  O or NR₁₇ mean or

  R₁₃ and R₁₄

  together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring may be substituted, for example, by C₁-C₃alkyl or halogen,

  Z.

  the carbon atoms required to complete a 5- or 6-membered aromatic heterocyclic ring, optionally with a fused benzene ring, and

  X ^⊖

  mean an anion which is omitted if an anionic group is already linked to the rest of the molecule;

• (b)
  
  wherein

  R₁, R₂, R₃ and X ^⊖

  have the meaning given for formula (a).

There are diffusible curing agents that have the same curing effect on all layers within a layer structure. But there are also layer-limited, non-diffusing, low molecular weight and high molecular hardener. They can be used to link individual layers, for example the protective layer, particularly strongly. This is important if the silver halide layer is hardened little because of the increase in silver opacity and the protective layer has to improve the mechanical properties (EP-A 0 114 699).

Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step. All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol 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-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine. Further useful color developers are described, for example, in J. Amer Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.

After the color development, an acidic stop bath or watering can follow.

Usually the material is bleached and fixed immediately after color development. As bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used. Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulfates and peroxides, e.g. Hydrogen peroxide.

The bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.

Favorable results can be obtained using a subsequent final bath which contains little or no formaldehyde.

However, the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent. When formaldehyde is added, this stabilizing bath also acts as a final bath.

In the case of color reversal materials, development is first carried out using a black and white developer whose oxidation product is not capable of reacting with the color couplers. This is followed by a diffuse second exposure and then development with a color developer, bleaching and fixing.

example 1

This example shows the advantages of the antifoggants according to the invention when used in color reversal materials.

Color photographic recording materials for reverse processing are produced by successively applying the layers listed below to a cellulose triacetate support provided with an adhesive layer.

Recording material

• 1. Eine rotsensibilisierte Silberhalogenidemulsion, mittlerer Korndurchmesser 0,5 µm, enthaltend pro kg 70 g Gelatine, 60 g Silber (davon 96 Mol-% in Form des Bromids und 4 Mol-% in Form des Iodids) und 55 g des Blaugrünkupplers BG 25.
  Der Silberauftrag pro m² beträgt 2,5 g Silbernitrat.
• 2. Eine 2 gew.-%ige wäßrige Gelatinelösung mit einem Naßauftrag von 60 g/m², enthaltend pro kg 4 g des in DE-A 23 04 319 beschriebenen polymeren Weißkupplers W-2.
• 3. Eine grünsensibilisierte Silberhalogenidemulsion, mittlerer Korndurchmesser 0,45 µm, enthaltend pro kg 70 g Gelatine, 60 g Silber (davon 96 Mol-% in Form des Bromids und 4 Mol-% in Form des Iodids) und 60 g des Purpurkupplers PP 12. Der Silberauftrag pro m² beträgt 2,8 g Silbernitrat.
• 4. Eine gelbe Silberdispersion, enthaltend pro kg die 1,8 g Silbernitrat entsprechende Menge Silber und 12 g Gelatine. Die Farbdichte der Gelbfilterschicht, gemessen hinter einem Blaufilter, beträgt 0,6; der Silberauftrag pro m² beträgt 0,2 g Silbernitrat.
• 5. Eine unsensibilisierte Silberhalogenidemulsion, mittlerer Korndurchmesser 0,6 µm, enthaltend pro kg 70 g Gelatine, 60 g Silber (davon 95 Mol-% in Form des Bromids und 5 Mol-% in Form des Iodids) und 140 g des Gelbkupplers GB 2.
  Der Silberauftrag pro m² beträgt 1,5 g Silbernitrat.
• 6. Eine 1 gew.-%ige Gelatinelösung mit einem Naßauftrag von 60 g pro m² .
• 7. Eine 1 gew.-%ige wäßrige Lösung des Härters H-1 mit einem Naßauftrag von 60 g pro m² :
  

Es wurde Proben des vorstehend beschriebenen fotografischen Umkehrmaterials hergestellt, wobei das Vergleichsmaterial Nr. 1 keine erfindungsgemäßen Antischleiermittel enthält. Den silberhalogenidhaltigen Gießlösungen der fotografischen Materialien 2 bis 7 sind bestimmte Mengen der erfindungsgemäßen Verbindungen zugesetzt.

• 1. A red-sensitized silver halide emulsion, average grain diameter 0.5 μm, containing 70 g of gelatin, 60 g of silver (thereof 96 mol% in the form of the bromide and 4 mol% in the form of the iodide) and 55 g of the cyan coupler BG 25 per kg .
  The silver application per m² is 2.5 g of silver nitrate.
• 2. A 2% by weight aqueous gelatin solution with a wet application of 60 g / m 2, containing 4 g of the polymeric white coupler W-2 described in DE-A 23 04 319 per kg.
• 3. A green-sensitized silver halide emulsion, average grain diameter 0.45 μm, containing 70 g gelatin, 60 g silver (thereof 96 mol% in the form of the bromide and 4 mol% in the form of the iodide) and 60 g of the purple coupler PP 12 per kg . The silver application per m² is 2.8 g of silver nitrate.
• 4. A yellow silver dispersion containing per kg the amount of silver corresponding to 1.8 g of silver nitrate and 12 g of gelatin. The color density of the yellow filter layer, measured behind a blue filter, is 0.6; the silver application per m² is 0.2 g silver nitrate.
• 5. An unsensitized silver halide emulsion, average grain diameter 0.6 μm, containing 70 g of gelatin, 60 g of silver (of which 95 mol% in the form of the bromide and 5 mol% in the form of the iodide) and 140 g of the yellow coupler GB 2 per kg .
  The silver application per m² is 1.5 g of silver nitrate.
• 6. A 1% by weight gelatin solution with a wet application of 60 g per m².
• 7. A 1% by weight aqueous solution of hardener H-1 with a wet application of 60 g per m²:
  

Samples of the photographic reversal material described above were prepared, with Comparative Material No. 1 not having anti-fogging agents according to the invention contains. Certain amounts of the compounds according to the invention are added to the silver halide casting solutions of the photographic materials 2 to 7.

The samples thus prepared were exposed under a step wedge and subjected to color reversal development as described in "Manual for Processing Kodak Ektachrome Film Using Process E 7", Eastman Kodak Company, 1977 (see Kodak Publication No. Z-119).

The following data for the yellow, purple and cyan layer were recorded in Table 1 below.

FA

=

γ¹

Anstieg der Gradationskurve zwischen den Punkten 0,2 über Schleier und dem Punkt der Gradationskurve, der bei 6,5 1g I · t geringerer Belichtung resultiert

Empfindlichkeit:

1g I · t-Wert bei Dichte 1,0

γ¹/D_max:

Normierung der Gradation bei unterschiedlichen Maximaldichten

The measurement parameters specified there are defined as follows:

FA

=

γ¹

Rise of the gradation curve between the points 0.2 over fog and the point of the gradation curve, which results at 6.5 1g I · t less exposure

Sensitivity:

1g I · t value at density 1.0

γ¹ / D _max :

Standardization of the gradation at different maximum densities

The measured values of the experiments show very clearly that when the compounds according to the invention are used, a significantly higher color yield is achieved without a simultaneous flattening of the gradation.

Example 2

A highly sensitive silver bromide iodide emulsion with 5 mol% iodide and a gelatin-silver weight ratio of 1.2 and a content of 150 g of silver nitrate per kg of emulsion was ripened with sulfur and gold compounds for optimum sensitivity.

The emulsion batch was divided into several parts and the following substances were added per kg of emulsion: 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazainden 1% by weight, aqueous alkaline solution 1.5 g Saponin 10 wt .-%, dissolved in water 3.5 g
and the substances according to the invention shown in Table 2 below (1% by weight dissolved in methanol) in the stated amounts.

und ein Netzmittel enthielt, mit einer Auftragsdicke von 2 g Gelatine/m² und 340 mg Härtungsmittel/m² aufgetragen.The emulsions were then poured onto a cellulose acetate support and dried (application 6.7 to 7.0 g, calculated as silver nitrate per m²). A protective layer, which is a hardening agent of the formula, was applied to the emulsion layer

and containing a wetting agent, applied at a coating thickness of 2 g gelatin / m² and 340 mg hardening agent / m².

The samples were then exposed in a sensitometer behind a gray wedge and developed in a developer of the following composition at 20 ° C. for 7 minutes. p-methylaminophenol 3.5 g Hydroquinone 3.5 g Sodium sulfite 70.0 g sodium 40.0 g Potassium bromide 2.0 g borax 7.0 g made up to 1 l with water.

The samples were then fixed in a customary manner in an acidic fixing bath and watered. The results of the sensitometric test are summarized in Table 2 below. It can be seen that the substances according to the invention reduce the fog and are therefore suitable as anti-fog agents, even if the material is stored at a higher temperature or humidity.

Example 3

To 1 kg of a green-sensitized silver bromide iodide emulsion with a silver (calculated as silver nitrate) / gelatin weight ratio of 1: 0.4 and a content of 0.91 mol of silver halide per kg of emulsion with 5 mol% of iodide was added to 1.2 g of 4-hydroxy -6-methyl-1,3,3a, 7-tetraazaindene was added in aqueous alkaline solution and the emulsion thus obtained was divided into several equal parts and the compounds according to the invention shown in Table 3 below were dissolved in methanol in the stated amounts in the individual samples added. Before the coating, the emulsion was added per kg:
75g of a 5% by weight gelatin solution;
109 g of a 11.1% by weight coupler dispersion of the PP 13 coupler
as well as wetting agents in aqueous solution and 1,180 ml of water.

in Mengen von 2,4·10⁻⁴ Mol/Mol Ag zugesetzt.The dye of the formula was used as a sensitizer

added in amounts of 2.4 · 10⁻⁴ mol / mol Ag.

The emulsions were poured onto the antihalation layer of a cellulose acetate support consisting of a silver dispersion with a silver coating corresponding to 2.2 to 2.3 g AgNO₃ / m².

A hardening layer was applied to each of the emulsion layers as in Example 2.

The samples were subjected to a fresh and an oven test for 3 days at 60 ° C and 34% rel. Humidity and a tropical cabinet test of 3 days at 35 ° C and 90% rel. Humidity subjected.

The samples were then exposed in a sensitometer behind a step wedge and developed in the following developer at 38 ° C for 3 1/4 minutes.

developer

1-hydroxyethane-1,1-diphosphonic acid Na₂ salt 2 g Ethylenediamine-N, N, N ′, N′-tetraacetic acid 2 g Potassium carbonate 34.1 g Sodium bicarbonate 1.55 g Sodium disulfite 0.28 g Sodium sulfite 3.46 g Potassium bromide 1.34 g Hydroxylamine sulfate 2.4 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline 4.7 g Make up to 1 liter with water.

The further processing includes the following baths: Stop bath 1 minute at 38 ° C; Bleach bath 3 1/4 minutes at 38 ° C; Water 3 1/2 minutes at 38 ° C; Fixer 3 1/4 minutes at 38 ° C; Water 5 minutes at 38 ° C.

The stop, bleaching and fixing baths used correspond to those commonly used (British Journal of Photography, 1974 , pages 597 and 598).

The results obtained are shown in Table 3.

The substances according to the invention reduce the high fog without significantly reducing the sensitivity and the gradation and improve the storage stability of the photographic material.

In contrast, the known triazole compounds I and II (identical to those from Example 2) result in less haze reduction.

Claims (3)

1. A photographic recording material comprising a layer support and at least one photosensitive silver halide emulsion layer arranged thereon, characterized in that the at least one silver halide emulsion layer contains an antifogging agent corresponding to formula (I):

   

   in which

   A   represents H, the cation of a metal atom or non-metal group, a group attached by a covalent bond to the nitrogen atom of the triazole which is only eliminated during processing of the material with release of the triazole and which is selected from the group consisting of:

   

   -CO-N(CH₃)₂, -CO-CH₃, -SO₂-N(CH₃)₂ and SO₂-CH₃,

   R₁   represents H, optionally substituted C₁₋₉ alkyl, C₂₋₈ alkenyl, C₆₋₁₀ aryl, SR₃,

   R₂   represents H, optionally substituted C₁₋₉ alkyl, C₂₋₈ alkenyl, C₆₋₁₀ aryl, C₅₋₁₀ heteroaryl, Cl, Br, -COOR₃, -COR₃, -OCOR₃,

   R₃   represents optionally substituted C₁₋₉ alkyl, C₂₋₈ alkenyl, C₆₋₁₀ aryl, C₅₋₁₀ heteroaryl,

   the sum of the carbon atoms in the substituents R₁, R₂ and R₃ being equal to or greater than 5 where R₂ is a carboxylic ester group.
2. A photographic recording material as claimed in claim 1, characterized in that at least one silver halide emulsion layer contains an antifogging agent corresponding to formula (I) in a quantity of from 10⁻⁵ to 10⁻² mol per mol silver halide.
3. A photographic recording material as claimed in claim 1, characterized in that it is a colour photographic recording material comprising a layer support and, arranged thereon, at least three photosensitive silver halide emulsion layers of different spectral sensitivity with which a yellow coupler, a magenta coupler and a cyan coupler are respectively spectrally associated.