EP0358071A2 - Photographic-recording material - Google Patents

Abstract

Colour-photographic silver halide material of the negative type, in which at least one silver halide emulsion layer contains a compound of the formula <IMAGE> adsorbed on the silver halide grain, A being a grain-active adhesion group of the formulae IIa to IId: <IMAGE> Z is a divalent bridge member, S<*> is a latent fogging agent group which on colour development becomes an active fogging agent (S), and n is 0 or 1, is distinguished by improved sensitivity.

Description

The invention relates to a negative type color photographic silver halide material with improved sensitivity.

It is known to increase the sensitivity of photographic silver halide materials with the aid of so-called DAR and FAR couplers (development accelerator releasing or fogging agent releasing couplers), which split off either a development accelerator or a fogging agent in the coupling reaction with the developer oxidation product. These couplers also include those compounds which split off a connecting part which has both a hydrazide group (fogging agent) and an adhesive group for adsorption on the silver halide grain (DE-A 33 33 355, 3 410 616, EP-A-0 118 087, 0 147 765 and US-A-4 656 123). However, the increase in sensitivity achieved in this way is not yet sufficient for many applications.

The object of the present invention was therefore to provide such additives for photographic materials, with which a further increase in sensitivity can be achieved.

It has now surprisingly been found that such an increase in sensitivity is achieved by adsorbing compounds having at least one grain-active adhesive group and at least one latent fogging agent group on the silver halide grain before the imagewise exposure.

Z₁ die restlichen Glieder zur Vervollständigung eines vorzugsweise 5- oder 6-gliedrigen Ringes, der we­nigstens ein weiteres Heteroatom wie ein Stick­stoff- oder Schwefelatom enthält und gegebenenfalls benzo- oder naphthokondensiert ist,
Z₂ die restlichen Glieder zur Vervollständigung eines vorzugsweise 5- oder 6-gliedrigen Ringes, der gege­benenfalls benzo- oder naphthokondensiert ist,
X -NH₂, -NHR -NH-NH₂, -NH-NHR, -SR,
Y -S-, -NH-, -NR-,
B, D Wasserstoff, R oder gemeinsam die restlichen Glieder eines 5- oder 6-gliedrigen Ringes,
R einen aliphatischen, aromatischen oder heterocycli­schen Rest,
Z ein zweiwertiges Zwischenglied,
S* eine latente Schleiermittelgruppe, die bei der Farbentwicklung zum aktiven Schleiermittel (S) wird, und
n 0 oder 1 bedeuten.The invention therefore relates to a color photographic silver halide material of the negative type, in which at least one silver halide emulsion layer is a compound of the formula
A― (Z) _n ―S * (I)
contains adsorbed on the silver halide grain,
where A is a grain-active adhesion group of the formulas IIa to IId:

Z₁ the remaining members to complete a preferably 5- or 6-membered ring which contains at least one further heteroatom such as a nitrogen or sulfur atom and is optionally benzo- or naphtho-condensed,
Z₂ the remaining members to complete a preferably 5- or 6-membered ring which is optionally benzo- or naphtho-condensed,
X -NH₂, -NHR -NH-NH₂, -NH-NHR, -SR,
Y -S-, -NH-, -NR-,
B, D is hydrogen, R or together the remaining members of a 5- or 6-membered ring,
R is an aliphatic, aromatic or heterocyclic radical,
Z is a divalent intermediate element,
S * a latent group of fogging agents, which becomes an active fogging agent (S) during color development, and
n is 0 or 1.

Preferred divalent intermediate members Z are alkylene groups, arylene groups, -COCH₂-, -COCH₂-S-, -COCH₂-O-,

wobei in Formel IIIc einer der Reste R₅, R₆,R₇ oder R₈ die Verknüpfungsstelle für den Rest A-(Z)_n- ist.Preferred latent fogging agent groups S * correspond to the formulas IIIa to IIIc:

wherein in formula IIIc one of the radicals R₅, R₆, R₇ or R₈ is the point of attachment for the radical A- (Z) _n -.

R₈ Wasserstoff, Alkoxy oder Acylamino
R₈ und R₆ zusammen die restlichen Glieder eines hetero­cyclischen Ringes, z.B. eines Imidazol- oder Pyri­donringes, der mit dem Naphtholring kondensiert ist,
R₉ eine gegebenenfalls substituierte aliphatische oder olefinische, cycloaliphatische oder cycloolefi­nische, aromatische oder heterocyclische Gruppe,
R₁₀ Wasserstoff, Alkyl, Aryl,
R₁₁ Alkyl, Aryl oder Hetaryl und
L eine zweiwertige Gruppe, die eine mit der Hydrazin­gruppe verknüpfte -CO-Gruppe enthält, z.B. -

-

oder -CH₂-

-.

R 1 is hydrogen, halogen, alkyl, alkoxy,
R₂ is an acyl group, for example -CHO, -COR₉, -COOR₉, -CONH₂, -CONHR₉, -SO₂R₉, -PO (R₉) ₂, -PO (OR₉) ₂,
R₃ is hydrogen, halogen, alkyl, alkoxy,
R₄ is hydrogen, halogen, alkyl, alkoxy, acylamino, nitro or sulfonyl,
R₅ hydrogen, -CONHR₉, -NHCOR₉, -SO₂NHR₉, -NHCOOR₉, -NHSO₂R₉, -NHCONHR₉,
R₆ is hydrogen or alkyl,
R₇ is hydrogen or acyl such as -COR₉, -COOR₉, -CONHR₉, SO₂NHR₃ or
R₆ and R₇ together are the remaining members of a heterocyclic ring or together with the nitrogen atom an azomething group

R₈ is hydrogen, alkoxy or acylamino
R₈ and R₆ together are the remaining members of a heterocyclic ring, for example an imidazole or pyridone ring, which is condensed with the naphthol ring,
R₉ is an optionally substituted aliphatic or olefinic, cycloaliphatic or cycloolefinic, aromatic or heterocyclic group,
R₁₀ hydrogen, alkyl, aryl,
R₁₁ alkyl, aryl or hetaryl and
L is a divalent group containing a -CO group linked to the hydrazine group, for example -

-

or -CH₂-

-.

worin
L₁ C₁-C₆-Alkylen,
L₂ ein Schwefelatom,
R₁₂ einen heterocyclischen Rest,
p 0 oder 1 und
q 0 oder 1 bedeuten.The compound I very particularly preferably corresponds to the formula (IV)

wherein
L₁ C₁-C₆ alkylene,
L₂ is a sulfur atom,
R₁₂ is a heterocyclic radical,
p 0 or 1 and
q is 0 or 1.

Preferred heterocyclic radicals R₁₂ are 2-mercapto-1,3,4-thiadiazol-5-yl, 1-amino-2-mercapto-1,3,4-triazol-5-yl, 1-methyl-2-mercapto-1 , 3,4-triazol-5-yl, 2-mercapto-5-phenyl-1,3,4-triazol-1-yl, 1,2,3-triazol-4-yl, 2-mercapto-4-methyl -1,3-thiazol-5-yl, benzotriazol-5-yl, imidazol-2-yl and 1,3,4-triazol-2-yl.

The compounds of formula I or IV are preferably added to the silver halide emulsion after spectral sensitization, in particular in amounts of 0.005 to 1 mmol / mol AgNO₃, preferably 0.01 to 0.1 mmol / mol AgNO₃.

If the photographic material contains light-sensitive layers of the same spectral sensitization but different sensitivity, the compounds I and IV are preferably added to the most sensitive layers. In particular, the compounds of the formulas I and IV are added to all highly sensitive layers.

Examples of compounds according to the invention are:

Some of the compounds are known from the literature or can be prepared by processes known from the literature.

The use of hydrazine derivatives in photography has long been known; the article reports in detail about it; Development nucleation by hydrazine and hydrazine derivatives, Research Disclosure No. 23 510, Nov. 1983.

Examples of negative type color photographic materials are color negative films and color photographic paper.

Suitable supports for the production of such color photographic materials are, for example, films and sheets 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 supports 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-vinylpyrolidone, 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, sugar, starch or alginates. Semi-synthetic gelatin substitutes are usually modified natural products. Examples of these are 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.

The binders should have a sufficient amount of functional groups, so that by reaction enough suitable layers can be produced 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 smallest possible amount 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 films, silver bromide iodide emulsions are usually used; in the case of color negative paper, silver chloride bromide emulsions are usually used. It can be about mainly compact crystals that are, for example, regular cubic or octahedral or can have transitional forms. However, platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which 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 both homo- and 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 Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.

The halide silver 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. Except through 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 take place predominantly by Ostwald ripening, a fine-grained, so-called Lippmann emulsion preferably being mixed with a less soluble emulsion and being redissolved on the latter.

Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe can 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).

Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (for example gold, platinum, palladium, iridium) Nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia of Industrial Chemistry, 4th edition, vol. 18, pp. 431 ff. and Research Disclosure No. 17643, Section III). Alternatively or additionally, a reduction sensitization with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidinesulfinic acid) can be carried out by hydrogen, by 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.

Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, 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. 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 benzothiazolium salts can also be used as antifoggants. 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 one produced according to the invention Photosensitive material 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 development acceleration, high contrast, sensitization, etc.) . In addition to natural surface-active compounds, for example saponin, synthetic surface-active compounds (surfactants) are mainly used: non-ionic surfactants, for example alkylene oxide compounds, glycerol compounds or glycidol compounds, cationic surfactants, for example higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an 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 and sulfur 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 Blausensilbilisatoren
  symmetrische oder asymmetrische Benzimidazo-, Oxa-, Thia- oder Selenacyanine mit mindestens einer Sulfoalkylgruppe am heterocyclischen Stickstoff und gegebenenfalls weiteren Substituierten am aromati­schen Kern, sowie Apomerocyanine mit einer Rhoda­ningruppe.

The following dyes, arranged according to spectral regions, are particularly suitable:

• 1. as red sensitizers
  9-ethyl carbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl, and 9-ethyl-naphthoxathia or -selencarbocyanines and 9- Ethyl-naphthothiaoxa- or -benzimidazocarbocyanine, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.
• 2. as green sensitizers
  9-ethylcarbocyanines 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 silbilizers
  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; R₄ = SO₃^⊖

H(C₂H₅)₃; 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-; R₄ = SO₃^⊖

H(C₂H₅)₃; 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;

Examples include, in particular for negative and reversal film, the red sensitizers RS, green sensitizers GS and blue sensitizers BS listed below, which can be used individually or in combination with one another, for example RS 1 and RS 2, and GS 1 and GS 2.

RS 1: R₁, R₃, R₇, R₉ = H; R₂, R₈ = Cl; R₄ = SO₃ ^⊖

H (C₂H₅) ₃; 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-; R₄ = SO₃ ^⊖

H (C₂H₅) ₃; 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;

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. The red-sensitive layers usually turn blue green couplers, 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 = -SO₂-CH₃
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-ChlorphenylColor 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 = -SO₂-CH₃
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 producing 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 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, the latter being able to be added in addition to the compounds according to the invention.

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-2 414 006, 2 610 546, 2 659 417, 2 754 281, 2 726 180, 3 626 219, 3 630 564, 3 636 824, 3 644 416 and 2 842 063. Further advantages for color rendering, that is, color separation and color purity, and for detail rendering, that is, 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. With this measurement, trouble-free development and processing consistency is achieved.

When using DIR couplers, especially those that release a well-diffusible development inhibitor, improvements in color rendering, e.g. achieve a more differentiated color rendering, as described, for example, in EP-A-115 304, 167 173, GB-A-2 165 058, DE-A-3 700 419 and US-A-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 insert a DIR coupler set, which forms in the respective layer in which it is introduced, a color different from the color to be generated 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-2 534 466, 3 209 110, 3 333 355, 3 410 616, 3 429 545, 3 441 823, in EP-A-89 834, 110 511, 118 087, 147 765 and described in US-A-4,628,572 and 4,656,123.

As an example of the use of DAR couplers, 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 by an intermolecular reaction of this group occurring after its release with another group according to DE-A-3 506 805.

Examples of DIR couplers are:

Examples of DAR couplers

Since with DIR, DAR or FAR couplers the effectiveness of the residue released during 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).

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-3 145 640, 2 515 213, 2 447 079 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-2 609 741 and DE-A-2 609 742.

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-2 541 230, DE-A-2 541 274, DE-A-2 835 856, 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 (eg 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 dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phylate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert-amylphenol, dioctyl acylate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-doxy-5-butyl-2-. -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). 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, with 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 / 1978, Chapter VII, 17.842 / 1979, pages 94-97 and 18.716 / 1979, page 650 and in EP-A-60 070, 98 072 , 124 877, 125 522 and in US-A-462 226.

R₁, R₂ = -t-C₈H₁₇
-sec-C₁₂H₂₅
-t-C₆H₁₃

Examples of particularly suitable compounds are:

R₁, R₂ = -t-C₈H₁₇
-sec-C₁₂H₂₅
-t-C₆H₁₃

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 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 Separate layers of other spectral sensitization. For example, all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A 1 958 709, DE-A 2 530 645, DE-A 2 622 922).

The photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _min dyes, additives for improving the stabilization of dyes, couplers and whites and for reducing the color fog 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 Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. Nos. 3,314,794 and 3,352,681), benzophenone compounds (JP-A 2784/71), cinnamic acid ester compounds (US Pat. Nos. 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-tert.
R = H; R₁ = sec-C₄H₉; R₂ = t-C₄H₉
R = Cl; R₁ = t-C₄H₉; R₂ = sec-C₄H₉
R = Cl; R₁, R₂ = t-C₄H₉
R = Cl; R₁ = t-C₄H₉-tert.; R₂ = -CH₂-CH₂-COOC₈H₁₇
R = H; R = iso-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

Examples of particularly suitable compounds are

R, R₁ = H; R₂ = t-C₄H₉
R = H; R₁, R₂ = t-C₄H₉
R = H; R₁, R₂ = t-C₅H₁₁-tert.
R = H; R₁ = sec-C₄H₉; R₂ = t-C₄H₉
R = Cl; R₁ = t-C₄H₉; R₂ = sec-C₄H₉
R = Cl; R₁, R₂ = t-C₄H₉
R = Cl; R₁ = t-C₄H₉-tert .; R₂ = -CH₂-CH₂-COOC₈H₁₇
R = H; R = iso-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 polymer 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 white toners are e.g. in Research Disclosure December 1978, page 22 ff. Unit 17,643, 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 3 331 542, DE-A 3 424 893, Research Disclosure December 1978, page 22 ff. Unit 17 643, 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.

Suitable formalin scavengers include

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, sterically 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 (deterioration or 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 magenta 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 are, for example, formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethyl urea), 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 (U.S. 3,017,280 and U.S. 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 2 225 230 and DE-A 2 439 551); Carbamoyloxypyridinium compounds (DE-A-2 408 814); 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); Halocarboxyladehydes 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 caused by the crosslinking reaction and the swelling of the layer structure occurs . 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.

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 Brüchenglied 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;

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

wherein
R₁ denotes 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, which ring can 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 link or a direct bond to a polymer chain, where
R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈, and R₁₉ are hydrogen or C₁-C₄-alkyl,
R₅ is hydrogen, C₁-C₄-alkyl or NR₆R₇,
R₈ -COR₁₀
R₁₀ NR₁₁R₁₂
R₁₁ C₁-C₄ alkyl or aryl, especially phenyl,
R₁₂ is hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,
R₁₃ is hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,
R₁₆ is hydrogen, C₁-C₄-alkyl, COR₁₈ or CONHR₁₉,
m is a number 1 to 3
n is a number 0 to 3
p is a number 2 to 3 and
YO or NR₁₇ mean or
R₁₃ and R₁₄ together represent the atoms necessary to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring can be substituted by C₁-C₃-alkyl or halogen, for example,
Z the C atoms and required to complete a 5- or 6-membered aromatic heterocyclic ring, optionally with a fused benzene ring
X ^{⊖ is} an anion which is omitted if an anionic group is already linked to the rest of the molecule;

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, diethyltriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulphates are also suitable as bleaching agents.

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 functions as a final bath.

Since the granularity increases in the region of low color densities as a result of the compounds according to the invention, it is advisable to add these compounds to the most sensitive partial layers in the case of materials which contain more than one layer for a spectral region.

worin
Z die zur Vervollständigung eines Oxazol- oder Oxazinringes erforderlichen Atome, und
Y ein ankondensiertes aromatisches Ringsystem mit mindestens einem aromatischen Ring, das mit einer sauren Gruppe substituiert sein kann, oder einen Substituenten mit einer sauren Gruppe bedeuten.As a rule, the substances according to the invention not only increase the developable density in the exposure area, but also that of a veil which may be present. The addition of the substances according to the invention is therefore expediently combined with the addition of suitable photographic stabilizers. For example, compounds of the general formula have proven successful

wherein
Z the atoms required to complete an oxazole or oxazine ring, and
Y is a fused-on aromatic ring system with at least one aromatic ring, which may be substituted with an acidic group, or a substituent with an acidic group.

Example 1 (single layers)

The following layers were applied to a transparent cellulose triacetate support.

The quantities given relate to 1 m². For the silver halide application, the equivalent amounts of AgNO₃ are given.

die 2,8 g Gelatine enthielt, wurden mit 0,03 mMol der erfindungsgemäßen kornaktiven latenten Schleiermittel oder der Vergleichsverbindung gemäß Tabelle 1 versetzt.4.0 g of AgNO₃ a spectrally green-sensitized Ag (Cl, Br, J) emulsion with 4.5 mol% I ^⊖ , 2.0 mol% Cl ^⊖ , average grain size 0.65 µm, crystallographically limited by 100 areas stabilized with 30 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and 80 mg of the stabilizer of the formula

containing 2.8 g of gelatin, 0.03 mmol of the grain-active latent fogging agent according to the invention or the comparison compound according to Table 1 were added.

in 0,8 g Trikresylphosphat wurden zugefügt.0.8 g of the color coupler of the formula

in 0.8 g of tricresyl phosphate were added.

gehärtet.The layers were coated with a protective gelatin layer (0.5 μm dry layer thickness) and with 0.3 g / m² of the hardening agent

hardened.

After imagewise exposure to white light with an exposure time of 1/100 sec behind a gray sensor wedge, the samples were processed using a color negative method, which is described in "The British Journal of Photography", 1974, pages 597 and 598.

The photographic sensitivities are shown in the table below.

Comparison connection:

Table 1 additive photogr. sensitivity connection Molecular weight mmol to 1 mol of AgNO₃ comparison without - - 23.2 DIN comparison Comparative compound 829.1 0.03 23.6 DIN invention 15 355.5 0.03 26.8 DIN invention 22 288.3 0.03 26.7 DIN invention 23 376.4 0.03 26.5 DIN invention 24th 347.4 0.03 26.8 DIN invention 25th 346.8 0.03 26.4 DIN invention 26 316 0.03 25.2 DIN

Example 2

As described below, by adding the comparison substance and the substances according to the invention to the highly sensitive partial layers 9, 11 and 13, the layer structures A to G and the comparison structure H were produced without the corresponding additives by successively casting the layers 1 to 14 on a transparent layer support.

Layer support, quantitative data and stabilization of the emulsions as in Example 1. 1st layer (antihalo layer) 0.2 g black colloidal silver 1.2 g gelatin 0.1 g UV absorber UV 1 0.2 g UV absorber UV 2 0.02 g Tricresyl phosphate 0.03 g Dibutyl phthalate 2nd layer (intermediate layer ) 0.4 g AgNO₃ a Mikrat-Ag (BrJ) emulsion, average grain diameter 0.05 µm, 2 mol% iodide 1.2 g gelatin 0.08 g colored coupler RM 1 0.15 g Dibutyl phthalate 3rd layer (low red sensitive layer) 2.0 g AgNO₃ a spectrally red-sensitized Ag (Br, J) emulsion with 3.5 mol% iodide, average grain diameter 0.42 µm 2.0 g gelatin 0.58 g colorless coupler C1 0.02 g DIR coupler DIR 1 0.02 g DIR coupler DIR 2 0.05 g colored coupler RM 1 0.40 g Tricresyl phosphate 0.15 g Dibutyl phthalate 4th layer (separation layer) 0.8 g gelatin 0.05 g 2,5-di-t-pentadecyl hydroquinone 0.05 g Tricresyl phosphate 0.05 g Dibutyl phthalate 5th layer (low green sensitive layer) 1.8 g AgNO₃ a spectrally green-sensitized Ag (Br, J) emulsion, 4.35 mol% iodide, average grain diameter 0.36 µm 1.6 g gelatin 0.45 g colorless coupler M 2 0.05 g DIR coupler DIR-2 0.12 g colored coupler YM 1 0.52 g Tricresyl phosphate 6th layer (yellow filter layer ) 0.02 g yellow colloidal silver, passivated by 6 mg 1-phenyl-5-mercaptotetrazole / g AgNO₃ 0.8 g gelatin 0.15 g 2,5-di-t-pentadecyl hydroquinone 7th layer (low blue-sensitive layer) 0.65 g a spectrally blue-sensitized Ag (Br, J) emulsion, 4.35 mol% iodide, average grain diameter 0.43 µm 1.95 g gelatin 0.85 g colorless coupler Y1 0.15 g DIR coupler DIR 3 0.90 g Tricresyl phosphate

8th layer (separation layer)

like 4th layer 9th layer (highly red-sensitive layer) 2.2 g AgNO₃ of the spectrally red-sensitized Ag (Br, J) emulsion, 6.3 mol% iodide, average grain diameter 0.82 µm, provided with the additives according to the invention or the comparative additives according to Table 2, 1.2 g gelatin 0.20 g colorless coupler C 2 0.01 g DIR coupler DIR-2 0.02 g colored coupler RM 1 0.15 g Tricresyl phosphate 0.10 g Dibutyl phthalate

10th layer (separating layer)

like 4th layer

12th layer (yellow filter layer )

like 6th layer

Tabelle 2 Schicht-Aufbau Zusatz Empfindlichkeit Art mMol auf 1 Mol AgNO₃ zur: bg pp gb 9.Schicht 11.Schicht 13.Schicht Vergleich H ohne - - - 26,2 26,4 27,0 Vergleich A Vergleichssubstanz 0,03 0,04 0,05 26,4 26,7 27,2 Erfindung B 15 0,03 0,04 0,05 27,8 28,0 29,2 Erfindung C 22 0,02 0,02 0,03 28,0 28,5 29,1 Erfindung D 23 0,03 0,04 0,04 28,2 28,5 29,0 Erfindung E 24 0,02 0,02 0,03 28,3 28,7 29,2 Erfindung F 25 0,03 0,03 0,03 28,1 28,6 29,4 Erfindung G 26 0,02 0,03 0,05 27,8 28,9 28,8 Substances used in example 2:

Table 2 Layer structure additive sensitivity Art mmol to 1 mol AgNO₃ for: bg pp gb 9th shift 11th shift 13.Layer comparison H without - - - 26.2 26.4 27.0 comparison A Reference substance 0.03 0.04 0.05 26.4 26.7 27.2 invention B 15 0.03 0.04 0.05 27.8 28.0 29.2 invention C. 22 0.02 0.02 0.03 28.0 28.5 29.1 invention D 23 0.03 0.04 0.04 28.2 28.5 29.0 invention E 24th 0.02 0.02 0.03 28.3 28.7 29.2 invention F 25th 0.03 0.03 0.03 28.1 28.6 29.4 invention G 26 0.02 0.03 0.05 27.8 28.9 28.8

Claims (7)

1. Color negative silver halide photographic material in which at least one silver halide emulsion layer is a compound of the formula
A― (Z) _n ―S * (I)
contains adsorbed on the silver halide grain,
where A is a grain-active adhesion group of formulas IIa to IId:

wherein
Z₁ the remaining members to complete a preferably 5- or 6-membered ring which contains at least one further heteroatom such as a nitrogen or sulfur atom and is optionally benzo- or naphtho-condensed,
Z₂ the remaining members to complete a preferably 5- or 6-membered ring which is optionally benzo- or naphtho-condensed,
X -NH₂, -NHR,

-NH-NH₂, -NH-NHR, -SR,
Y -S-, -NH-, -NR-,
B, D is hydrogen, R or together the remaining members of a 5- or 6-membered ring,
R is an aliphatic, aromatic or heterocyclic radical,
Z is a divalent intermediate element,
S * a latent group of fogging agents, which becomes an active fogging agent (S) during color development, and
n is 0 or 1. 2. Color photographic silver halide material according to claim 1, characterized in that
Z alkylene, arylene, -COCH₂-, -COCH₂-S-, -COCH₂O-,

S * a rest of the formulas

in which
in formula IIIc one of the radicals R₅, R₆, R₇ or R₈ is the point of attachment for the radical A- (Z) _n -,
R₁ is hydrogen, halogen, alkyl, alkoxy,
R₂ is an acyl group, for example -CHO-, -COR₉, -COOR₉, -CONH₂, -CONHR₉, -SO₂R₉, -PO (R₉) ₂, -PO (OR₉) ₂,
R₃ is hydrogen, halogen, alkyl, alkoxy,
R₄ is hydrogen, halogen, alkyl, alkoxy, acylamino, nitro or sulfonyl,
R₅ hydrogen, -CONHR₉, -NHCOR₉, -SO₂NHR₉, -NHCOOR₉, -NHSO₂R₉, -NHCONHR₉,
R₆ is hydrogen or alkyl,
R₇ is hydrogen or acyl such as -COR₉, -COOR₉, -CONHR₉, SO₂NHR₃ or
R₆ and R₇ together the remaining members of a heterocyclic ring or together with the Nitrogen atom an azomething group

R₈ is hydrogen, alkoxy or acylamino,
R₈ and R₆ together are the remaining members of a heterocyclic ring that is condensed with the naphthol ring,
R₉ is an optionally substituted aliphatic or olefinic, cycloaliphatic or cycloolefinic, aromatic or heterocyclic group,
R₁₀ hydrogen, alkyl, aryl,
R₁₁ alkyl, aryl or hetaryl and
L is a divalent group containing a -CO group linked to the hydrazine group,
mean. 3. Color photographic silver halide material according to claim 1, characterized in that the compound I corresponds to the formula (IV)

wherein
L₁ C₁-C₆ alkylene,
L₂ is a sulfur atom,
R₁₂ is a heterocyclic radical,
p 0 or 1 and
q is 0 or 1. 4. Color photographic silver halide material according to claim 1, characterized in that the compound I of the silver halide emulsion is added after the spectral sensitization in an amount of 0.005 to 1 mmol / mol AgNO₃. 5. Color photographic silver halide material according to claim 1, characterized in that it contains layers of the same spectral sensitization but different sensitivity, the compound of formula (I) being in the most sensitive layer. 6. A color photographic material as claimed in claim 1, which has at least one red-sensitive layer containing at least one cyan coupler, at least one green-sensitive layer containing at least one magenta coupler and at least one blue-sensitive layer containing a yellow coupler. 7. The color photographic material as claimed in claim 6, which contains at least two red-sensitive, at least two green-sensitive and at least two blue-sensitive layers, all highly sensitive layers containing a compound of the formula (I).