EP0373339B1 - Silver halide recording material - Google Patents

Description

The invention relates to a silver halide recording material with improved latent image stabilization.

When a silver halide photographic material is exposed, a latent image is initially formed, which is developed into a visible silver image by the developer during development. There are often longer periods between exposure and development in which the latent image is broken down again. The result is unsatisfactory recordings.

For this reason, so-called latent image stabilizers are added to the photographic materials, which are intended to prevent the latent image from degrading over long periods of time.

Examples of compounds which are intended to act as latent image stabilizers are, for example, in GB 1 308 777, DE 2 325 039, 2 335 093, 2 304 322, 3 308 203, JA 50/94918, 57/100 424, JP 116 167, GB 1 458 197 and US 4,334,014 and 4,378,426.

The known compounds, which are intended to stabilize the latent image of photographic emulsions, have the disadvantage that, depending on the amount added per mole of silver halide (and depending on the pH and pAg of the emulsion layer) when the exposed emulsion is stored, either the decrease in the latent image is insufficient slow down or stabilize the latent image to a satisfactory extent, but at the same time cause the fog of the photographic emulsion to increase to an increased extent during storage.

Furthermore, compounds of the following formula II are known as latent image stabilizers from EP-A-234 392. However, their effect is insufficient.

It is known to add anti-fogging agents to the emulsions in addition to the latent image stabilizers mentioned above, e.g. 5-methyl-benzotriazole, 1-phenyl-5-mercapto-tetrazole, 2,5-dimercapto-1,3,4-thiadiazole etc. Such antifoggants are able to inhibit the increase in fog caused by the latent image stabilizers during storage, without breaking latent image stabilization.

However, a disadvantage of this latent image stabilization method is that the antifoggants have to be added in amounts which significantly reduce the sensitivity of the emulsion.

The object of the invention was therefore to find measures to effectively stabilize the latent image and at the same time to minimize the increase in fog and loss of sensitivity.

The object is achieved in that the silver halide emulsions of the photographic material are each added at least one compound from at least two different classes of substances specified below.

• A) Verbindungen der allgemeinen Formel I
  
  worin

  R₁

  Wasserstoff; Alkyl mit bis zu 9 C-Atomen, das beispielsweise durch Chlor, Brom, Fluor, Cyan, Hydroxy, Alkoxy wie Methoxy, Alkylthio, Carboxy, Alkoxycarbonyl, Carbonamido substituiert sein kann; Aryl wie Phenyl; Aralkyl wie Benzyl; Cycloalkyl wie Cyclohexyl; oder einen Heterocyclus wie Furyl, Thienyl, Pyridyl;

  R₂

  Wasserstoff; Alkyl, das substituiert oder unsubstituiert sein kann, Alkenyl wie Allyl; Aryl wie Phenyl; oder -NR₄R₅;

  R₃

  Wasserstoff oder eine bei der Entwicklung abspaltbare Gruppe wie -COR₉ oder COOR₁₀;

  R₄, R₅

  R₁ oder -COR₆, -CONHR₇ oder -COOR₈;

  R₆

  Alkyl oder Cycloalkyl mit bis zu 8 C-Atomen, das substituiert oder unsubstituiert sein kann, beispielsweise Methyl, Butyl, Cyclohexyl, Methoxymethyl und Methylmercaptomethyl; Allyl; Benzyl; Aryl wie Phenyl, 4-Chlorphenyl, 4-Sulfophenyl;

  R₇

  Wasserstoff oder R₆;

  R₈, R₉, R₁₀

  Alkyl oder Cycloalkyl, das substituiert oder unsubstituiert sein kann, mit bis zu 8 C-Atomen wie Methyl, Ethyl und Isopropyl; Aryl wie Phenyl bedeuten;

• B) Verbindungen der allgemeinen Formel II
  
  oder Tautomeren davon, worin

  Z

  die zur Vervollständigung eines Oxazol- oder Oxazinringes erforderlichen Atome und

  Y

  ein ankondensiertes aromatisches Ringsystem mit mindestens einem aromatischen Ring, das mit wenigstens einer sauren Gruppe substituiert ist, bedeuten;

• C) Verbindungen der allgemeinen Formel (III)
  
  worin

  R₁₁, R₁₂

  gleich oder verschieden sind und Wasserstoff, C₁-C₃-Alkyl wie Methyl und Ethyl

  R₁₃, R₁₄

  gleich oder verschieden sind und Wasserstoff, C₁-C₆-Alkyl, wie Methyl und Ethyl; Cycloalkyl wie Cyclohexyl; Aryl wie Phenyl, einen Heterocyclus wie Furyl oder Thienyl, Carboxyl oder Aminocarbonyl und

  n

  1 oder 2 bedeuten; und

• D) Verbindungen der allgemeinen Formal IV
  
  worin

  R₁₅

  Wasserstoff, C₁-C₈-Alkyl, das substituiert oder unsubstituiert sein kann wie Methyl, Ethyl, Isopropyl, Methoxymethyl, Chlorethyl, Cyanethyl, Methylthiomethyl und Carboxymethyl; Allyl; Benzyl; eine Gruppe der Formeln -COR₂₀, -COOR₂₁ oder

  

  R₁₆, R₁₇

  Wasserstoff oder C₁-C₃-Alkyl,

  R₁₈

  Wasserstoff, -COR₂₂, -CONHR₂₃;

  R₁₉

  Wasserstoff oder C₁-C₁₀-Alkyl,

  R₂₀,R₂₁,R₂₂

  Alkyl oder Cycloalkyl mit bis zu 8 C-Atomen, das substituiert sein kann wie Methyl, Ethyl, Cyclohexyl oder Benzyl; Allyl; Aryl wie Phenyl,

  R₂₃

  Wasserstoff oder R₂₀

  X

  eine direkte Bindung oder Alkylen mit bis zu 6 C-Atomen und

  m

  0 oder 1 bedeuten.

The invention therefore relates to a light-sensitive silver halide material with a support and at least one light-sensitive silver halide emulsion layer, the emulsion of which contains at least one compound from at least two of the compound classes A, B, C and D listed below in an effective amount.

• A) Compounds of the general formula I.
  
  wherein

  R₁

  Hydrogen; Alkyl with up to 9 carbon atoms, which can be substituted, for example, by chlorine, bromine, fluorine, cyano, hydroxy, alkoxy such as methoxy, alkylthio, carboxy, alkoxycarbonyl, carbonamido; Aryl such as phenyl; Aralkyl such as benzyl; Cycloalkyl such as cyclohexyl; or a heterocycle such as furyl, thienyl, pyridyl;

  R₂

  Hydrogen; Alkyl, which may be substituted or unsubstituted, alkenyl such as allyl; Aryl such as phenyl; or -NR₄R₅;

  R₃

  Hydrogen or a group which can be split off during development, such as -COR₉ or COOR₁₀;

  R₄, R₅

  R₁ or -COR₆, -CONHR₇ or -COOR₈;

  R₆

  Alkyl or cycloalkyl with up to 8 carbon atoms, which can be substituted or unsubstituted, for example methyl, butyl, cyclohexyl, methoxymethyl and methyl mercaptomethyl; Allyl; Benzyl; Aryl such as phenyl, 4-chlorophenyl, 4-sulfophenyl;

  R₇

  Hydrogen or R₆;

  R₈, R₉, R₁₀

  Alkyl or cycloalkyl, which can be substituted or unsubstituted, with up to 8 carbon atoms, such as methyl, ethyl and isopropyl; Mean aryl such as phenyl;

• B) Compounds of the general formula II
  
  or tautomers thereof, wherein

  Z.

  the atoms required to complete an oxazole or oxazine ring and

  Y

  is a fused aromatic ring system having at least one aromatic ring substituted with at least one acidic group;

• C) compounds of the general formula (III)
  
  wherein

  R₁₁, R₁₂

  are identical or different and are hydrogen, C₁-C₃-alkyl such as methyl and ethyl

  R₁₃, R₁₄

  are identical or different and are hydrogen, C₁-C₆-alkyl, such as methyl and ethyl; Cycloalkyl such as cyclohexyl; Aryl such as phenyl, a heterocycle such as furyl or thienyl, carboxyl or aminocarbonyl and

  n

  1 or 2; and

• D) Compounds of the general Formal IV
  
  wherein

  R₁₅

  Hydrogen, C₁-C₈-alkyl, which may be substituted or unsubstituted such as methyl, ethyl, isopropyl, methoxymethyl, chloroethyl, cyanoethyl, methylthiomethyl and carboxymethyl; Allyl; Benzyl; a group of the formulas -COR₂₀, -COOR₂₁ or

  

  R₁₆, R₁₇

  Hydrogen or C₁-C₃-alkyl,

  R₁₈

  Hydrogen, -COR₂₂, -CONHR₂₃;

  R₁₉

  Hydrogen or C₁-C₁₀ alkyl,

  R₂₀, R₂₁, R₂₂

  Alkyl or cycloalkyl with up to 8 carbon atoms, which can be substituted such as methyl, ethyl, cyclohexyl or benzyl; Allyl; Aryl such as phenyl,

  R₂₃

  Hydrogen or R₂₀

  X

  a direct bond or alkylene with up to 6 carbon atoms and

  m

  0 or 1 mean.

R₁

Wasserstoff, C₁-C₉-Alkyl, unsubstituiert oder durch C₁-C₄-Alkoxy, Carboxy, Hydroxy, Halogen, C₁-C₄-Alkoxycarbonyl, C₁-C₄-Alkylcarbonyloxy oder Phenoxy substituiert, Phenyl, unsubstituiert oder durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen substituiert, Cyclohexyl, Benzyl, Pyridyl oder Furyl,

R₂

Wasserstoff, gegebenenfalls durch Carboxy, C₁-C₄-Alkoxycarbonyl oder 1-Piperidino substituiertes C₁-C₄-Alkyl, Allyl, Phenyl oder -NR₄R₅,

R₃

Wasserstoff, C₁-C₄-Alkylcarboyl oder C₁-C₆-Alkoxycarbonyl,

R₄

Wasserstoff, C₁-C₄-Alkylcarbonyl, Hydroxyethyl, C₁-C₄-Alkylaminocarbonyl, Cyclohexylaminocarbonyl, Sulfophenyl, Sulfophenylcarbonyl, Methylthioacetyl oder C₁-C₄-Alkoxycarbonyl,

R₅

Wasserstoff, C₁-C₄-Alkylcarbonyl oder C₁-C₄-Alkoxycarbonyl;

für B die Formel V

worin

R₂₄ bis R₂₇

gleich oder verschieden, Wasserstoff oder Alkyl, insbesondere mit 1 bis 4 C-Atomen, und wobei zwei der Substituenten R₂₄-R₂₇ zusammen den Rest zur Vervollständigung eines Ringes, insbesondere eines ankondensierten Phenylringes bedeuten können, mit der Maßgabe, daß wenigstens einer der Substituenten R₂₄-R₂₇ einen sauren Substituenten enthält oder ein saurer Substituent ist;

R₁₁ und R₁₂

unabhängig voneinander Wasserstoff oder Methyl,

R₁₃

Wasserstoff oder Methyl,

R₁₄

Wasserstoff, Methyl, Furyl, Methylfuryl, Thienyl, Bromthienyl, Cyclohexyl, Phenyl, Carboxy oder Aminocarbonyl,

n

1 oder 2,

R₁₅

Wasserstoff, C₁-C₄-Alkyl, Carboxy-C₁-C₄-alkyl, Allyl, C₁-C₄-Alkoxycarbonyl, Benzyl oder

R₁₆

Wasserstoff,

R₁₇

Wasserstoff oder Methyl,

R₁₈

C₁-C₄-Alkylcarbonyl, Aminocarbonyl,

R₁₉

Wasserstoff oder C₁-C₁₀-Alkyl,

X

eine direkte Bindung oder C₂-C₄-Alkylen und

m

0 oder 1.

The following substituent meanings or formula apply to preferred compounds A, B, C and D:

R₁

Hydrogen, C₁-C₉-alkyl, unsubstituted or substituted by C₁-C₄-alkoxy, carboxy, hydroxy, halogen, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyloxy or phenoxy, phenyl, unsubstituted or by C₁-C₄-alkyl, C₁ -C₄-alkoxy or halogen substituted, cyclohexyl, benzyl, pyridyl or furyl,

R₂

Hydrogen, optionally substituted by carboxy, C₁-C₄-alkoxycarbonyl or 1-piperidino, C₁-C₄-alkyl, allyl, phenyl or -NR₄R₅,

R₃

Hydrogen, C₁-C₄-alkylcarboyl or C₁-C₆-alkoxycarbonyl,

R₄

Hydrogen, C₁-C₄-alkylcarbonyl, hydroxyethyl, C₁-C₄-alkylaminocarbonyl, cyclohexylaminocarbonyl, sulfophenyl, sulfophenylcarbonyl, methylthioacetyl or C₁-C₄-alkoxycarbonyl,

R₅

Hydrogen, C₁-C₄ alkylcarbonyl or C₁-C₄ alkoxycarbonyl;

for B the formula V

wherein

R₂₄ to R₂₇

the same or different, hydrogen or alkyl, in particular with 1 to 4 carbon atoms, and where two of the substituents R₂₄-R₂₇ together can represent the remainder of a ring, in particular a fused phenyl ring, with the proviso that at least one of the substituents R₂₄ -R₂₇ contains an acidic substituent or is an acidic substituent;

R₁₁ and R₁₂

independently of one another hydrogen or methyl,

R₁₃

Hydrogen or methyl,

R₁₄

Hydrogen, methyl, furyl, methylfuryl, thienyl, bromthienyl, cyclohexyl, phenyl, carboxy or aminocarbonyl,

n

1 or 2,

R₁₅

Hydrogen, C₁-C₄-alkyl, carboxy-C₁-C₄-alkyl, allyl, C₁-C₄-alkoxycarbonyl, benzyl or

R₁₆

Hydrogen,

R₁₇

Hydrogen or methyl,

R₁₈

C₁-C₄ alkylcarbonyl, aminocarbonyl,

R₁₉

Hydrogen or C₁-C₁₀ alkyl,

X

a direct bond or C₂-C₄ alkylene and

m

0 or 1.

Examples of compounds of formula 1 are:

Heterocyclic systems of the formula II are, for example, benzoxazole, naphtha [1,2: d] oxazole, naphtha [2,3: d] oxazole, naphtha [2,1: d] oxazole, oxazine, naphtha [1,8: de] oxazine . The oxazole or oxazine rings contain substituents with acidic groups or fused aromatic rings with preferably attached acidic groups, examples of acidic groups are -COOH and -SO₃H groups.

The compounds of the formula II can be further substituted by halogen atoms, alkyl, ether and ester groups.

Examples of compounds of the formulas II and V are:

• B-1 2-Mercapto-8-sulfonaphth [1,2-d] oxazole
• B-2 2-mercapto-7-sulfonaphth [2,3-d] oxazole
• B-3 2-mercapto-5-sulfonaphth [2,1-d] oxazole
• B-4 2-mercapto-6-sulfonaphth [1,2-d] oxazole
• B-5 2-mercapto-8-sulfonaphth [1,8-de] oxazine
• B-6 2-mercapto-5,8-disulfonaphth [1,8-de] oxazine
• B-7 2-mercapto-5,7-disulfonaphth [2,3-d] oxazole
• B-8 2-mercapto-5-chloro-7-sulfobenzoxazole
• B-9 2-mercapto-5-sulfobenzoxazole
• B-10 2-mercapto-5-sulfo-7-chlorobenzoxazole
• B-11 2-mercapto-5-carboxybenzoxazole
• B-12 2-mercapto-7-carboxybenzoxazole
• B-13 2-mercapto-5-aminosulfonylbenzoxazole
• B-14 2-mercapto-7-aminosulfonylbenzoxazole
• B-15 2-mercapto-5-methyl-7-sulfobenzoxazole

Examples of compounds of the formula III are

• C-1 4-carboxythiazolidine
• C-2 4-Carboxy-5,5-dimethylthiazolidine
• C-3 2,2-dimethyl-4-carboxythiazolidine
• C-4 2- (2-furyl) -4-carboxythiazolidine
• C-5 2- (2-thienyl) -4-carboxythiazolidine
• C-6 2-Cyclohexyl-4-carboxythiazolidine
• C-7 2- (2-thienyl) -4-carboxy-5,5-dimethylthiazolidine
• C-8 2- (5-Methylfuryl-2) -4-carboxythiazolidine
• C-9 2- (5-bromothienyl-2) -4-carboxythiazolidine
• C-10 2-phenyl-4-carboxythiazolidine
• C-11 3-aza-4-carboxythian, hydrochloride
• C-12 2-methyl-2,4-dicarboxythiazolidine
• C-13 2-methyl-2-aminocarbonyl-4-carboxythiazolidine
• C-14 2- (3-thienyl) -4-carboxythiazolidine

Examples of compounds of the formula IV are:

• D-1 Cystein
• D-2 2-Amino-4-mercaptobuttersäure
• D-3 S-Methylcystein
• D-4 Cysteinoctylesterhydrochlorid
• D-5 N-Aminocarbonylcystein
• D-6 S-Carboxymethylcystein
• D-7 S-(2-Carboxyethyl)-cystein
• D-8 S-Ethylcystein
• D-9 N-Anilinocarbonylcystein
• D-10 S-Allylcystein
• D-11 2-Amino-3-methyl-3-mercaptobuttersäure
• D-12 N-Acetylcystein
• D-13 Cysteinmethylesterhydrochlorid
• D-14 Di-S-cysteino-1,3-propan
• D-15 N-Benzoylcystein
• D-16 Methionin
• D-17 N-Acetyl-S-methylcystein
• D-18 N-Acetyl-S-methyl-cysteinmethylester
• D-19 S-Methoxycarbonylcystein
• D-20 S-Benzylcystein
• D-21 Cystin
• D-22 Di-S-cysteino-1,2-ethan

Es ist günstig, die erfindungsgemäßen Verbindungen in Form von Lösungen zuzusetzen. Geeignet als Lösungsmittel sind beispielsweise niedere Alkohole, Tetrahydrofuran, N-Methylpyrrolidon oder Aceton, soweit die erfindungsgemäßen Verbindungen nicht in Wasser löslich sind. Die erfindungsgemäß zu verwendenden Verbindungen der Klassen A und B werden vorzugsweise in Mengen von 10⁻⁵ bis 10⁻², vorzugsweise insbesondere von 3.10⁻⁵ bis 10⁻³ Mol pro Mol Silberhalogenid eingesetzt, die Verbindungen der Klassen C und D vorzugsweise in Mengen von 10⁻⁶ bis 10⁻³, vorzugsweise insbesondere in Mengen von 3.10⁻⁶ bis 3.10⁻⁴ Mol pro Mol Silberhalogenid.

• D-1 cysteine
• D-2 2-amino-4-mercaptobutyric acid
• D-3 S-methylcysteine
• D-4 cysteine octyl ester hydrochloride
• D-5 N-aminocarbonylcysteine
• D-6 S-carboxymethylcysteine
• D-7 S- (2-carboxyethyl) cysteine
• D-8 S-ethyl cysteine
• D-9 N-anilinocarbonylcysteine
• D-10 S allyl cysteine
• D-11 2-Amino-3-methyl-3-mercapto butyric acid
• D-12 N-acetylcysteine
• D-13 cysteine methyl ester hydrochloride
• D-14 Di-S-cysteino-1,3-propane
• D-15 N-benzoylcysteine
• D-16 methionine
• D-17 N-acetyl-S-methylcysteine
• D-18 N-acetyl-S-methyl-cysteine methyl ester
• D-19 S-methoxycarbonylcysteine
• D-20 S-benzylcysteine
• D-21 cystine
• D-22 Di-S-cysteino-1,2-ethane

It is advantageous to add the compounds according to the invention in the form of solutions. Suitable solvents are, for example, lower alcohols, tetrahydrofuran, N-methylpyrrolidone or acetone if the compounds according to the invention are not soluble in water. The compounds of classes A and B to be used according to the invention are preferably used in amounts of 10⁻⁵ to 10⁻², preferably in particular 3.10⁻⁵ to 10⁻³ mol per mole of silver halide, the compounds of classes C and D preferably in amounts of 10⁻⁶ to 10⁻³, preferably in particular in amounts of 3.10⁻⁶ to 3.10⁻⁴ mol per mol of silver halide.

In combination with the stabilizers according to the invention, the emulsions can contain further antifoggants and stabilizers. Azaindenes are particularly suitable, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are described, for example, in the article by Birr, Z. Wiss. Phot. 47 , (1952), pp. 2-58.

Additional stabilizers and antifoggants, such as those listed in Research Disclosure No. 17643 of December 1978, Section VI, published by Industrial Opportunities Ltd., Homewell Havant, Hampshire, PO9 1 EF in Great Britain, can be added insofar as they are do not interfere with the action according to the invention of the compounds of classes A, B, C and D.

The silver halide recording material according to the invention can be a black and white or a color photographic material.

Examples of color photographic materials are 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.

Suitable supports for the production of color photographic materials are e.g. Films and foils of semi-synthetic 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 (e.g. 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, sugar, 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. It can also oxidized gelatin can be used. The preparation of such gelatins is described, for example, in The Science and Technology of Gelatine, edited by AG 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 with a high chloride content are used up to pure silver chloride emulsions. 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, 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, where the ratio of diameter to thickness is much greater than 5: 1, e.g. 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 Emulsion, 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 take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less 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 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 that act as supersensitizers.

• 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 in the 5- and / or 6-position can be substituted 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:

R₂ = H

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 des gelben Teilfarbenbildes sind in der Regel Kuppler mit einer offenkettigen Ketomethylengruppierung, insbesondere Kuppler vom Typ des α-Acylacetemids; 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:

R₂ = H

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 generating the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the α-acylacetemide 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 or. FAR coupler.

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 be schrieben.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 an easily diffusible development inhibitor, suitable measures can be taken to improve the 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-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 (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 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.

With a suitably low intrinsic sensitivity of the green or Red-sensitive layers can be selected without the yellow filter layer, other layer arrangements 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 e.g. 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, 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 (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).

R =

t-C₈H₁₇; R₁ = CH₃

R =

n-C₈H₁₇; R₁ = i-C₃H₇

R, R₁ =

t-C₄H₉

R, R₁ =

t-C₅H₁₁

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

R =

t-C₈H₁₇; R₁ = CH₃

R =

n-C₈H₁₇; R₁ = i-C₃H₇

R, R₁ =

t-C₄H₉

R, R₁ =

t-C₅H₁₁

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 immediately after casting, at the latest after 24 hours, preferably after 8 hours at the latest, so 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.

• (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, which contain at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfone-amidoethyl) -3-methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine. Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 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

Anschließend wurden 2,0 mmol 6-Methyl-4-hydroxy-1,3,3a,7-tetraazainden/molAg zugesetzt, um die Emulsion zu stabilisieren. Die Emulsion wurde aufgeteilt.A cubic silver chloride bromide iodide emulsion with 3 mol% chloride and 4.5 mol% iodide, in which the diameters of the spheres equal in volume to the emulsion grains were 90%> 0.40 µm and 90% <0.87 µm and the most common occurring diameter was 0.58 µm, 8.4 µmol sodium thiosulfate / molAg, 6.3 µmol sodium dithiosulfato-aurate (I) / molAg and 441 µmol ammonium thiocyanate / molAg were ripened at 58 ° C for two hours and 0.188 µmol / MolAg des Dye I and 0.325 µmol / MolAg of dye II spectrally sensitized.

Then 2.0 mmol of 6-methyl-4-hydroxy-1,3,3a, 7-tetraazaindene / molAg were added in order to stabilize the emulsion. The emulsion was divided.

Various portions of this emulsion were mixed with latent image stabilizers in accordance with Table 1, Experiments Nos. 1 to 8. These portions were each brought to a gelatin content of 221 g gelatin / molAg by gelatin addition, adjusted to pH 6.7 and pAg 9.0, applied to a transparent layer support (silver application 32 mmolAg / m²) and hardened by means of a protective layer.

The film samples were exposed in a sensitometer behind a ³√2 step gray wedge, the development at 20 ° C in a commercially available black and white developer (refinal) for 16 minutes. A sample was freshly processed (= not stored, within 6 hours after exposure) to determine the positional behavior; a second sample was exposed, then stored for 14 days at 57 ° C. and 35% relative humidity and then processed; A third sample was stored at 57 ° C. and 35% relative humidity for 14 days before exposure, then exposed and processed within 6 hours after exposure. Table 1 shows that the compounds A-3, A-4, A-23 and B-8 individually have a more or less stabilizing effect on the latent image, but significantly reduce the sensitivity of the fresh material. If one stabilizes the latent image with two compounds, one of which belongs to compound class A and the other to compound class B, the sensitivity is always higher, although on the entire amount of latent image stabilizer nothing was changed per mole of silver halide (namely 600 µmol / molAg).

Example 2

The experiments listed in Table 2 were carried out with a compound from compound class C using the emulsion given in Example 1.

The latent image stabilizations with the combinations of a compound of the compound classes A and C each show a higher sensitivity than the latent image stabilizations with the respective compounds of the compound class A alone, as a comparison with Table 1 shows; latent image stabilization with C-4 alone is weaker than with A-3, A-4, A-23 or B-8 alone and leads to higher fog at the same time.

The three-combination of a connection of the connection classes A, B, and C provides somewhat higher sensitivities than the two-combination, while the stabilization of the latent image is retained.

Example 3

The results shown in Table 3 are obtained with a compound from compound class D and the emulsion given in Example 1. Analogously to Example 2, it is found that it is advantageous not to use a compound with a latent image stabilizing effect individually, but for combinations of compounds from two different classes of compounds (A + D or B + D) or from three different classes of compounds (A + B + D).

Claims (4)

1. A photosensitive silver halide material comprising a support and at least one photosensitive silver halide emulsion layer, of which the emulsion contains an effective quantity of at least one compound of each of at least two of the classes A, B, C and D defined hereinafter:

   A) compounds corresponding to the general formula:

   

   in which

   R₁   is hydrogen; alkyl containing up to 9 carbon atoms which may be substituted, aryl, aralkyl, cycloalkyl or a heterocycle;

   R₂   represents hydrogen, alkyl which may be substituted or unsubstituted, alkenyl, aryl or -NR₄R₅;

   R₃   represents hydrogen or a group releasable during development;

   R₄ and R₅   have the same meaning as R₁ or represent -COR₆, -CONHR₇ or -COOR₈;

   R₆   represents alkyl or cycloalkyl containing up to 8 carbon atoms, which may be substituted or unsubstituted, allyl; benzyl or aryl;

   R₇   represents hydrogen or R₆;

   R₈   represents alkyl or cycloalkyl, which may be substituted or unsubstituted, containing up to 8 carbon atoms or aryl;

   B) compounds corresponding to the general formula:

   

   or tautomers thereof,
   in which

   Z   represents the atoms required to complete an oxazole or oxazine ring and

   Y   represents a fused aromatic ring system comprising at least one aromatic ring substituted by at least one acidic group;

   C) compounds corresponding to the general formula:

   

   in which

   R₁₁ and R₁₂   may be the same or different and represent hydrogen or C₁₋₃ alkyl;

   R₁₃ and R₁₄   may be the same or different and represent hydrogen, C₁₋₆ alkyl, cycloalkyl, aryl, a heterocycle, carboxyl or aminocarbonyl;

   n =   1 or 2; and

   D) compounds corresponding to the general formula:

   

   in which

   R₁₅   represents hydrogen, C₁₋₈ alkyl, which may be substituted or unsubstituted, allyl, benzyl, a group corresponding to the formulae -COR₂₀, -COOR₂₁ or

   

   R₁₆ and R₁₇   represent hydrogen or C₁₋₃ alkyl,

   R₁₈   represents hydrogen, -COR₂₂, -CONHR₂₃,

   R₁₉   represents hydrogen, C₁₋₁₀ alkyl,

   R₂₀, R₂₁ and R₂₂   represent alkyl or cycloalkyl containing up to 8 carbon atoms, which may be substituted, allyl or aryl;

   R₂₃   is hydrogen or R₂₀,

   X   is a direct bond or alkylene containing up to 6 carbon atoms and

   m =   0 or 1.
2. A photosensitive silver halide material as claimed in claim 1, in which in the compounds A

   R₁   is hydrogen, C₁₋₉ alkyl, unsubstituted or substituted by C₁₋₄ alkoxy, carboxy, hydroxy, halogen, C₁₋₄ alkoxycarbonyl, C₁₋₄ alkyl carbonyloxy or phenoxy; phenyl unsubstituted or substituted by C₁₋₄ alkyl, C₁₋₄ alkoxy or halogen; cyclohexyl, benzyl, pyridyl or furyl,

   R₂   is hydrogen, C₁₋₄ alkyl optionally substituted by carboxy, C₁₋₄ alkoxycarbonyl or 1-piperidino; allyl, phenyl or -NR₄R₅,

   R₃   is hydrogen, C₁₋₄ alkylcarbonyl or C₁₋₆ alkoxycarbonyl,

   R₄   is hydrogen, C₁₋₄ alkylcarbonyl, hydroxyethyl, C₁₋₄ alkylaminocarbonyl, cyclohexylaminocarbonyl, sulfophenyl, sulfophenylcarbonyl, methyl thioacetyl or C₁₋₄ alkoxycarbonyl,

   R₅   is hydrogen, C₁₋₄ alkylcarbonyl or C₁₋₄ alkoxycarbonyl;

   the compounds B correspond to the formula:

   

   in which

   R₂₄ to R₂₇   may be the same or different and represent hydrogen or alkyl; two of the substituents R₂₄ to R₂₇ together may represent the atoms required to complete a ring, with the proviso that at least one of the substituents R₂₄ to R₂₇ contains an acidic substituent or is an acidic substituent;

   in the compounds C

   R₁₁ and R₁₂   independently of one another represent hydrogen or methyl,

   R₁₃   represents hydrogen or methyl,

   R₁₄   represents hydrogen, methyl, furyl, methyl furyl, thienyl, bromothienyl, cyclohexyl, phenyl, carboxy or aminocarbonyl,

   n =   1 or 2,

   in the compounds D

   R₁₅   represents hydrogen, C₁₋₄ alkyl, carboxy-C₁₋₄-alkyl, ally], C₁₋₄ alkoxycarbonyl, benzyl or

   

   R₁₆   represents hydrogen,

   R₁₇   represents hydrogen or methyl,

   R₁₈   represents C₁₋₄ alkylcarbonyl, aminocarbonyl,

   R₁₉   represents hydrogen or C₁₋₁₀ alkyl,

   X   represents a direct bond or C₂₋₄ alkylene and

   m =   0 or 1.
3. A photosensitive silver halide material as claimed in claim 1, characterized in that 10⁻⁵ to 10⁻² mol of compound class A, 10⁻⁵ to 10⁻² mol compound class B, 10⁻⁶ to 10⁻³ mol compound class C and 10⁻⁶ to 10⁻³ mol compound class D are used per mol silver halide.
4. A photosensitive silver halide material as claimed in claim 1, characterized in that it is a color photographic silver halide material comprising a support, at least one red-sensitive layer with which a cyan coupler is associated, at least one green-sensitive layer with which a magenta coupler is associated and at least one blue-sensitive layer with which a yellow coupler is associated.