EP0370226B1 - Photographic silver halide material, and method of processing it - Google Patents

Description

The invention relates to a photographic silver halide material comprising a support, at least one light-sensitive silver halide emulsion layer applied to the support, a hardening layer and optionally further light-sensitive and light-insensitive layers, which shows a reduction in dirt acceptance during processing.

From EP-A-259 855 it is known to process photographic materials, in particular X-ray materials in automatically working processing machines, which contain an organic compound in one layer, in particular the gelatin-containing protective layer, for example polyacrylamide, sucrose or dextran, of which at least 10% by weight. -% are washed out during processing. This measure is intended to speed up drying, scratch resistance and sensitivity the material is improved and the residual staining is reduced by the sensitizer.

The production of such a material, in particular the hardening, presents difficulties, the dirt acceptance of the surface is not reduced compared to a material without the addition of the high-molecular organic substances.

It was an object of the present invention to provide a photographic, in particular a color photographic, silver halide material which is distinguished by a particularly low level of dirt acceptance during processing.

Research Disclosure 13 433 discloses using immediate hardeners together with polystyrene sulfonic acid in a top layer. FR-A-2 267 569 describes the use of certain cellulose sulfates together with instant hardeners in a top layer. These combinations are intended to achieve other tasks than the present invention.

• a) einen Härter der Formel
  
  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; (Soforthärter)

• (b) ein wasserlösliches, mit der Härtersubstanz praktisch nicht reagierendes Verdickungsmittel, wobei als Verdickungsmittel Polyacrylamid, Polymethacrylsäure- und Polyacrylsäuresalze, Copolymerisate aus Acrylamid und Methacylsäure- bzw. Acrylsäuresalzen, Copolymere aus 2-Acrylamido-2-methylpropansulfonsäuren und deren Salzen in einer Menge von 2 bis 500 mg/m², insbesondere 10 bis 300 mg/m², vorzugsweise 100 bis 200 mg/m² fotografisches Material eingesetzt werden, die nicht-ionisch oder anionisch sind, als 0,5 gew.-%ige wäßrige Lösung bei 25°C eine scheinbare Viskosität von 2 bis 200 mPa.s bei D = 100 s⁻¹, vorzugsweise 10 bis 80 mPa.s bei D = 100 s⁻¹, wobei die scheinbare Viskosität in einem Rotationsviskosimeter der Firma Contraves, Zürich (Rheomat 30) mit verschiedenen Drehzahlen, die einer Schergeschwindigkeit von D = 100 s⁻¹ bzw. D = 1000 s⁻¹ entsprechen, gemessen wird, eine Null-Viskosität (extrapoliert für D = 0) von 2 bis 100 000, vorzugsweise 20 bis 20 000 mPa.s und einen Ostwald-Index (O.I.) von 0,25 bis 1,00, vorzugsweise von 0,35 bis 0,90, wobei der Ostwald-Index als Maß für die Strukturviskosität (Pseudoplastizität) nach der Formel
  
  berechnet wird,
  besitzen,
• c) und weniger als 0,5 mg/m² Gelatine enthält, vorzugsweise gelatinefrei ist.

It has now been found that this object can be achieved with a photographic silver halide material of the type mentioned at the outset if the hardening layer is applied as the layer which is the most distant from all layers of the support,

• a) a hardener of the formula
  
  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, which ring can be substituted, for example, by C₁₋ C₃ alkyl 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; (Emergency hardener)

• (b) a water-soluble thickener which does not react practically with the hardening substance, polyacrylamide, polymethacrylic acid and polyacrylic acid salts, copolymers of acrylamide and methacrylic acid or acrylic acid salts, copolymers of 2-acrylamido-2-methylpropanesulfonic acids and their salts in an amount of 2 to 500 mg / m², in particular 10 to 300 mg / m², preferably 100 to 200 mg / m² of photographic material are used, which are non-ionic or anionic, as a 0.5 wt .-% aqueous solution at 25 ° C. an apparent viscosity of 2 to 200 mPa.s at D = 100 s⁻¹, preferably 10 to 80 mPa.s at D = 100 s⁻¹, the apparent viscosity in one Rotational viscometer from Contraves, Zurich (Rheomat 30) is measured at different speeds, which correspond to a shear rate of D = 100 s⁻¹ or D = 1000 s⁻¹, a zero viscosity (extrapolated for D = 0) of 2 to 100,000, preferably 20 to 20,000 mPa.s and an Ostwald index (OI) of 0.25 to 1.00, preferably from 0.35 to 0.90, the Ostwald index as a measure of the structural viscosity ( Pseudoplasticity) according to the formula
  
  is calculated,
  have,
• c) and contains less than 0.5 mg / m² of gelatin, preferably gelatin-free.

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

Alkyl, unless otherwise defined, is especially C₁-C₂₀-alkyl optionally substituted by halogen, hydroxy, sulfo, C₁-C₂₀-alkoxy.

Aryl, unless otherwise defined, is in particular optionally substituted by halogen, sulfo, C₁-C₂₀-alkoxy or C₁-C₂₀-alkyl C₆-C₁₄ aryl. Aralkyl, unless otherwise defined, is in particular C Halogen-C₂₀-aralkyl substituted by halogen, C₁-C₂₀-alkoxy, sulfo or C₁-C₂₀-alkyl. Alkoxy, unless otherwise defined, is in particular C₁-C₂₀ alkoxy.

X ^⊖ is preferably a halide ion such as Cl ^⊖ , Br ^⊖ or BF₄ ^⊖ , NO₃ ^⊖ , (SO₄ ^2⊖ ) _1/2 , ClO₄ ^⊖ , CH₃OSO₃ ^⊖ , PF₆ ^⊖ , CF₃SO₃ ^⊖ .

Alkylene is especially C₂-C₂₀ alkylene; Arylene in particular phenylene, aralkylene in particular benzylene and alkaralkylene in particular xylylene.

Suitable N-containing ring systems that can represent Z are shown below. The pyridine ring is preferred.

Die Verbindungen sind in einfacher und aus der Literatur bekannter Weise darstellbar. Aus den sekundären Aminen stellt man z.B. mit Phosgen die Carbaminsäurechloride her, die dann unter Lichtabschluß mit aromatischen, heterocyclischen stickstoffhaltigen Verbindungen umgesetzt werden. Die Herstellung der Verbindung 3 wird in den Chemischen Berichten 40, (1907), Seite 1831, beschrieben. Weitere Angaben zur Synthese finden sich in DE-OS 2 225 230, DE-OS 2 317 677 und DE-OS 2 439 551.Preferred hardeners are listed below: x

The compounds can be prepared in a simple manner known from the literature. The carbamic acid chlorides are produced from the secondary amines, for example with phosgene, which are then reacted with aromatic, heterocyclic nitrogen-containing compounds in the absence of light. The preparation of compound 3 is described in Chemical Reports 40, (1907), page 1831. Further information on the synthesis can be found in DE-OS 2 225 230, DE-OS 2 317 677 and DE-OS 2 439 551.

In particular, 50 to 500 mg / m², preferably 200 to 400 mg / m², of hardener are used.

The casting solution for the hardening layer has in particular a viscosity of 1 to 30 mPa.s; the hardening layer in particular a wet layer thickness of 3 to 30 microns.

The thickener should not react with the hardening agent or other substances present in the casting solution or only to such a limited extent that no flocculation or cloudiness greater than 50 NTU (Nephelometric Turbidity Unit; LABO, March 1987), preferably greater than 20 NTU occur.

Viscosity-increasing agents which do not meet these requirements are unsuitable because of a reduction in the hardening activity, insufficient increase in viscosity or deterioration in the surface properties of the finished material, such as, for example, wet scratch resistance and dirt acceptance.

Examples of particularly suitable viscosity-increasing agents are:

In order to ensure that the casting solution containing the viscosity-increasing agent runs smoothly, surface-active agents are expediently added. Examples of suitable surfactants are:
Alkyl esters of sugar; anionic surface-active agents which contain acidic groups, for example a carboxy group, a sulfo group, a phospho group, a sulfate group and a phosphate group, for example alkylcarboxylic acid salts, alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkylsulfates, alkylphosphates, nuccinate, n-acylates, n-acylates, n-acylates Sulfoalkyl polyoxyethylene alkylphenyl ether and polyoxyethylene alkyl phosphates; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines and amine oxides; and cationic surfactants such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts, for example pyridinium and imidazolium compounds and aliphatic or heterocyclic phosphonium or sulfonium surface-active salts. In addition, fluorinated surfactants can be used.

Of these surface active agents, anionic surface active agents having a sulfo group and fluorinated surface active agents are particularly preferred.

The hardening layer is preferably applied to a carrier material together with other layers using a so-called V-caster. V casters are e.g. known from DE-A-32 38 905.

The casting solution for the hardening layer preferably only meets the casting solutions for the other layers at the pouring edge on which the free-falling curtain forms.

A gelatin-containing protective layer is preferably provided between the hardening layer and the uppermost light-sensitive layer.

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

The color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, in addition to the hardening layer, optionally 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. Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose, as well as gelatin derivatives, by reaction with alkylating or acylating agents or by grafting polymerizable monomers are examples of this.

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

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

The silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide. For example, the halide content of at least one layer can be 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol%. consist of bromide.

In particular, the photographic material according to the invention is a color photographic material with a reflective base (color paper), the silver halide emulsions of which are either silver bromide chlorides with ≦ 25 mol% silver chloride or silver halides with at least 90 mol% silver chloride, preferably at least 95 mol% silver chloride and 0 to 10 mol% preferably contain 0 to 5 mol% of silver bromide.

The silver halides are preferably free of iodide. It can be predominantly compact crystals, e.g. are 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, 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 doping of the individual grain areas, being different. The middle The 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, for example 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 optionally combined one after the other after the single-jet or simultaneously according to the double-jet process or any combination of both 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 added to any Make the time ineffective, for example by changing the pH value 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). Thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic compounds can also be used 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) 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. Furthermore, salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can 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 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, 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 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-ethyl carbocyanines with benzothiazole, 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 benzimidazocarbocyanines, 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 benzimidazocarbocyanines, which may also be further substituted and must also 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.

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, cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.

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

Color couplers for generating the partial partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type.

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 are α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers.

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

DIR couplers, the development inhibitors of the azole type, e.g. Triazoles and benzotriazoles are released 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 described. Further advantages for color rendering, i.e. color separation and color purity, and for detail rendering i.e. sharpness and granularity can be achieved with such DIR couplers which e.g. do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after a further subsequent reaction, which is achieved, for example, with a timing group. Examples of these are in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-157 146 and 204 175, in US-A-4 146 396 and 4 438 393 and in GB -A-2 072 363.

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

When using DIR couplers, in particular those which release a well-diffusible development inhibitor, improvements in color rendering, for example more differentiated color rendering, can be achieved by suitable measures in the optical sensitization, for example in EP-A-115 304, 167 173 , GB-A-2 165 058, DE-A-3 700 419 and US-A-4 707 436.

The DIR couplers can be added to a wide variety of layers in a multilayer photographic material, e.g. also light-insensitive or intermediate layers. However, they are preferably added to the photosensitive silver halide emulsion layers, the characteristics of the silver halide emulsion, e.g. whose iodide content, the structure of the silver halide grains or their grain size distribution influence 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 can be advantageous to use a DIR coupler which forms a color in the coupling in the respective layer in which it is introduced, which color differs from the color to be produced in this layer.

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-4,618,572 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 in that an intermolecular reaction of this group occurs after its release with another group according to DE-A-3 506 805.

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

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

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

The non-light-sensitive intermediate layers, which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent an 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 scavengers, 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-69 070, 98 072 , 124 877, 125 522 and in US-A-463 226.

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 1 958 709, DE-A 2 530 645, DE-A 2 622 922).

The photographic material may further 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-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).

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 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 layers of binder, in particular the layer furthest away from the carrier, but also occasionally intermediate layers, especially if they represent the layer furthest away from the carrier during production, can contain photographically inert particles of an inorganic or organic nature, e.g. as matting agents or as spacers ( 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.

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, spirochromans, 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 impairment (deterioration or degradation) of yellow color images as a result of 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).

The invention further relates to a processing method in which the material according to the invention is imagewise exposed, developed, bleached, fixed, washed or stabilized and finally dried, characterized in that the development is free of benzyl alcohol and preferably in less than two and a half minutes, in particular in less than one Minute.

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. 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.

It is advantageous if at least 90% by weight of the thickener is detached from the material during processing. Since the amount of thickener in the material is small, its accumulation in the processing baths does not impair the processing process.

The compositions and processing times of the development and bleach-fix bath in which the material according to the invention is processed are given below:

a) Color developer - 45 s - 35 ° C

Triethanolamine 9.0 g / l NN-diethylhydroxylamine 4.0 g / l 3-methyl-4-amino-N-ethyl-N-methanesulfonamidoethyl aniline sulfate 5.0 g / l Potassium sulfite 0.2 g / l Potassium carbonate 22 g / l Potassium hydroxide 0.4 g / l Ethylenediaminetetraacetic acid di-Na salt 2.2 g / l Potassium chloride 2.5 g / l 1,2-Dihydroxybenzene-3,4,6-trisulfonic acid trisodium salt 0.3 g / l make up to 1,000 ml with water; pH 10.0

b) bleach-fix bath - 45 s - 35 ° C

Ammonium thiosulfate 75 g / l Sodium bisulfite 13.5 g / l Ammonium acetate 2.0 g / l Ethylenediaminetetraacetic acid (iron ammonium salt) 57 g / l 25% ammonia 9.5 g / l acetic acid 9.0 g / l make up to 1,000 ml with water; pH 5.5

c) Soak - 2 min - 33 ° C

example

A color photographic recording material which is suitable for a rapid processing process was produced by applying the following layers in the order given to a layer support on paper coated on both sides with polyethylene. The amounts given relate in each case to 1 m 2. For the silver halide application, the corresponding amounts of AgNO₃ are given.

Layer structures 1 to 4

• 1. Schicht (Substratschicht):
  0,2 g Gelatine
• 2. Schicht (blauempfindliche Schicht):
  blauempfindliche Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,8 µm) aus 0,63 g AgNO₃ mit
  1,38 g Gelatine
  0,95 g Gelbkuppler GB
  0,2 g Weißkuppler W
  0,29 g Trikresylphosphat (TKP)
• 3. Schicht (Zwischenschicht)
  1,1 g Gelatine
  0,06 g 2,5-Dioctylhydrochinon
  0,06 g Dibutylphthalat (DBP)
• 4. Schicht (grünempfindliche Schicht)
  grünsensibilisierte Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,6 µm) aus 0,45 g AgNO₃ mit
  1,08 g Gelatine
  0,41 g Purpurkuppler PP
  0,08 g 2,5-Dioctylhydrochinon
  0,34 g DBP
  0,04 g TKP
• 5. Schicht (UV-Schutzschicht)
  1,15 g Gelatine
  0,6 g UV-Absorber UV
  0,045 g 2,5-Dioctylhydrochinon
  0,04 g TKP
• 6. Schicht (rotempfindliche Schicht)
  rotsensibilisierte Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,5 µm) aus 0,3 g AgNO₃ mit
  0,75 g Gelatine
  0,36 g Blaugrünkuppler BG
  0,36 g TKP
• 7. Schicht (UV-Schutzschicht)
  0,35 g Gelatine
  0,15 g UV-Absorber UV
  0,2 g TKP
• 8. Schicht (Schutzschicht)
  Verdicker 10 mg YM 4
  0,3 g Härtungsmittel 55
  10 mg Netzmittel

Ein Vergleichsaufbau enthielt keinen Verdicker, war aber ansonsten gleich aufgebaut.

• 1st layer (substrate layer):
  0.2 g gelatin
• 2nd layer (blue-sensitive layer):
  blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 µm) from 0.63 g AgNO₃ with
  1.38 g gelatin
  0.95 g yellow coupler GB
  0.2 g white coupler W
  0.29 g tricresyl phosphate (CPM)
• 3rd layer (intermediate layer)
  1.1 g gelatin
  0.06 g 2,5-dioctyl hydroquinone
  0.06 g dibutyl phthalate (DBP)
• 4th layer (green-sensitive layer)
  Green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.6 µm) from 0.45 g AgNO₃ with
  1.08 g gelatin
  0.41 g PP purple coupler
  0.08 g 2,5-dioctyl hydroquinone
  0.34 g DBP
  0.04 g CPM
• 5th layer (UV protective layer)
  1.15 g gelatin
  0.6 g UV absorber UV
  0.045 g 2,5-dioctyl hydroquinone
  0.04 g CPM
• 6th layer (red-sensitive layer)
  Red-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 µm) from 0.3 g AgNO₃ with
  0.75 g gelatin
  0.36 g blue-green coupler BG
  0.36 g CPM
• 7th layer (UV protective layer)
  0.35 g gelatin
  0.15 g UV absorber UV
  0.2 g CPM
• 8th layer (protective layer)
  Thickener 10 mg YM 4
  0.3 g of curing agent 55
  10 mg of wetting agent

A comparison setup did not contain a thickener, but was otherwise constructed the same.

The layers are applied by means of a curtain coater according to DE-A-32 38 905, the pouring solution for the 8th layer only meeting the layer package of the other casting solutions at the coater edge.

The layer structures were exposed behind a gray wedge and subjected to a rapid processing process, the literature-known RA-4 process.

• a) gußtechnische Beurteilung: ausgezeichnete Gußqualität (Gleichmäßigkeit auch bei langer Gußdauer über mehrere Tage bei Gießgeschwindigkeiten von 150-250 m/min Bahngeschwindigkeit
• b) Schmutzaufnahme
  Beurteilung nach Verarbeitung in einer handelsüblichen Walzentransport-Entwicklungsmaschine für Colorpapier z.B. AGFAPRO, wobei der Entwickler sich im Gebrauchszustand befindet. Die Maschine war vor dem Schmutzaufnahmetest mindestens 3 Tage unter normalen Bedingungen unbenutzt. Da das oberste Walzenpaar beim früheren Einsatz von der Entwicklerflüssigkeit benetzt war und nicht in der Entwicklerlösung eingetaucht ist, oxidiert der Entwickler auf diesem Walzenpaar ein. Schickt man nach dieser Stehzeit die zu verarbeitende Blattware durch die Maschine, so dringt der vom ersten Walzenpaar abgeklatschte Schmutz (oxidierter Entwickler) in der Regel in die obersten Schutzschichten ein und ist als fleckenförmige, graue bis braune, nicht abwaschbare Abfärbung erkennbar. Diese Anfärbung wird nach der in der folgenden Tabelle angegebenen Benotung bewertet:

  Note 1:

  kein zurückbleibender Schmutz, kein Schleier

  Note 2:

  geringfügiger Schmutz, geringer Schleier

  Note 3:

  starker Schmutz, fleckiger Schleier

Results:

• a) Casting assessment: excellent casting quality (uniformity even with long casting times over several days at casting speeds of 150-250 m / min web speed
• b) Dirt pick-up
  Assessment after processing in a commercial roller transport developing machine for Color paper eg AGFAPRO, whereby the developer is in the state of use. The machine was unused for at least 3 days under normal conditions before the dirt pick-up test. Since the uppermost pair of rollers was wetted by the developer liquid during previous use and is not immersed in the developer solution, the developer oxidizes on this pair of rollers. If the sheet material to be processed is sent through the machine after this idle time, the dirt (oxidized developer) removed from the first pair of rollers usually penetrates into the uppermost protective layers and is recognizable as spot-like, gray to brown, non-washable discolouration. This staining is rated according to the rating given in the following table:

  Note 1:

  no dirt left behind, no veil

  Grade 2:

  slight dirt, slight veil

  Note 3:

  heavy dirt, stained veil

Claims (6)

1. A photographic silver halide material comprising a support, at least one light-sensitive silver halide emulsion layer applied to the support, a hardening layer and optionally other light-sensitive and light-insensitive layers, characterised in that the hardening layer is applied as the layer furthest removed of all the layers from the layer support and contains

   a) a hardener corresponding to the following formula

   

   wherein

   R₁   denotes alkyl, aryl or aralkyl,

   R₂   has the same meaning as R₁ or denotes alkylene, arylene , aralkylene or alkaralkylene and the second bond is linked to a group of the following formula:

   

   or

   R₁ and R₂   together denote the atoms required for completing an optionally substituted heterocyclic ring, which ring may be substituted, e.g. by C₁-C₃-alkyl or by halogen,

   R₃   denotes hydrogen, alkyl, aryl, alkoxy, NR₄-COR₅, -(CH₂)_m-NR₈R₉, -(CH₂)_n-CONR₁₃R₁₄ or

   

   or a bridging member or a direct link to a polymer chain,

   R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈ and R₁₉   denote hydrogen or C₁-C₄-alkyl,

   R₅   denotes hydrogen, C₁-C₄-alkyl or NR₆R₇,

   R₈   denotes COR₁₀,

   R₁₀   denotes NR₁₁R₁₂,

   R₁₁   denotes C₁-C₄-alkyl or aryl,

   R₁₂   denotes hydrogen, C₁-C₄-alkyl or aryl,

   R₁₃   denotes hydrogen, C₁-C₄-alkyl or aryl,

   R₁₆   denotes hydrogen, C₁-C₄-alkyl, COR₁₈ or CONHR₁₉,

   m   denotes a number from 1 to 3,

   n   denotes a number from 0 to 3,

   p   denotes a number from 2 to 3 and

   Y   denotes O or NR₁₇ or

   R₁₃ and R₁₄   together denote the atoms required for completing an optionally substituted heterocyclic ring, which ring may be substituted by C₁-C₃-alkyl or by halogen,

   Z   denotes the carbon atoms required for completing a 5-membered or 6-membered aromatic heterocyclic ring optionally carrying a condensed benzene ring and

   X^⊖   denotes an anion, which is absent if an anionic group is already attached to the remainder of the molecule,

   b) a water-soluble thickener which is virtually unreactive with the hardening substance, the thickener used being polyacrylamide, polymethacrylic acid salts or polyacrylic acid salts, copolymers of acrylamide and methacrylic acid salts or acrylic acid salts, copolymers of 2-acrylamide-2-methylpropanesulphonic acids and their salts, used in a quantity of from 2 to 500 mg/m² of photographic material, which thickeners are non-ionic or anionic and have an apparent viscosity as 0.5% by weight aqueous solutions of from 2 to 200 mPa.s at D = 100 s⁻¹, a zero viscosity of from 2 to 100,000 mPa.s and an Ostwald index from 0.25 to 1.00, and

   c) less than 0.5 mg/m² of gelatine.
2. A photographic silver halide material according to Claim 1, characterized in that the hardener is used in a quantity of from 50 to 500 mg/m² of the photographic material.
3. A photographic silver halide material according to Claim 1, characterized in that the apparent viscosity of the thickener as a 0.5% by weight aqueous solution is from 10 to 80 mPa.s at D = 100 s⁻¹, the zero viscosity is from 20 to 20,000 mPa.s and the Ostwald-Index is from 0.35 to 0.90.
4. A colour photogrepahic silver halide material according to Claim 1, characterised in that it contains, on a paper laminated with a polyolefin on both sides, at least one blue-sensitive layer associated with a yellow coupler, at least one red-sensitive layer associated with a cyan coupler and at least one green-sensitive layer associated with a magenta coupler, the silver halides of the said layers containing at least 90 mol-% of silver chloride.
5. A process for the production of a coloured image viewed by reflected light, by imagewise exposure, development, bleaching, fixing, washing and stabilization and drying of a colour photographic silver halide material according to Claim 4, characterised in that development is carried out free from benzyl alcohol.
6. A process according to Claim 5, characterised in that at least 90% by weight of the thickener is dissolved from the material during processing.