EP0464409B1 - Colour photographic recording material - Google Patents

Description

The invention relates to a color photographic recording material which is characterized by a particularly low silver coating and which is processed in an environmentally friendly manner without an actual color developing bath being necessary.

It is known to process color photographic silver halide materials with a low silver coating with an amplification bath containing H₂O₂ following the color development bath, so-called amplification processes (e.g. DE 3 228 192).

It has now been found that color photographic silver halide materials with a low silver application can be processed into excellent color images by the amplification process without a color developing bath being run through if the color photographic materials in the color coupler-containing layers in dissolved hydrophobic oil droplets contain at least one p-phenylenediamine compound with a primary amino group and at least one ballast residue.

The invention relates to a color photographic recording material having at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler and at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler and customary intermediate and protective layers, characterized in that the silver halide is applied all light-sensitive layers, given as AgNO₃, is not more than 0.3 g / m and the color coupler-containing layers dissolved in hydrophobic oil droplets contain at least one p-phenylenediamine compound with at least one primary amino group and at least one ballast residue.

The color photographic material preferably contains in at least one light-sensitive layer as an emulsion a silver chloride bromide emulsion with 0.05 to 3 mol% of silver bromide. In particular, at least 50% of the silver bromide is on the surface of the silver halide grains. Such emulsions are obtained in particular by treating AgCl emulsions and AgClBr emulsions with a lower bromide content than desired after sensitization with the aqueous solution of a bromide.

The emulsions of all the light-sensitive layers are preferably AgClBr emulsions of the type mentioned, it being possible for the bromide fractions to differ from layer to layer within the inserted frame.

The silver halides preferably have a bromide content of 0.2-2 mol%.

In addition, the silver halide grains can contain up to 0.5 mol% of silver iodide, but are preferably free of silver iodide.

Color coupler and p-phenylene diamine compound are preferably dissolved together in a high-boiling hydrophobic solvent ("oil-forming agent"), and this solution is emulsified in an aqueous gelatin solution.

worin Ballast ein Ballastrest, insbesondere ein C₁₀-C₂₀-Alkylrest,

R₁

ein gegebenenfalls substituierter Alkylrest mit 2 bis 4 C-Atomen, der als Substituenten insbesondere wenigstens einen OH-, SO₃H-, COOH-oder CH₃SO₂NH-Rest aufweist,

R₂ und R₃

Wasserstoff oder C₁-C₄-Alkyl bedeuten.

Geeignete Verbindungen entsprechen den folgenden Formeln:

The p-phenylenediamine compound corresponds in particular to the formula

wherein ballast is a ballast radical, in particular a C₁₀-C₂₀ alkyl radical,

R₁

an optionally substituted alkyl radical having 2 to 4 carbon atoms, as a substituent in particular has at least one OH, SO₃H, COOH or CH₃SO₂NH radical,

R₂ and R₃

Is hydrogen or C₁-C₄ alkyl.

Suitable compounds correspond to the following formulas:

P-Phenylenediamine compounds with at least one ballast residue are also those p-phenylenediamine compounds with which a latex is loaded.

Another possibility is to load latices, identical or different, both with color couplers and with p-phenylenediamine compounds. This technique is described, for example, in 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 and US-A 3,291,113.

The color photographic recording material preferably consists of a reflective support on which, in the order given, a layer sensitive to blue, containing at least one yellow coupler, a layer sensitive to green, to some extent containing a purple coupler, and a layer sensitive to red, containing at least one cyan coupler, and customary intermediate and protective layers are applied .

The silver halide coating, indicated as AgNO₃, is preferably 0.05 to 0.3 g / m.

Another object of the invention is an image forming method for the above material, in which the material is treated with aqueous H₂O₂ after imagewise exposure.

The concentration of H₂O₂ is preferably 0.5 to 25 g / l.

In a preferred embodiment, the color photographic material or the intensifying bath contains a black and white developer substance (e.g. Phenidon®, Hydroquinone, Metol®, Amidol® in an amount of 0.01 to 1.0 g / l.

The reinforcement can be followed by the usual steps of bleaching, fixing, washing and drying, whereby bleaching and fixing can be carried out in one bath (bleach-fix bath). A particular advantage of the method, however, is that the small amount of silver halide produces such a weak silver image that the color image is no longer disturbed and the silver image therefore does not need to be removed. The bleaching can thus be omitted. Fixing (dissolving the unexposed silver halide) can also be omitted if the silver halide is converted into a light-insensitive silver complex salt by a stabilizing bath. In this case, drying can immediately follow the stabilization.

In addition to the silver halide grains and the color couplers, the silver halide emulsion layers essentially contain a binder, which is also the main constituent of the intermediate and protective 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. Oxidized gelatin can also be used. The preparation of such gelatins is described, for example, in The Science and Technology of Gelatine, published 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 halides used according to the invention can be predominantly compact crystals, which e.g. are regular cubic or octahedral or can have transitional forms. The silver halides can also be in the form of platelet-shaped crystals whose average ratio of diameter to thickness is e.g. is 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 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%. Homodisperse silver halide emulsions or mixtures thereof are preferred. 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 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, preferably during the precipitation the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is run through 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, for example by pasta and washing, by flaking 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 17643 (Dec. 1978), Chapter III) may be added, as an alternative or in addition, 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 also 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 17643 (Dec. 1978), Chapter 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, for preventing electrical charging, for improving the sliding properties, for emulsifying the dispersion, for preventing adhesion and for improving 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. Also suitable are fluorine-containing surfactants, which are known for example from GB-PS 1 330 356, 1 524 631 and US-PS 3 666 478 and 3 689 906.

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 (Dec. 1978), Chapter IV, provides an overview of the polymethine dyes suitable as spectral sensitizers, their suitable combinations and combinations having 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 benzthiazole, benzselenazole or naphthothiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl and 9-ethyl-naphthoxathia or -selencarbocyanines and 9- Ethyl naphthothiaoxa or benzimidazocarbocyanines, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.
• 2. as green sensitizers
  9-ethyl carbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzothiazole 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.

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 purple 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 of the benzoylacetanilide and α-pivaloylacetanilide type. Numerous examples of the couplers are described in the literature.

The couplers can also be of high molecular weight, so-called latex couplers.

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, the p-phenylenediamine derivatives or other compounds can be incorporated into silver halide emulsion layers in such a way that a solution, dispersion or emulsion is first prepared from the compound in question and then added to the casting solution for the layer in question. The selection of the suitable solvent or dispersing agent depends 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 used using high-boiling solvents, so-called oil formers, be introduced into the casting solution. 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 diffusion-resistant incorporation of anionic water-soluble compounds (e.g. dyes) can also be carried out with the help 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, NN-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-t-amylphenol, dioctyl acylate, glycerol tributyrate, isostearyl lactate, Trioctyl citrate, N, N-dibutyl-2-butoxy-5-t-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.

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), chapters VII, 17 842 (Feb. 1979) and 18 716 (Nov. 1979), page 650 and in EP A-0 069 070, 0 098 072, 0 124 877, 0 125 522.

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 to protect the image dyes from fading due to UV-rich daylight. 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).

Particularly suitable UV absorbers should absorb light up to 400 nm and have a steep drop in their light absorption capacity at wavelengths above 400 nm.

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

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

R⁴ = -CO-OC₈H₁₇
R¹, R = -C₂H₅; R³ =

R₄ = -COO-C₁₂H₂₅
R¹, R = -CH₂=CH-CH₂;   R³, R⁴ = -CN

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

Examples of particularly suitable compounds are

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

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

R⁴ = -CO-OC₈H₁₇
R¹, R = -C₂H₅; R³ =

R₄ = -COO-C₁₂H₂₅
R¹, R = -CH₂ = CH-CH₂; R³, R⁴ = -CN

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

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 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 be photographically inert

Contain particles of inorganic or organic nature, for example as matting agents or as spacers (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.

Additives to improve dye, coupler and whiteness stability and to reduce the color fog (Research Disclosure 17 643 (Dec. 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 the deterioration of yellow color images due to the development of heat, moisture and light. About the impairment of purple color images, especially their impairment as a result of exposure to prevent light, spiroindanes (JP-A-159 644/81) and chromanes substituted by hydroquinone diether or monoether (JP-A-89 835/80) are particularly effective.

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 929183); N-carbonyloximide compounds (JP-A-43353181); 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 with two or more N-acyloximino groups (US Pat. No. 4,052,373), epoxy compounds (US Pat. No. 3,091,537), Isoxazole type compounds (US-A-3 321 313 and US-A-3 543 292); Halocarboxyaldehydes such as mucochloric acid; Dioxane derivatives such as dihydroxydioxane and di-chlorodioxane; and inorganic hardeners such as chrome alum and zirconium sulfate.

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

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

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

   worin

R¹

Alkyl, Aryl oder Aralkyl bedeutet,

R

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 R

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 -(CH₂)_p

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

NR¹¹R¹

R¹¹

C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

R¹

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

R¹³

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

R¹⁶

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

m

eine Zahl 1 bis 3

n

eine Zahl 0 bis 3

p

eine Zahl 2 bis 3 und

Y

O oder NR¹⁷ bedeuten oder

R¹³ und R¹⁴

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

Z

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

X^⊖

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

   worin

R¹, R, R³ und X^⊖

die für Formel (a) angegebene Bedeutung besitzen.

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

wherein

R¹

Means alkyl, aryl or aralkyl,

R

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

is linked, or

R¹ and R

together the to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring required atoms, where the 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 - (CH₂) _p

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

NR¹¹R¹

R¹¹

C₁-C₄ alkyl or aryl, especially phenyl,

R¹

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;

wherein

R¹, R, 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 and high-molecular hardeners. With them, individual layers, e.g. crosslink 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 mechanical layer has to be improved with the protective layer (EP-A-0 114 699).

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-N-hydroxyethyl-ethylenediaminetriacetic 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 watering can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent. This stabilizing bath also takes on the function of a final bath when formaldehyde is added.

example 1

A color photographic recording material was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene. The quantities are based on 1 m. For the silver halide application, the corresponding amounts of AgNO₃ are given. All emulsions were stabilized with 0.8 g butylbenzotriazole / 100 g AgNO₃. Before casting, all casting solutions were adjusted to pH 5.5.

Layer structure 1 (comparison)

• 1st layer (substrate layer):
  0.3 g gelatin
• 2nd layer (blue-sensitive layer)
  0.09 g AgNO₃ of a spectrally blue sensitized AgCl _0.994 Br _0.005 I _0.001 emulsion, average grain diameter 0.8 µm
  1.42 g gelatin
  0.95 g yellow coupler GB 1
  1.0 g tricresyl phosphate
• 3rd layer (intermediate layer)
  1.1 g gelatin
  0.06 g 2,5-dioctyl hydroquinone
  0.06 g dibutyl phthalate
• 4th layer (green-sensitive layer):
  0.62 g AgNO₃ of a spectrally green sensitized AgCl _0.995 Br _0.005 emulsion, average grain diameter 0.6 µm,
  1.20 g gelatin,
  0.41 g purple coupler PP 1
  0.35 g dibutyl phthalate,
  0.25 g tricresyl phosphate
• 5th layer (V protective layer)
  1.3 g gelatin
  0.56 g UV absorber of the formula
  
  
  0.3 g tricresyl phosphate
• 6th layer (red-sensitive layer) 0.054 g AgNO₃ of a spectrally red-sensitized AgCl _0.993 Br _0.007 emulsion with an average grain diameter of 0.55 µm,
  0.85 g gelatin
  0.38 g blue-green coupler BG 1
  0.38 g tricresyl phosphate
• 7th layer (UV protective layer)
  0.60 g gelatin
  0.2 g UV absorber (as in the 5th layer)
  0.1 g tricresyl phosphate
• 8th layer (hardener layer)
  0.9 g gelatin
  0.2 g hardening agent of the formula
  

Color couplers used:

Layer structure B (comparison)

Like layer structure 1A, however
Add 0.10 g phenidone / m to the 2nd layer, 0.08 g Phenidon / m to the 4th layer, and 0.07 g Phenidon to the 6th layer

Layer structure C (according to the invention)

Like layer structure A, however
in the second layer 0.95 g GB 1 and 0.5 g E 6 emulsified together in CPM;
in the 4th layer 0.41 g PP 1 and 0.28 g E 6 emulsified together in CPM
in the 6th layer 0.38 g BG 1 and 0.30 g E 6 emulsified together in CPM.

Layer structure D (according to the invention)

Like layer structure C, but additionally the amounts of phenidone mentioned in layer structure B for the 2nd, 4th and 6th layers.

Layer structure E (according to the invention)

Like layer structure C, but the same amount of E 2 instead of E 6; E 2 was emulsified in TKP separately from the color coupler.

Layer structure F (according to the invention)

Like layer structure E, but with the addition of the amounts of phenidone mentioned in layer structure B in the 2nd, 4th and 6th layers.

The layer structures A to F produced in this way were exposed in a sensitometer behind a gray scale wedge for 1/100 s and processed with the following belts:

Booster bath I

Developer amplifier solution Polyglycol P 400 22 ml Diethyl hydroxylamine (85% by weight) 6 ml Color developer CD 3 10th G Potassium sulfite 0.33 G 1-hydroxyethane-1,1-diphosphonic acid 0.14 G Potassium hydrogen carbonate 5 G Potassium carbonate 22 G Potassium hydroxide 8th G Dodecylbenzenesulfonate 0.02 G Hydrogen peroxide 35% by weight 10th ml make up to 1000 ml with water; pH 10.6

Since the color developer slowly reacts with the hydrogen peroxide in the solution, this solution was freshly prepared shortly before use.

Booster bath II

Adjust aqueous 0.5% by weight hydrogen peroxide to pH 10.6 with KOH, then add 0.5 g phenidone to 1000 ml

Booster bath III

Like booster bath II, but without phenidone.

Fixing solution

Ammonium thiosulfate 50 G Sodium sulfite 5 G Sodium bisulfite 2nd G make up to 1000 ml with water; pH 6.0

Processing samples A to F:

Booster bath: 35 ° C 20 sec Fixing bath: 23 ° C 20 sec Watering: 23 ° C 60 sec

Since the amount of silver developed was very small in all samples and all processing, a bleaching stage was dispensed with.

The color density curves of the samples A to F processed in this way were measured behind blue, green and red filters; the sensitometric data are summarized in Table 1.

As can be seen from this table, with the phenidone-free, color developer-free, environmentally friendly booster bath III, useful sensitometric data (ie those as in comparative bath I) are obtained only with the layer structures D and F according to the invention; on the other hand, with the phenidone-containing, color developer-free, environmentally friendly bath, useful sensitometric data are also obtained with the (phenidone-free) layer structures C and E.

Claims (9)

1. A colour photographic recording material comprising at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler and at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler and typical intermediate and protective layers, characterized in that the silver halide coating of all the photosensitive layers, expressed as AgNO₃, amounts to no more than 0.3 g/m and the colour-coupler-containing layers contain at least one p-phenylenediamine compound containing at least one primary amino group and at least one ballast group or a latex charged with a p-phenylenediamine compound dissolved in hydrophobic oil droplets.
2. A colour photographic recording material as claimed in claim 1, characterized in that a silver chloride bromide emulsion containing 0.05 to 3 mole-% of silver bromide is used as the emulsion in at least one photosensitive layer.
3. A colour photographic recording material as claimed in claim 2, in which at least 50% of the silver bromide is present at the surface of the silver halide crystals.
4. A colour photographic recording material as claimed in claim 2, characterized in that the silver bromide content is from 0.2 to 2 mole-% and the silver halide emulsion is iodide-free.
5. A colour photographic recording material as claimed in claim 1, characterized in that the emulsions of all the photosensitive layers are AgClBr emulsions containing 0.05 to 3 mole-% of silver bromide.
6. A colour photographic recording material as claimed in claim 4, characterized in that the bromide contents of the silver chlorobromides of the individual photosensitive layers are different.
7. A colour photographic recording material as claimed in claim 1, characterized in that the silver halide coating, expressed as AgNO₃, amounts to between 0.05 and 0.2 g/m.
8. A colour photographic development process, characterized in that an exposed material according to claim 1 is subjected to intensification with H₂O₂ in the presence of a black-and-white developer substance.
9. A process as claimed in claim 8, in which there is no bleaching step.