EP0709731A2 - Color photographic silverhalide material - Google Patents

Abstract

Colour photographic Ag halide (AgX) material has a base; red- (RS), green- (GS) and blue-sensitive (BS) AgX emulsion layer(s) contg. cyan, magenta and yellow coupler respectively; and spacer layer(s) (Z-1) under the lowest RS emulsion layer and/or spacer layer(s) (Z-2) under the lowest GS emulsion layer. The novelty is that Z-1 and/or Z-2 contains a AgX emulsion contg. tabular grains with an aspect ratio of >2 and an average dia. (ds) of the sphere of equal vol. is ≥ 0.3 mu and the dia. (dc) of the circle of equal projection area is ≥ 0.3 mu .

Description

The invention relates to a color photographic silver halide material with a support, at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one intermediate layer Z-1 under the bottom layer Silver halide emulsion layer and / or at least one intermediate layer Z-2 under the lowermost green-sensitive silver halide emulsion layer, which is characterized by an improved red and / or green sensitivity.

In particular, the invention relates to a color photographic silver halide material with camera sensitivity, preferably a color negative film with a transparent support.

Color negative films must have a certain minimum sensitivity in order to achieve blur-free shots with them in all commercially available cameras, ie shots with a short shutter speed of the camera. This minimum sensitivity means that the silver halide emulsions required for this are silver bromide iodide emulsions which have a high intrinsic sensitivity in the blue region of the visible spectrum. This intrinsic sensitivity of the silver bromide iodide emulsions in turn means that the blue-sensitive layers are usually arranged farthest from the support and that a yellow filter layer is located between them and the green- and red-sensitive layers is arranged to prevent incorrect exposure of the green and red sensitive layers with blue light.

In the currently customary layer structure of color negative films, the red-sensitive, cyan-green coupling layers are arranged closest to the support. They have several disadvantages compared to the other layers because (1) some of the red light in the layers above has already been lost due to absorption or scattering (2) when developing the developer due to consumption in the layers above it no longer has the highest concentration and (3) simultaneously with the developer, substances diffuse into the red-sensitive layers which slow down the development, for example the bromide ions released by the development in the layers above. This also applies to a lesser extent to the green-sensitive, purple-coupling layers.

These disadvantages have a negative impact on the sensitivity of the red and green sensitive layers.

The object of the invention was therefore to increase the sensitivity to red and / or green in a silver halide material of the type mentioned at the outset.

It has now surprisingly been found that the object can be achieved in that Z-1 and / or Z-2 contains a silver halide emulsion which has tabular grains with an aspect ratio> 2, an average diameter of the volume-equal sphere of ≧ 0 , 3 µm and a diameter of the circular projection surface of the tabular grains of ≧ 0.3 µm.

Preferably, the tabular grains make up at least 50% of the projection area of said emulsion. The aspect ratio is preferably 4 to 15. The silver halide emulsions of the intermediate layers Z-1 and Z-2 are in particular not spectrally sensitized.

In particular, the material according to the invention has 2 or 3 red-sensitive, cyan-coupling silver halide emulsion layers, 2 or 3 green-sensitive, purple-coupling silver halide emulsion layers and 2 or 3 blue-sensitive, yellow-coupling silver halide emulsion layers, in addition to which the intermediate layers Z-1 and Z-2, a yellow filter layer between the green-sensitive and the blue-sensitive silver halide emulsion layers and, if necessary, further intermediate, protective and top layers are added.

The tabular grain silver halide emulsion found in Z-1 and / or Z-2 consists in particular of 0 to 40 mol% AgI, 0 to 100 mol% AgCl and 0 to 100 mol% AgBr.

In a particularly preferred embodiment, the tabular grains consist of AgBr, have an average diameter of the same-volume sphere from 0.45 to 0.55 μm, an average diameter of the projection area of 0.67 to 1.10 μm, and an average crystal thickness of 0.075 to 0.165 µm and an average aspect ratio of 5 to 12. The emulsion of the intermediate layer is used in an amount which corresponds to 0.1 to 2.0 g AgNO₃ per m², preferably 0.5 to 1.5 g AgNO₃ / m².

Suitable transparent supports for the production of color photographic materials are e.g. Films and sheets of semi-synthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polyethylene naphthalate and polycarbonate. These carriers can also be colored black for the purpose of shielding light. The surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer. The back of the carrier can be provided with a magnetic layer and an antistatic layer.

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 wholly or partly by other synthetic, semi-synthetic or naturally occurring Polymers to be replaced. 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 gelatin can also be replaced in whole or in part by silica sol.

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

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

The silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide. For example, the halide content of at least one layer can consist of 0 to 40 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide. It can be predominantly compact crystals, which are, for example, regularly cubic or octahedral or can have transitional forms. However, platelet-shaped crystals can also preferably be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain. However, the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, for example 12: 1 to 30: 1. Tabular silver halide crystals with a hexagonal shape are particularly preferred.

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

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

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

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 Sensitivity and fog optimum subjected. The procedure is described, for example, by H. Frieser "The Basics of Photographic Processes with Silver Halides" page 675-734, Akademische Verlagsgesellschaft (1968).

The 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), and thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic compounds 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). As an alternative or in addition, a reduction sensitization can be carried out with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid) using hydrogen, by means of low pAg (eg less than 5) and / or high pH (eg above 8) .

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

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 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, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics ( eg acceleration of development, high contrast, sensitization etc.). In addition to natural surface-active compounds, e.g. Saponin, mainly synthetic surface-active compounds (surfactants) are used: non-ionic surfactants, e.g. Alkylene oxide compounds, glycerin compounds or glycidol compounds, cationic surfactants, e.g. higher alkyl amines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.

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

Research Disclosure 17643 (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-Ethylnaphthoxathia- bzw. -selencarbocyanine und 9-Ethyl-naphthothiaoxa bzw. - benzimidazocarbocyanine, vorausgesetzt, daß die Farbstoffe mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff tragen.
• 2. als Grünsensibilisatoren
  9-Ethylcarbocyanine mit Benzoxazol, Naphthoxazol oder einem Benzoxazol und einem Benzthiazol als basische Endgruppen sowie Benzimidazocarbocyanine, die ebenfalls weiter substituiert sein können und ebenfalls mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff enthalten müssen.
• 3. als Blausensibilisatoren
  symmetrische oder asymmetrische Benzimidazo-, Oxa-, Thia- oder Selenacyanine mit mindestens einer Sulfoalkylgruppe am heterocyclischen Stickstoff und gegebenenfalls weiteren Substituenten am aromatischen Kern, sowie Apomerocyanine mit einer Rhodaningruppe.

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

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

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 purple partial color image are usually couplers of the pyrazolone or of the pyrazolotriazole type.

Color couplers for producing the yellow partial color image are generally couplers of the acylacetanilide type.

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 which contain a cleavable residue in the coupling site, 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 ( e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolds, e.g. 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 which release development inhibitors of the azole type, for example triazoles and benzotriazoles, are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416. Further advantages for color reproduction, ie color separation and color purity, and for detail reproduction, ie sharpness and granularity, can be achieved with those DIR couplers which, for example, do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after one Another follow-up reaction, for example with a timing group is achieved. Examples of these are in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-0 157 146 and 0 204 175, in US-A-4 146 396 and 4 438 393 as well 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-0 167 168 and 0 219 713. This measure ensures trouble-free development and processing consistency.

When using DIR couplers, in particular those which split off a well-diffusible development inhibitor, improvements in the color rendering, e.g. achieve a more differentiated color rendering, as described, for example, in EP-A-0 115 304, 0 167 173, GB-A-2 165 058, DE-A-37 00 419 and US-A-4 707 436.

The DIR couplers can be added to a wide variety of layers in a multilayer photographic material, 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 described, for example, in DE-A-25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-0 089 834, 0 110 511, 0 118 087, 0 147 765 and in US-A-4 618 572 and 4 656 123.

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

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

Since with DIR, DAR or FAR couplers mainly the effectiveness of the residue released during coupling is desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-15 47 640).

The cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).

The material may further contain compounds other than couplers, which can 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-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.

High-molecular 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 described. 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. 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 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-O 043 037.

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

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

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, for example, 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-t-amylphenol, dioctyl azate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-octoxy-5-butyl-2-butyl , Paraffin, dodecylbenzene and diisopropylnaphthalene.

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.

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, e.g. separated by layers of other spectral sensitization. For example, all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).

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

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

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

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

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

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

Additives to improve dye, coupler and whiteness stability and to reduce the color haze (Research Disclosure 17 643 (Dec. 1978), chapter VII) can belong to the following chemical classes of substances: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, spiroindanes, p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines derivatives with esterified metal complexes or etherified phenol complexes, etherified phenol groups.

Compounds which 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 as a result of the development of heat, moisture and light. In order to prevent the deterioration of magenta color images, in particular their deterioration as a result of exposure to light, spiroindanes (JP-A-159 644/81) and chromanes which are substituted by hydroquinone diethers or monoethers (JP-A-89 835 / 80) 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-113 929/83); N-carbonyloximide compounds (JP-A-43353/81); N-sulfonyloximido compounds (US-A-4 111 926), dihydroquinoline compounds (US-A-4 013 468), 2-sulfonyloxypyridinium salts (JP-A-110 762/81), formamidinium salts (EP-A-0 162 308) , Compounds with two or more N-acyloximino groups (US-A-4 052 373), epoxy compounds (US-A-3 091 537), compounds of Isoxazole type (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 that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.

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

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

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

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

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

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

example 1

A color photographic recording material for color negative color development was produced (layer structure 1A) by applying the following layers in the order given to a transparent layer support made from cellulose triacetate. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given; the silver halides are stabilized with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

1st layer (antihalo layer)

0.3 g

black colloidal silver

1.2 g

gelatin

0.4 g

UV absorber UV 1

0.02 g

Tricresyl phosphate (CPM)

2nd layer (intermediate layer )

1.0 g

gelatin

3rd layer (low red sensitive layer)

2.7 g

AgNO₃ a spectrally red-sensitized Ag (Br, J) emulsion with 4 mol% iodide, average grain diameter 0.5 µm

2.0 g

gelatin

0.88 g

colorless coupler C1

0.02 g

DIR coupler D 1

0.05 g

colored coupler RC-1

0.07 g

colored coupler YC-1

0.75 g

CPM

4th layer (highly red-sensitive layer)

2.2 g

AgNO₃ of the spectrally red-sensitized Ag (Br, J) emulsion, 12 mol% iodide, average grain diameter 1.0 µm,

1.8 g

gelatin

0.19 g

colorless coupler C 2

0.17 g

CPM

5th layer (intermediate layer )

0.4 g

gelatin

0.15 g

White coupler W-1

0.06 g

Aluminum salt of aurintricarboxylic acid

6th layer (low green sensitive layer)

1.9 g

AgNO₃ a spectrally green sensitized Ag (Br, J) emulsion, 4 mol% iodide, average grain diameter 0.35 µm

1.8 g

gelatin

0.54 g

colorless coupler M-1

0.24 g

DIR coupler D-1

0.065 g

colored coupler YM-1

0.6 g

CPM

7th layer (highly green-sensitive layer)

1.25 g

AgNO₃ a spectrally green-sensitized Ag (Br, J) emulsion, 9 mol% iodide, average grain diameter 0.8 µm, 1.1 g gelatin

0.195 g

colorless coupler M-2 0.05 g colored coupler YM-2

0.245 g

CPM

8th layer (yellow filter layer )

0.09 g

yellow colloidal silver

0.25 g

gelatin

0.08 g

Scavenger SC1

0.40 g

Formaldehyde scavenger FF-1

0.08 g

CPM

9th layer (low blue-sensitive layer)

0.9 g

a spectrally blue-sensitized Ag (Br, J) emulsion, 6 mol% iodide, average grain diameter 0.6 µm

2.2 g

gelatin

1.1 g

colorless coupler Y-1

0.037 g

DIR coupler D-1

1.14 g

CPM

10th layer (highly blue-sensitive layer)

0.6 g

AgNO₃ of a spectrally blue-sensitized Ag (Br, J) emulsion, 10 mol% iodide, average grain diameter 1.2 µm,

0.6 g

gelatin

0.2 g

colorless coupler Y-1

0.003 g

DIR coupler D-1

0.22 g

CPM

11th layer (Mikrat layer)

0.06 g

AgNO₃ a Mikrat-Ag (Br, J) emulsion, average grain diameter 0.06 µm,

0.5

Mol% iodide,

1 g

gelatin

0.3 g

UV absorber UV-2

0.3 g

CPM

12th layer (protective and hardening layer )

0,25 g

Gelatine

0,75 g

Härtungsmittel der Formel

   sodaß der Gesamtschichtaufbau nach der Härtung einen Quellfaktor ≦ 3,5 hatte.

0.25 g

gelatin

0.75 g

Hardening agent of the formula

so that the total layer structure had a swelling factor ≦ 3.5 after curing.

Substances used in example 1:

Example 2

A color photographic recording material was produced according to Example 1 with the following changes:
The second layer contained in a quantity corresponding to 1 g AgNO₃ / m² a tabular, unsensitized AgBr emulsion with the following characteristics:
More than 90% of the projection area were tabular crystals with an average diameter of the same-volume sphere of 0.5 µm, an average diameter of the circle-equal projection area of 0.87 µm and an aspect ratio of 7.9.

Example 3

A color photographic recording material was produced in accordance with Example 2; the amount of the tabular unsensitized silver bromide emulsion was 2 g AgNO₃ / m².

Example 4

A color photographic recording material was produced in accordance with Example 2; Instead of the tabular emulsion, an unsensitized, cubic silver bromide emulsion was used in an amount corresponding to 1 g AgNO₃ / m² with the following characteristics:
Average diameter of the same-volume sphere: 0.55 µm.

Examples 2 and 3 are according to the invention; Examples 1 and 4 comparative examples.

Gray wedges were exposed on the materials of Examples 1 to 4; the exposed materials were processed according to "The British Journal of Photography", 1974, pages 597 and 598.

The following results are found: material Gradation 1 Gradation 2 Gradation 3 Red sensitivity (0.2 over fog in log I · t) veil 1 (comparison) 0.96 1.07 0.58 1.00 0.39 2 (invention) 0.99 1.03 0.57 1.12 0.38 3 (invention) 1.01 1.01 0.53 1.19 0.42 4 (comparison) 0.97 1.08 0.58 1.01 0.41

The green and blue sensitivities remained practically unchanged.

Example 5

A color photographic recording material was produced according to Example 1 with the following changes:
The 5th layer contained an amount corresponding to 1 g AgNO₃ / m² of a tabular, unsensitized AgBr emulsion with the following characteristics:
More than 90% of the projection area were tabular crystals with an average diameter of the same-volume sphere of 0.5 µm, an average diameter of the circle-equal projection area of 0.87 µm and an aspect ratio of 7.9.

Example 6

A color photographic recording material was produced in accordance with Example 5; the amount of the tabular unsensitized silver bromide emulsion was 2 g AgNO₃ / m².

Example 7

A color photographic recording material was produced in accordance with Example 5; Instead of the tabular emulsion, an unsensitized, cubic silver bromide emulsion was used in an amount corresponding to 1 g AgNO₃ / m² with the following characteristics:
Average diameter of the same-volume sphere: 0.55 µm.

Examples 5 and 6 are according to the invention; Examples 1 and 7 comparative examples.

Gray wedges were exposed on the materials of Examples 1 and 5 to 7; the exposed materials were processed according to "The British Journal of Photography", 1974, pages 597 and 598.

The following results are found: material Gradation 1 Gradation 2 Gradation 3 Green sensitivity (0.2 over veil in log I · t) veil 1 (comparison) 0.96 1.07 0.58 1.00 0.39 5 (invention) 0.99 1.09 0.59 1.15 0.43 6 (invention) 1.01 1.02 0.61 1.20 0.40 7 (comparison) 1.00 1.01 0.56 0.98 0.38

The red and blue sensitivities remained practically unchanged.

Claims (10)

Color photographic silver halide material with a support, at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one intermediate layer Z-1 silver and the lower halide or red sensitive layer at least one intermediate layer Z-2 under the lowermost green-sensitive silver halide emulsion layer, characterized in that Z-1 and / or Z-2 contains a silver halide emulsion which has tabular grains with an aspect ratio> 2, an average diameter of the same-volume sphere of ≧ 0, 3 µm and a diameter of the circular projection surface of the tabular grains of at least 0.3 µm. Color photographic material according to claim 1, wherein the red-sensitive and the green-sensitive layer each consist of 2 or 3 sub-layers of different photographic sensitivity. The color photographic material of claim 1, wherein the tabular grains make up at least 50% of the projection area of the total emulsion and the aspect ratio is 4 to 15. Color photographic material according to claim 1, characterized in that the silver halide emulsion in the intermediate layer Z-1 and / or Z-2 is not spectrally sensitized. Color photographic material according to claim 1, characterized in that the silver halide emulsion with the tabular grains in Z-1 and / or Z-2 from 0 to 40 mol% AgI, 0 to 100 mol% AgCl and 0 to 100 mol% AgBr consists. Color photographic material according to claim 1, characterized in that the tabular silver halide grains have an average diameter of the same-volume sphere of 0.45 to 0.55 µm, an average diameter of the circular projection area of 0.67 to 1.10 µm, an average crystal thickness of 0.075 up to 0.165 µm and have an average aspect ratio of 5 to 12. Color photographic material according to claim 1, characterized in that the tabular silver halide emulsion is used in an amount which corresponds to 0.1 to 2.0 g AgNO₃ / m². Color photographic material according to claim 1, characterized in that the tabular silver halide emulsion is used in an amount which corresponds to 0.5 to 1.5 g AgNO₃ / m². Color photographic material according to claim 4, characterized in that the silver halide emulsions of the 2 or 3 red-sensitive, the 2 or 3 green-sensitive and the 2 or 3 blue-sensitive silver halide emulsion layers to 0 to 40 mol% of AgI, 0 to 100 mol% of AgCl and 0 to 100 mol% consist of AgBr. Color photographic material according to claim 1, characterized in that all green-sensitive silver halide emulsion layers are arranged closer to the support than all blue-sensitive silver halide emulsion layers, all red-sensitive silver halide emulsion layers are arranged closer to the support than all green-sensitive silver halide emulsion layers, Z-1 between the support and the red-sensitive silver halide emulsion layers the red-sensitive and the green-sensitive silver halide emulsion layers are arranged and Z-1 and Z-2 are coupler-free.