DE3926849A1 - COLOR PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL - Google Patents

Description

The invention relates to a color photographic silver halide negative material with improved graininess and improved color rendering.

It is known from DE-A-32 41 635 for multi-layer color photographic recording materials the sensitivity and sharpness through the use of tabular To increase silver halide grains, that is, from silver halide grains, their thickness - with a diameter of at least 0.6 microns - less than 0.5 microns which is an average aspect ratio, defined as the ratio of grain diameter have a thickness greater than 8: 1, whereby that the diameter of a grain is defined as that Diameter of a circle with a circle content accordingly the projected area of the grain.

Such materials contain at least two layers different sensitivity to the same  Spectral range are sensitized, at least contains the most sensitive layer the above tabular silver halide grains.

Despite the improved properties, these materials have Disadvantages because of graininess and color rendering do not meet the requirements.

The object of the invention is to provide color photographic silver halide recording materials to create that at improved sensitivity and sharpness also regarding Graininess and color rendering are improved, whereby as a measure of the color rendering of the inter-image effect (IIE) serves.

It has now been found that this problem is solved if you have at least three for a spectral range Provides layers of different sensitivity, the different silver halide emulsions, below other tabular silver halide emulsions.

The object of the invention is therefore a color photographic Silver halide material with a support and photosensitive silver halide emulsion layers for the red, green and blue spectral range, the Teal, magenta and yellow couplers are complementarily assigned are, at least for a spectral range at least three sub-layers of different sensitivity are provided which, seen from the carrier, the greater the sensitivity with increasing distance have, characterized in that the most sensitive  Partial layer of tabular silver halide grains and at least one of the medium sensitive sub-layers Silver halide grains with layered grain structure contain.

Preferably the green and / or red sensitive Layers built up at least three layers, the lowest sensitive sublayer in particular one Contains fine grain emulsion, the mean spherical equivalent Grain diameter is at most 0.40 µm.

Preferably at least 80% by weight of the silver halide grains are one of the sub-layers specified above Grains of the specified habit, of the specified Structures or the specified size.

In a preferred embodiment of the invention both the green sensitive and the red sensitive Split the layer into at least 3 sub-layers. Also preferred is the color coupler equivalent ratio to silver halide in the sublayer with the lowest sensitivity greater and in the sub-layer with the highest sensitivity smaller too choose as in at least one of the medium sensitive Sub-layers for the same spectral range.

It is also preferred to have the lowest sensitivity in the partial layer and in the sub-layer of highest sensitivity Incorporate couplers, their coupling speed is larger than that of the medium-sensitive coupler Layers for the same spectral range.  

The tabular silver halide grains are marked by an aspect ratio (definition like DE-A-32 41 635) of at least 5: 1, the proportion such tabular silver halide grains as a proportion of the projection surface of such tabular Grains on the projection surface of all silver halide grains the emulsion, at least 50%, preferably is at least 70%, in particular at least 90%. The average diameter of tabular silver halide grains (Definition like DE-A-32 41 635) preferably at least 1.5 µm. The halide distribution of tabular silver halide grains from mixed Silver halides can be homogeneous or inhomogeneous, e.g. B. from the crystal center to the edge of the parallel main crystal faces different in at least two zones Halide composition can be divided, where the zone boundary can be sharp or flowing. The amount the zones can be the same or different from each other be spoken of a zone only then if it is at least 1%, preferably at least Accounts for 5% of the total grain volume and in this partial volume the same halide composition everywhere is present.

The tabular silver halide grains can range from 0 to 15 mol% silver iodide, 0 to 100 mol% silver bromide and 0 to 100 mol% of silver chloride exist. Are preferred Silver bromide iodide grains with a maximum of 15 mol% of silver iodide, being particularly in a zone that is not that The crystal center or edge is the silver iodide content larger than in the grain center or at the grain edge is.  

Silver halide grains with a layered grain structure are those containing more than one halide and one have non-homogeneous halide distribution such that around a core at least one shell with different from the core Halide composition is appropriate. The boundaries between core and shell or between each two envelopes can be sharp or flowing. Of a Core or shell can only be spoken if he (she) accounts for at least 5% of the total volume and the same halide composition everywhere in this partial volume is present.

The grains with layered grain structure can be tabular or be compact, for example cubic, octahedral, tetradecahedral or irregular. They have preferably an average spherical equivalent grain diameter (average diameter of the same volume Sphere) of at most 0.6 µm. The grain size distribution can be heterodisperse or homodisperse, of which homodisperse grain size distribution is then spoken if S / 0.15, where

r _{i is} the size of a single granule and n _{i is} the number of granules of a size r _i .

Homodisperse silver halide emulsions are preferred. The silver halide emulsions with layered grain structure contain in particular 0 to 10 mol% of silver iodide, 0 to 99.5 mol% of silver bromide and 0 to 99.5 mol% of silver chloride.

Silver bromide iodide emulsions with 0.5 to 10 mol% of silver iodide, in particular 1 to 5 mol% of silver iodide.

The crystals of the silver halide emulsion of the partial layer with the lowest sensitivity the least three sub-layers of different sensitivity for the same spectral range can be tabular or compact with homogeneous or inhomogeneous halide distribution be. With inhomogeneous halide distribution one also speaks of layered grain structure. The compact For example, crystals can be cubic, octahedral, tetradecahedral or irregular Have crystal habit. The tabular crystals the average aspect ratio is at least 5: 1 and the mean diameter at most 1 µm (definitions DE-A-32 41 635). The projection surface of these grains makes at least 50% of the projection area of all grains this layer. The compact or tabular emulsion consists of 0 to 15 mol% of iodide, 0 to 100 mol% from bromide and 0 to 100 mol% of chloride, preferably it is a silver bromide iodide emulsion with up to 15 mol% silver iodide. Your grain size distribution can be homodisperse or heterodisperse.  

There can also be two in each of the individual sub-layers or several types of silver halide emulsions be prepared separately, used as a mixture.

The photographic emulsions can be different Methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman et al., Making and Coating Photographic Emulsion, The Focal Press, London (1966) soluble silver salts and soluble halides will.

The silver halide is preferably precipitated in Presence of the binder, e.g. B. the gelatin and can carried out in the acidic, neutral or alkaline pH range are, preferably silver halide complexing agents can also be used. The latter include z. B. ammonia, thioether, imidazole, ammonium thiocyanate or excess halide. The merge the water-soluble silver salts and the halides optionally takes place one after the other after the single jet or at the same time according to the double-jet process or by any combination of both methods. Prefers the dosage becomes with increasing inflow rates, where the "critical" feed rate at which just no new germs are emerging, not exceeded should be. The pAg range can be changed during the Precipitation can vary within wide limits, preferably the so-called pAg-controlled method is used, at which a certain pAg value is kept constant or  run through a defined pAg profile during the precipitation becomes. In addition to the preferred precipitation with excess halide is also the so-called inverse Precipitation possible with excess silver ions. Except through The silver halide crystals can also precipitate physical ripening (Ostwald ripening), in the presence of excess halide and / or silver halide complexing agent to grow. The growth of the emulsion grains can even predominantly through Ostwald ripening take place, preferably a fine-grained, so-called Lippmann emulsion, with a poorly soluble Emulsion mixed and redissolved on the latter.

During precipitation and / or physical ripening The silver halide grains can also contain salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe to be available.

The precipitation can also be carried out in the presence of sensitizing dyes respectively. Complexing agent and / or dyes can be any Make time ineffective, e.g. B. by changing the pH Value or by an oxidative treatment.

After crystal formation is complete or already closed the soluble salts are removed at an earlier point in time the emulsion removed, e.g. B. by pasta and washing, by flaking and washing, by ultrafiltration or through ion exchangers.

The silver halide emulsion generally becomes one chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide  and sensitizer concentration - until it is reached of the optimum sensitivity and fog.

The procedure is e.g. B. with H. Frieser "The basics of the photographic processes with silver halides " Pages 675-734, Academic Publishing Company (1968).

The chemical sensitization can add of compounds of sulfur, selenium, tellurium and / or Compounds of metals of subgroup VIII Periodic table (e.g. gold, platinum, palladium, iridium) can take place, furthermore thiocyanate compounds, surface-active Compounds such as thioethers, heterocyclic Nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described e.g. with F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmann's Encyclopedia of Technical Chemistry, 4th edition, vol. 18, p. 431 ff. And Research Disclosure No. 17643, section III) can be added. Alternatively or in addition, a reduction sensitization with the addition of reducing agents (tin-II salts, Amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid) by hydrogen, by low pAg (e.g. less than 5) and / or high pH (e.g. above 8) will.

The photographic emulsions can be compounds to Prevention of fog or for stabilization the photographic function during production, the Storage or photographic processing included.  

Azaindenes, preferably tetrahedra, are particularly suitable. and pentaazaindenes, especially those containing Hydroxyl or amino groups are substituted. Such Connections are e.g. B. von Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Can continue as Antifoggant 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 Benztriazoles or Benzthiazoliumsalze used will. Mercapto groups are particularly suitable containing heterocycles, e.g. B. mercaptobenzthiazoles, Mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, Mercaptopyrimidines, these mercaptoazoles also a water solubilizing group, e.g. B. a carboxyl group or sulfo group. Further suitable compounds are in Research Disclosure No. 17643 (1978) Section VI.

The stabilizers can the silver halide emulsions before, during or after their ripening. Of course, the connections can also be made to others photographic layers that are a layer of halogen silver are assigned.

Mixtures of two or more of the above can also be used Connections are used.

The photographic emulsion layers or other hydrophilic Colloid layers of the one produced according to the invention Photosensitive material can be surface active  Contain funds for various purposes, such as coating aids, to prevent electrical charging Improvement of the sliding properties, for emulsifying the Dispersion, to prevent adhesion and to improve the photographic characteristics (e.g. acceleration of development, high contrast, sensitization etc.). In addition to natural surface-active compounds, e.g. B. saponin, find mainly synthetic surface-active compounds (surfactants) Use: non-ionic surfactants, e.g. B. alkylene oxide compounds, Glycerin compounds or glycidol compounds, cationic Surfactants, e.g. B. higher alkylamines, quaternary ammonium salts, Pyridine compounds and other heterocyclic Compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing one Acid group, e.g. B. carboxylic acid, sulfonic acid, a phosphoric acid, Sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, e.g. B. amino acid and Aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters an amino alcohol.

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

An overview of those suitable as spectral sensitizers Polymethine dyes, their suitable combinations and super-sensitizing combinations contains e.g. B. Research Disclosure 17643/1978 in Department IV.  

In particular, the following dyes are ordered by spectral areas - suitable:

• 1. as red sensitizers:
  9-ethyl carbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl, and 9-ethyl-naphthoxathia or -selencarbocyanines and 9- Ethyl-naphthothiaoxa- or -benzimidazocarbocyanine, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.
• 2. as green sensitizers:
  9-ethyl carbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzthiazole as basic end groups, and also benzimidazocarbocyanines, which may also be further substituted and must likewise contain at least one sulfoalkyl group on the heterocyclic nitrogen.
• 3. as blue sensitizers:
  symmetrical or asymmetrical benzimidazo, oxa, thia or selenacyanines with at least one sulfoalkyl group on the heterocyclic nitrogen and optionally further substituents on the aromatic nucleus, and apomerocyanines with a rhodanine group.

Gelatin is preferably used as the binder. However, this can be wholly or partly by others synthetic, semi-synthetic or also naturally occurring Polymers to be replaced. Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N vinyl pyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are, for example other proteins like 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, which by implementation with alkylating or acylating agents or by Grafting polymerizable monomers obtained are examples of this.

The binders should have a sufficient amount of functional groups so that by implementation sufficiently resistant with suitable hardening agents Layers can be created. Such functional Groups are especially amino groups, but also Carboxyl groups, hydroxyl groups and active methylene groups.

The gelatin which is preferably used can be acidic or alkaline digestion. It can also oxidized gelatin can be used. The production  such gelatin is described, for example, in The Science and Technology of Gelatine, edited by A.G. Ward and A. Courts, Academic Press 1977, page 295ff. The gelatin used should be as possible low level of photographically active impurities included (inert gelatin). Gelatin with high viscosity and low swelling are special advantageous.

Suitable supports for the production of color photographic materials are z. B. Films and foils of semi-synthetic and synthetic polymers such as cellulose nitrate, Cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, Polyethylene terephthalate and polycarbonate. These carriers can be mixed with dyes and pigments, for example Titanium dioxide, colored. You can also colored black for the purpose of shielding light be. The surface of the carrier is generally subjected to a treatment to improve the adhesion of the photographic To improve the emulsion layer, for example a corona discharge with subsequent application a substrate layer.

Sensitizers can be dispensed with if for intrinsic sensitivity in a certain spectral range of the silver halide is sufficient, for example the blue sensitivity of silver bromides.  

The differently sensitized emulsion layers become non-diffusing monomeric or polymeric color couplers assigned which is in the same shift or in a layer adjacent to it. Usually the red-sensitive layers are cyan couplers, the green-sensitive layers of purple couplers and the blue-sensitive layers of yellow couplers assigned.

Color coupler for generating the blue-green partial color image are usually phenol or α-naphthol type couplers, those of the 2-ureidophenol type and / or of the 1,5- Aminonaphthol type are preferred for this invention; Color coupler for generating the purple partial color image are usually couplers of the 5-pyrazolone type Indazolons or the pyrazoloazole, those of the acylaminopyrazolone type and / or pyrazoloazole type are used for this Invention preferred; Color coupler for the generation of the yellow Partial color images are usually couplers with a open chain ketomethylene grouping, in particular Α-arylacetamide type couplers; those of the α-benzoylacetanilide type and / or α-pivaloylacetanilide type preferred for this invention.

The color couplers can be 4-equivalent couplers, but also act as 2-equivalent couplers. Latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point, which is split off at the clutch. To the 2- Equivalent couplers are to be expected that are colorless  are, as well as those that have an intense intrinsic color have, which disappears with the color coupling or replaced by the color of the image dye produced becomes (mask coupler), and the white couplers that react with color developer oxidation products essentially result in colorless products. This preferably contains material according to the invention blue-green coupling red mask couplers with an escape group bound by oxygen. Such couplers are also to the 2-equivalent couplers to be expected, which is a detachable in the coupling point Rest included when reacting with color developer oxidation products is set free and either directly or after from the primary split off rest one or more other groups have been split off (e.g. DE-A-27 03 145, DE-A- 28 55 697, DE-A-31 05 026, DE-A-33 19 428), a specific one desired photographic effectiveness unfolds, e.g. B. as a development inhibitor or accelerator. Examples the known are for such 2-equivalent couplers DIR couplers as well as DAR or FAR couplers.

DIR couplers, the development inhibitors of the azole type, e.g. B. triazoles and benzotriazoles are released in DE A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 27 26 180, 36 26 219, 36 30 564, 36 36 824, 36 44 416 and 28 42 063 described. Other advantages for color rendering, d. i.e., color separation and color purity, and for detail reproduction, d. i.e., sharpness and graininess, are with such To achieve DIR couplers, the z. B. the development inhibitor not immediately as a result of the clutch split off with an oxidized color developer, but  only after another subsequent reaction, for example is achieved with a timing group. Examples for this are in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-1 57 146 and 2 04 175, in US-A- 41 46 396 and 44 38 393 and in GB-A-20 72 363.

DIR couplers that release a development inhibitor that in the developer bath is essentially photographically ineffective Products are decomposed, for example in DE-A-32 09 486 and in EP-A-1 67 168 and 2 19 713. With this measure, a trouble-free Development and processing consistency achieved.

When using DIR couplers, especially those that split off a diffusible development inhibitor, can be taken by taking appropriate measures at the spectral sensitization improvements in color rendering, e.g. B. a more differentiated color rendering, achieve, such as in EP-A-1 15 304, 1 67 173, GB-A-21 65 058, DE-A-37 00 419 and US-A-47 07 436.

The DIR couplers can be used in a multi-layer photographic Material added to different layers be, e.g. B. also light-insensitive or intermediate layers. However, they are preferably the photosensitive silver halide emulsion layers added, the characteristic properties the silver halide emulsion, e.g. B. their iodide content, the  Structure of the silver halide grains or their grain size distribution of influence on the photographic achieved Properties are. The influence of the released Inhibitors can be installed, for example an inhibitor scavenger layer according to DE-A-24 31 223 limited will. For reasons of reactivity or stability it may be advantageous to use a DIR coupler the one in the respective layer in which it is introduced is one of those to be generated in this layer Color deviates from the color of the coupling.

To increase sensitivity, contrast and DAR or FAR Couplers are used that are a development accelerator or split off an fogger. links 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-89 834, 1 10 511, 1 18 087, 1 47 765 and in US-A- 46 18 572 and 46 56 123.

As an example for the use of BAR couplers (Bleach Accelerator Releasing Coupler) is published on EP-A-1 93 389 referred.

It can be beneficial to combine the effects of one Coupler split off photographically effective group by modifying an intermolecular reaction this group after their release with a another group according to DE-A-35 06 805.

In the present invention are particularly advantageous DIR coupler in the or one of the medium sensitive Silver halide emulsion layers of the least  three sub-layers of different sensitivity but used the same spectral sensitization, being DIR couplers with inhibitors of high diffusibility are particularly preferred.

Examples of DIR couplers are:

As with the DIR, DAR and FAR couplers mainly the effectiveness of the released at the clutch Remaining is desired and it is less on the color-forming Properties of these couplers are well received DIR, DAR or FAR couplers suitable for the Coupling result in essentially colorless products (DE- A-15 47 640).

The detachable residue can also be a ballast residue, see above that in the reaction with color developer oxidation products Coupling products are obtained that are diffusible are or at least a weak or restricted one Have mobility (US-A-44 20 556).  

The material can still be different from couplers Contain compounds which contain, for example, a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, an fogger or a Free antifoggants, for example so-called DIR hydroquinones and other compounds, as for example in US-A-46 36 546, 43 45 024, 46 84 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-1 98 438 are described. These Connections perform the same function as the DIR, DAR or FAR couplers, except that they are not coupling products form.

High molecular weight color couplers are for example in DE-C- 12 97 417, 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-40 80 211 described. The high molecular color couplers are used in usually by polymerization of ethylenically unsaturated monomeric color couplers. You can but also obtained by polyaddition or polycondensation will.

Incorporation of couplers or other connections in silver halide emulsion layers can in the way done that first of the connection in question a solution, a dispersion or an emulsion and then the casting solution for that one Layer is added. Choosing the right one  Solvent or dispersant depends on the particular Solubility of the compound.

Methods of introducing into water essentially are insoluble compounds by grinding processes for example in DE-A-26 09 741 and DE-A-26 09 742 described.

Hydrophobic compounds can also be made using high-boiling solvents, so-called oil formers, be introduced into the casting solution. Appropriate methods are described, for example, in US Pat. No. 2,322,027, US Pat. 28 01 170, US-A-28 01 171 and EP-A-00 43 037.

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

The compounds can also be in the form of loaded latices be introduced into the casting solution. Is referred for example on DE-A-25 41 230, DE-A-25 41 274, DE-A- 28 35 856, EP-A-00 14 921, EP-A-00 69 671, EP-A- 01 30 115, US-A-42 91 113.

The diffusion-resistant storage of anionic water-soluble Compounds (e.g. from dyes) can also be used With the help of cationic polymers, so-called pickling polymers respectively.  

Suitable oil formers are e.g. B. alkyl phthalates, Phosphonic acid esters, phosphoric acid esters, citric acid esters, Benzoic acid esters, amides, fatty acid esters, trimesic acid esters, Alcohols, phenols, aniline derivatives and Hydrocarbons.

Examples of suitable oil formers are dibutyl phthalate, Dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, Tricyclohexyl phosphate, tri-2- ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate, Trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, 2-ethylhexyl benzoate, dodecyl benzoate, 2- Ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N- Tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert.- amylphenol, dioctylacelate, glycerol tributyrate, isostearyl lactate, Trioctyl citrate, N, N-dibutyl-2-butoxy-5- tert-octylaniline, paraffin, dodecylbenzene and diisopropylnaphthalene.

This can be done for the two remaining spectral ranges Material a single layer or two or more Silver halide emulsion partial layers include (DE-C- 11 21 470). There are red sensitive silver halide emulsion layers often arranged closer to the substrate as green-sensitive silver halide emulsion layers and these in turn closer than blue-sensitive, generally between green sensitive Layers and blue-sensitive layers not one photosensitive yellow filter layer.  

If the green sensitivity is suitably low, or red-sensitive layers can be omitted other layer arrangements on the yellow filter layer choose in which on the carrier z. B. the blue-sensitive, then the red sensitive and finally the green sensitive layers follow.

The usually different between layers Spectral sensitivity arranged non-photosensitive Intermediate layers can contain agents which is an undesirable diffusion of developer oxidation products from a photosensitive to a other photosensitive layer with different prevent spectral sensitization.

Appropriate agents that include scavengers or EOP scavengers Research Disclosure 17,643 (Dec. 1978), Chapter VII, 17 842/1979, pages 94-97 and 18.716 / 1979, page 650 and in EP-A-69 070, 98 072, 1 24 877, 1 25 522 and in US-A-4 63 226.

If there are several sub-layers of the same spectral sensitization before, so sub-layers of the same spectral Sensitization adjacent to or through other layers, e.g. B. by layers of other spectral Sensitization must be separate. So z. B. all highly sensitive and all low sensitive layers each be combined into a shift package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).

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

Compounds that absorb UV light are said to be on the one hand the image dyes before fading by UV-rich Protect daylight and on the other hand as filter dyes the UV light in daylight during exposure absorb and thus improve the color rendering of a film. Usually for the two tasks Connections of different structures used. Examples are aryl-substituted benzotriazole compounds (US-A-35 33 794), 4-thiazolidone compounds (US A-33 14 794 and 33 52 681), benzophenone compounds (JP- A-2784/71), cinnamic acid ester compounds (US-A-37 05 805 and 37 07 375), butadiene compounds (US-A-40 45 229) or benzoxazole compounds (US-A-37 00 455).

Ultraviolet absorbing couplers (such as Cyan couplers of the α-naphthol type) and ultraviolet absorbing Polymers are used. These ultraviolet absorbents can be done by pickling in a special Layer fixed.

Include filter dyes suitable for visible light Oxonol dyes, hemioxonol dyes, styryl dyes, Merocyanine dyes, cyanine dyes and azo dyes.  Of these dyes, oxonol dyes, Hemioxonol dyes and merocyanine dyes used particularly advantageously.

Suitable whiteners are e.g. B. in Research Disclosure 17,643 (Dec. 1978), Chapter V, in US-A-26 32 701, 32 69 840 and in GB-A-8 52 075 and 13 19 763 described.

Certain layers of binder, especially those of Carrier most distant layer, but also occasionally Intermediate layers, especially if they during the manufacturing process the furthest from the wearer distant layer can be photographically inert Contain particles of inorganic or organic nature, e.g. B. 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-soluble and can be insoluble in alkali or be alkali-soluble, the alkali-soluble generally in an alkaline development bath the photographic material are removed. Examples suitable polymers are polymethyl methacrylate, copolymers from acrylic acid and methyl methacrylate as well Hydroxypropylmethyl cellulose hexahydrophthalate.  

Additives to improve the dye, coupler and White stability and to reduce the color fog (Research Disclosure 17 643/1978, Chapter VII) can belong to the following chemical classes: Hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, Spirochromanes, spiroindanes, p-alkoxyphenols, steric hindered phenols, gallic acid derivatives, methylenedioxybenzenes, Aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, Metal complexes.

Compounds that are both sterically hindered amine Partial structure as well as a sterically hindered Phenol partial structure in one molecule (US A-42 68 593) are particularly effective for prevention the impairment (deterioration or degradation) of yellow color images as a result of the development of heat, Moisture and light. To the impairment (deterioration or the degradation) of purple color images, especially their impairment (deterioration or degradation) as a result of the action of Light to prevent are spiroindane (JP-A-159 644/81) and chromanes by hydroquinone diether or monoether (JP-A-89 835/80) are particularly substituted effective.  

The layers of the photographic material can with the usual hardening agents are hardened. Suitable Hardening agents are e.g. B. formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and others Compounds containing reactive halogen (US-A- 32 88 775, US-A-27 32 303, GB-A-9 74 723 and GB-A- 11 67 207) divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro- 1,3,5-triazine and other compounds, which contain a reactive olefin bond (US-A- 36 35 718, US-A-32 32 763 and GB-A-9 94 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-27 32 316 and US-A-25 86 168); Isocyanates (US-A- 31 03 437); Aziridine compounds (US-A-30 17 280 and US-A-29 83 611); Acid derivatives (US-A-27 25 294 and US-A- 27 25 295); Carbodiimide type compounds (US-A- 31 00 704); 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 Binding (JP-A-113 929/83); N-carbonyloximide compounds (JP-A-43353/81); N-sulfonyloximido compounds (US-A-41 11 926), dihydroquinoline compounds (US-A-40 13 468), 2-sulfonyloxypyridinium salts (JP-A- 110 762/81), formamidinium salts (EP-A-01 62 308), compounds with two or more N-acyloximino groups (US A-40 52 373), epoxy compounds (US-A-30 91 537), Isoxazole type compounds (US-A-33 21 313 and US-A- 35 43 292); 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 that the hardening agent of the casting solution for the hardening layer is added, or in that the Layer to be hardened is covered with a layer which contains a diffusible hardening agent.

Among the classes listed there are slow-acting ones and fast-acting hardening agents as well as so-called Instant hardeners that are particularly beneficial. Under Immediate hardeners are understood as connections that are suitable Crosslink the binder so that immediately after Watering, preferably after 24 hours, preferably The hardening is completed after 8 hours at the latest is that no more through the crosslinking reaction conditional change in sensitometry and Swelling of the layer structure occurs. Under swelling is the difference between the wet film thickness and dry film thickness in the aqueous processing of the film understood (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Closely. (1972), 449).

These hardening agents that react very quickly with gelatin is it z. B. carbamoylpyridinium salts, those with free carboxyl groups of gelatin able to react, so that the latter with free amino groups gelatin to form peptide bonds and crosslinking of the gelatin react.  

Color photographic negative materials are common by developing, bleaching, fixing and watering or by developing, bleaching, fixing and stabilizing processed without subsequent rinsing, bleaching and fixing combined into one processing step could be. Leave as a color developer compound use all developer connections that the Possess ability in the form of their oxidation product with color couplers to azomethine or indophenol dyes to react. Suitable color developer compounds are aromatic, at least one primary amino group p-phenylenediamine type containing compounds, for example N, N-dialkyl-p-phenylenediamines such as N, N- Diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) - 3-methyl-p-phenylenediamine, 1- (N-ethyl-N- hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl- N-methoxyethyl) -3-methyl-p-phenylenediamine. Further usable color developers are 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 follow a watering.

Usually the material is immediately after the Color development bleached and fixed. As a bleach can e.g. B. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes be used. Are particularly preferred  Iron (III) complexes of aminopolycarboxylic acids, in particular e.g. B. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, Diethylenetriaminepentaacetic acid, Nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethyl ethylenediaminetriacetic acid, alkyliminodicarboxylic acids and of corresponding phosphonic acids. Suitable persulphates and peroxides are also bleaches, e.g. B. hydrogen peroxide.

The bleach-fixable or fixing bath is usually followed by one Irrigation, which is carried out as countercurrent irrigation or consists of several tanks with their own water supply.

Favorable results can be obtained by using one on it following final bath, the little or no Contains formaldehyde can be obtained.

However, the watering can be completed by a stabilizing bath to be replaced, usually in countercurrent to be led. This stabilizing bath takes over when formaldehyde is added also the function of a final bath.

In the case of color reversal materials, development initially takes place with a black and white developer whose oxidation product not able to react with the color couplers is. It usually includes a chemical Obfuscation and / or a diffuse second exposure and then development with a color developer, bleaching and Freeze on.  

Example 1

A color photographic recording material for the Color negative color development was produced (layer structures 1A to 1E) by clicking on a transparent Cellulose triacetate supports the following Apply layers in the order given were. The quantities given relate to 1 m². For the silver halide application, the corresponding Amounts of AgNO₃ indicated. All silver halide emulsions were per 100 g of AgNO₃ with 0.1 g 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazainden stabilized.

Layer structure 1A (comparison)

Layer 1 (antihalo layer)
black colloidal silver sol with
0.2 g Ag
1.2 g gelatin

Layer 2 (Mikrat intermediate layer)
Mikrat-silver bromide iodide emulsion (0.5 mol% iodide; average grain diameter 0.07 µm)
0.25 g AgNO₃, with
1.0 g gelatin
0.05 g RM-1 red mask

Layer 3 (1st red-sensitized layer, slightly sensitive)
0.60 g AgNO₃ of the red-sensitized silver bromide iodide emulsion VN (1) with
1.15 g gelatin
0.32 g of cyan coupler C-1
0.03 g RM-1 red mask
0.35 g tricresyl phosphate (CPM)
0.25 g dibutyl phthalate (DBP)

Layer 4 (2nd red-sensitized layer, medium sensitive)
1.52 g of AgNO₃ the red-sensitized silver bromide iodide emulsion VM (1) with
1.40 g gelatin
0.45 g cyan coupler C-2
0.04 g RM-1 red mask
0.04 g DIR coupler DIR-3
0.02 g DIR coupler DIR-1
0.30 g CPM
0.25 g DBP

Layer 5 (3rd red-sensitized layer, highly sensitive)
1.35 g AgNO₃ of the red-sensitized silver bromide iodide emulsion VH (1) with
1.24 g gelatin
0.16 g of cyan coupler C-3
0.03 g RM-2 red mask
0.10 g CPM
0.08 g DBP

Layer 6 (intermediate layer)
0.8 g gelatin
0.05 g 2,5-di-t-pentadecyl hydroquinone
0.05 g CPM
0.05 g DBP
Layer 7 (1st green-sensitized layer, slightly sensitive)
0.45 g AgNO₃ of the green-sensitized silver bromide iodide emulsion VN (1) with
0.85 g gelatin
0.24 g purple coupler M-1
0.04 g yellow mask YM-1

Layer 8 (2nd green-sensitized layer, medium-sensitive)
1.2 g of AgNO₃ the green-sensitized silver bromide iodide emulsion VM (1) with
1.05 g gelatin
0.30 g purple coupler M-2
0.04 g yellow mask YM-2
0.01 g DIR coupler DIR-9
0.03 g DIR coupler DIR-18
0.35 g CPM
0.15 g DBP

Layer 9 (3rd green-sensitive layer, highly sensitive)
1.0 g of AgNO₃ the green-sensitized silver bromide iodide emulsion VH (1) with
1.1 g gelatin
0.11 g purple coupler M-3
0.02 g yellow mask YM-1
0.10 g CPM
0.10 g DBP

Layer 10 (intermediate layer)
like layer 6

Layer 11 (yellow filter layer)
0.04 g Ag with yellow colloidal silver sol
0.8 g gelatin
0.15 g of 2,5-di-t-pentadecyl hydroquinone
0.40 g CPM

Layer 12 (1st blue-sensitive layer, slightly sensitive)
0.3 g of AgNO₃ the blue-sensitized silver bromide iodide emulsion VN (1) and
0.2 g AgNO₃ of the blue-sensitized silver bromide iodide emulsion VM (1)
1.2 g gelatin
0.8 g yellow coupler Y-1
0.20 g DIR coupler DIR-18
0.70 g CPM
0.20 g DBP

Layer 13 (2nd blue-sensitive layer, highly sensitive)
0.75 g of AgNO₃ the blue-sensitized silver bromide iodide emulsion VH (1) with
0.25 g yellow coupler Y-1
1.0 g gelatin
0.20 g CPM

Layer 14 (protective and hardening layer)
Mikrat-silver bromide iodide emulsion (0.5 mol% iodide; average grain diameter 0.04 µm)
0.5 g of AgNO₃ with
1.2 g gelatin
0.4 g of H-1 curing agent
1.0 g formaldehyde scavenger FF

Teal coupler

Purple coupler

Yellow coupler

Red mask

Yellow masks

Formaldehyde scavenger FF

Table 1/1

Overview of the emulsions used in Example 1

The following layer structures 1B, 1C, 1D and 1E are produced by placing them in the individual sub-layers the emulsions VN (1), VM (1) and VH (1) against the Emulsions EN (1), EM (1) and EH (1) were exchanged so as shown in Table 1/1.

One sample each of the layer structures 1A to 1E was behind a gray step wedge exposed to white light (Exposure time: 0.01s) and after a color negative Processing methods as described in "The British Journal of Photography "(1974), pages 597 and 598. As a measure of the color granularity, the RMS Values (= mean squares of fluctuation) with a measuring aperture of 48 µm diameter with different color densities determined. The measurement method is described in: T. H. James, The Theory of the Photographic Process, 4th ed., Mac Millan Publ. Co., New York (1977) p. 619, numerical values for the five layer structures 1A to 1E are in the table 1/2 specified.

The interimage effect (IIE) was carried out according to T. H. James, The Theory of the Photographic Process, 4th edition, Mc Millan Co. N.Y. (1977) pp. 574 and 614 as percentages Division of the color gradation with color separation exposure with light of the corresponding spectral range in relation to the color gradation that is found in additive Exposes exposure to white light, measured.  

Table 1/2

Color granularity and interimage effects from Example 1

Emulsions

Emulsions

Emulsions

Example 2

Layer support, quantities and stabilization of the Emulsions, layers 1 and 2 as in Example 1.

Layer structure 2 A (comparison)

Layer 3 (1st red-sensitive layer, slightly sensitive)
0.4 g of AgNO₃ the red-sensitized silver bromide iodide emulsion VN (2) with
0.55 g gelatin
0.20 g cyan coupler C-4
0.10 g of cyan coupler C-5
0.05 g DIR coupler DIR-19
0.25 g CPM
0.10 g DBP

Layer 4 (2nd red sensitive layer, medium sensitive)
1.35 g AgNO₃ of the red-sensitized silver bromide iodide emulsion VM (2) with
1.55 g gelatin
0.38 g of cyan coupler C-4
0.03 g RM-2 red mask
0.025 g DIR coupler DIR-21
0.015 g DIR coupler DIR-22
0.25 g CPM
0.20 g DBP

Layer 5 (intermediate layer)
like layer 6 from example 1

Layer 6 (1st green-sensitive layer, slightly sensitive)
0.5 g of AgNO₃ the green-sensitized silver bromide iodide emulsion VN (2) with
0.75 g gelatin
0.32 g purple coupler M-4
0.03 g yellow mask YM-1
0.04 g DIR coupler DIR-22
0.05 g CPM

Layer 7 (2nd green sensitive layer, medium sensitive)
1.1 g AgNO₃ of the green-sensitized silver bromide iodide emulsion VM (2) with
0.82 g gelatin
0.26 g purple coupler M-5
0.05 g yellow mask YM-3
0.03 g DIR coupler DIR-22
0.01 g DIR coupler DIR-9
0.05 g CPM
0.04 g DBP

Layer 8 (yellow filter layer)
yellow colloidal silver sol,
0.02 g Ag
0.8 g gelatin
0.15 g of 2,5-di-t-pentadecyl hydroquinone
0.20 g CPM

Layer 9 (1st blue-sensitive layer, slightly sensitive)
0.3 g AgNO₃ of the blue-sensitized silver bromoiodide emulsion VN (2)
0.85 g gelatin
0.65 g yellow coupler Y-3
0.15 g DIR coupler DIR-20
0.30 g CPM
0.20 g DBP

Layer 10 (2nd blue sensitive layer, medium sensitive)
0.25 g of AgNO₃ the blue-sensitized silver bromide iodide emulsion VM (2) with
0.60 g gelatin
0.45 g yellow coupler Y-2
0.10 g DIR coupler DIR-20
0.20 g CPM
0.15 g DBP

Layer 11 (intermediate layer)
like layer 5

Layer 12 (3rd red-sensitive layer, highly sensitive)
1.35 g AgNO₃ of the red-sensitized silver bromide iodide emulsion VH (2) with
1.30 g gelatin
0.12 g cyan coupler C-6
0.01 g red mask RM-2
0.10 g CPM
0.05 g DBP

Layer 13 (intermediate layer)
like layer 5

Layer 14 (3rd green-sensitive layer, highly sensitive)
1.0 g of AgNO₃ of the green-sensitized silver bromide iodide emulsion VH (2)
1.05 g gelatin
0.14 g purple coupler M-6
0.01 g yellow mask YM-1
0.12 g CPM
0.05 g DBP

Layer 15 (yellow filter layer)
like layer 8

Layer 16 (2nd blue-sensitive layer, highly sensitive)
0.80 g AgNO₃ of the blue-sensitized silver bromide iodide emulsion VH (2)
0.85 g gelatin
0.12 g yellow coupler Y-3
0.10 g CPM

Layer 17 (protective and hardening layer)
Mikrat-silver bromide iodide emulsion (2.0 mol% iodide; average grain diameter 0.08 µm)
0.4 g AgNO, with
1.0 g gelatin
0.5 g hardening agent of the formula

The layer structures 2B, 2C, 2D and 2E made by those listed in Table 2/1 Emulsions instead of those mentioned in the layer structure 2A be used.

The samples were exposed, processed and evaluated analogous to Example 1. The image quality data obtained are listed in Table 2/2.

Teal coupler

Purple coupler

Yellow coupler

Red mask

Yellow masks

Table 2/1

Overview of the emulsions used in Example 2

Table 2/2

Color granularity and interimage effects from Example 2

Claims (6)

1. Color photographic silver halide material with a support and light-sensitive silver halide emulsion layers for the red, green and blue spectral range, to which cyan, magenta and yellow couplers are complementarily assigned, at least three sub-layers of different sensitivity being provided for at least one spectral range, which, seen from the support , have a higher sensitivity with increasing distance, characterized in that the highly sensitive partial layer contains tabular silver halide grains and at least one of the medium sensitive partial layers contains silver halide grains with a layered grain structure. 2. Color photographic silver halide material according to claim 1, characterized in that the three Sub-layers are sensitive to green and / or red. 3. Color photographic silver halide material according to claim 1, characterized in that the lowest sensitive Partial layer of a fine grain emulsion contains whose mean sphere equivalent Grain diameter is at most 0.40 µm. 4. Color photographic silver halide material according to claim 1, characterized in that the equivalent ratio Color coupler to silver halide in  the sub-layer with the lowest sensitivity larger and in the sub-layer with the highest sensitivity is smaller than in at least one of the medium sensitive sub-layers for the same Spectral range. 5. Color photographic silver halide material according to claim 1, characterized in that in the sub-layers with the highest and with the lowest Sensitivity couplers are incorporated whose Coupling speed is greater than that of the Coupler of the medium sensitive layers for the same spectral range. 6. Color photographic silver halide material according to claim 1, characterized in that it

• a) 2-equivalent yellow coupler of the benzoylacetanilide type and / or pivaloylacetanilide type
• b) Purple couplers of the pyrazolo-azole type and / or acylaminopyrazolone type
• c) cyan couplers of the 2-ureidophenol type and / or 1,5-aminonaphthol type and
• d) contains blue-green coupling red mask couplers with an oxygen-bonded escape group.