EP0495364A2 - Colour photographic negative recording material with DIR compounds - Google Patents

Abstract

Using a colour-photographic negative recording material, which contains, for at least one of the blue, green and red spectral regions, a laminate containing silver halide, consisting of a plurality of part layers, and colour coupler, and consisting of at least one central part layer B and part layers A, A', A'', A''', ..., located above and below, the central part layer B having a sensitivity which is at least 3 DIN higher than that of any of the part layers A, A', A'', A''', ..., and the part layer B containing a DIR compound which is capable of releasing an inhibitor having a diffusibility of not less than 0.4, low colour graininess and high interimage effects are obtained together with a reduced application of silver halide.

Description

The invention relates to a color photographic negative recording material with at least one color coupler-containing photosensitive silver halide emulsion layer for each of the spectral ranges blue, green, red, for at least one of the spectral ranges blue, green, red a silver halide and color coupler consisting of several partial layers and in at least one of the laminates contains a DIR connection. Through a special selection and arrangement of the individual sub-layers within the laminate mentioned and through a special selection of suitable DIR compounds, in particular DIR couplers, a color photographic negative recording material is created which, with a comparatively low silver halide application, enables a good color granularity and high interimage effect.

To improve the color rendering, modern color photographic recording materials based on silver halide generally contain so-called DIR couplers (DIR = development inhibitor releasing). Due to the inhibitory effect of these DIR couplers in the development of the silver halide emulsion layer, a flat gradation is created in the layer structure after white exposure than after color separation exposure (e.g. only with red, only with green or only with blue light). This effect is referred to in the literature as the inter-image effect (IIE).

The IIE (TH James, The Theory of the Photographic Process, 4th edition, Mc Millan Co. NY (1977) pp. 574 and 614) is measured as a percentage distribution of the color gradation with color separation exposure with light of the corresponding spectral range in relation to that color gradation , which arises when exposed to white light.

Further advantageous effects of DIR couplers consist in the improved color granularity and in the improved sharpness due to high so-called edge effects (literature: CR Barr, JR Thistle, PW Vittum: "Development-Inhibitor-Releasing (DIR) Couplers in Color Photography", Phot. Sci. Eng. 13 , 74, 214 (1969)).

Modern color photographic recording materials also generally contain not only a silver halide layer for each of the spectral ranges blue, green, red, but several sub-layers that are separate differ in their sensitivity (e.g. DE-C-1 121 470). Such partial layers of the same spectral sensitivity can each be arranged adjacent to one another in the layer structure in the form of double or multiple layer packages; However, layer structures are also known where individual partial layers (each separated from one another by separating or filter layers) are arranged alternately (for example DE-A-1 958 709, DE-A-25 30 645; DE-A-26 22 922). DE-A-31 13 003 describes a photographic recording material with a laminate consisting of several sub-layers, in which a comparatively more sensitive silver halide emulsion (sub) layer is enclosed between comparatively less sensitive sub-layers containing color couplers. DIR couplers can be present in both the more sensitive and the less sensitive sub-layers. This material is said to achieve improved sharpness and graininess with higher sensitivity.

DIR couplers can be contained in one or more silver halide emulsion layers of a color photographic recording material, depending on the intended use. Appropriately, at least one blue-sensitive, one green-sensitive and one red-sensitive layer each contain a suitable DIR coupler, and if there are several sub-layers of different sensitivity for one or more of the spectral ranges blue, green, red, the DIR coupler is expediently at least in one less sensitive sub-layer of a multi-layer system has essentially the same spectral sensitivity. DIR-couplers which are able to release an inhibitor with a high diffusibility ("diffusive development inhibitor-releasing compound") can also be used in such a way that their amount is greatest in a less sensitive partial layer (EP-A-0 318 992) . In order to achieve the greatest possible effect in one way or another with the smallest possible amount of a DIR coupler used, it is favorable to use those DIR couplers which release inhibitors with the greatest possible inhibition strength during development.

The aim of the invention is to provide a color photographic negative recording material which, with a given photosensitivity and a given exposure latitude, has the least possible granularity and the highest possible interimage effects with as little silver halide application per m² as possible.

For ecological reasons, photographic materials with the lowest possible silver halide application (AgX) per m² are aimed for, since layers with less AgX require less aggressive processing baths, shorter regeneration times and less watering.

On the other hand, merely reducing the amount of silver halide applied in conventional layer structures either reduces the photographic sensitivity, reduces the exposure latitude (expressed by maximum color density and / or gradation) or increases the color grain. In addition, it is difficult to achieve sufficiently high interimage effects with layer structures of low silver halide application.

The present invention has for its object to provide a color negative photographic material in which the silver halide can be reduced without loss of light sensitivity, exposure latitude or interimage effects or deterioration in color grain.

The invention relates to a color photographic negative recording material with at least one color-coupler-containing light-sensitive silver halide emulsion layer for each of the spectral ranges blue, green, red, which contains a silver halide and color coupler consisting of several sub-layers for at least one of the spectral ranges blue, green, red at least one middle sub-layer B and sub-layers A, A ', A' ', A' '', ..... arranged above and below, the middle sub-layer B having a sensitivity which is at least 3 DIN higher than that of each of the sub-layers A, A ', A' ', A' '', ..., characterized in that the sub-layer B contains a DIR compound which is able to release an inhibitor with a diffusibility of not less than 0.4.

For at least one of the spectral ranges blue, green, red, preferably for each of these spectral ranges, there is a laminate consisting of several sub-layers. These laminates have, for example, one of the following structures:

However, there may also be further partial layers (A, A '...) of a comparatively lower sensitivity. Likewise, the comparatively more sensitive sub-layer B can itself be subdivided into further sub-layers. The difference in light sensitivity between sub-layer B and each of sub-layers A, A ', A' ', A' '', .... is at least 3 DIN, preferably at least 5 DIN.

Within a laminate, the sub-layers A, A ', A' ', A' '', ..., if they are at all appreciably sensitive to light, have the same or a similar spectral sensitivity as the sub-layer B, i.e. the sub-layers of a laminate are essentially sensitive to light of the same spectral range.

The partial layers A, A ', A' ', A' '' ..., like the light-sensitive partial layer B, can contain light-sensitive silver halide; however, the type and composition of the silver halide can differ from one another. The partial layers of a laminate, but at least one or more of them, contain color couplers for the chromogenic narrowing of an image dye which is generally complementary to the spectral sensitivity of the laminate.

The recording material according to the invention also contains, in at least one comparatively more sensitive sub-layer B, a DIR compound which during development can release an inhibitor with a diffusibility D _f of not less than 0.4.

With regard to the definition of diffusibility D _f and a method for its determination, reference is made to EP-A-0 115 302.

Diffusibility D _f is determined and defined for the purposes of the present invention using the following method:
Multilayer test materials A and B were made as follows:

Test material A

Schicht 1

rotsensibilisierte Silberhalogenidemulsion der angegebenen Art aus 4,57 g AgNO₃
0,754 g Blaugrünkuppler K, gelöst in
0,6 g Dibutylphthalat und dispergiert
0,603 g Gelatine

Schicht 2

unsensibilisierte Silberhalogenidemulsion
aus
2,63 g AgNO₃
2,63 g AgNO₃
0,38 g Weißkuppler L
1,17 g Gelatine

Schicht 3

Schutzschicht mit
1,33 g Gelatine

Schicht 4

Härtungsschicht mit
0,82 g Gelatine
0,54 g Carbamoylpyrimiumsalz (CAS Reg.
No. 65411-60-1).

The following layers are applied to a transparent cellulose triacetate support in the order given.
The quantities refer to 1 m². For the silver halide application, the corresponding amount of AgNO₃ is given. The silver halide emulsions are stabilized with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per 100 g of AgNO₃.
Silver halide emulsion: Silver bromide iodide emulsion with 7 mol% iodide, average grain diameter 0.5 µm, cube-shaped crystals with rounded corners.

Layer 1

red-sensitized silver halide emulsion of the specified type from 4.57 g AgNO₃
0.754 g cyan coupler K, dissolved in
0.6 g dibutyl phthalate and dispersed
0.603 g gelatin

Layer 2

unsensitized silver halide emulsion
out
2.63 g AgNO₃
2.63 g AgNO₃
0.38 g white coupler L
1.17 g gelatin

Layer 3

Protective layer with
1.33 g gelatin

Layer 4

Hardening layer with
0.82 g gelatin
0.54 g carbamoyl pyrimium salt (CAS Reg.
No. 65411-60-1).

Test material B

A test material B was also produced in the same way, but with the change compared to test material A that layer 2 is composed
0.346 g white coupler and
0.900 g gelatin.

The test materials A and B are exposed in a dark room under room lighting with a 100 watt incandescent lamp at a distance of 1.5 m and an exposure time of 15 min.

Development is carried out as described in "The Journal of Photography", 1974 , pages 597 and 598, with the change that the developer has been diluted by 20% with water.

Modified developers containing the development inhibitor to be tested are prepared in such a way that a 0.02 molar solution of the inhibitor in a methanol / water mixture (8: 2), which, if necessary, NaOH up to a pH of 9 contains, the developer is added and a 20% by volume diluted developer results by adding water.

Test materials A and B are each developed in the (modified) developer containing the inhibitor and in the developer not containing the inhibitor and processed in the further steps.

The resulting blue green densities are measured with a densitometer.

worin bedeuten:

D_Ao, D_Bo

Farbdichte der Testmaterialien A bzw. nach Entwicklung in dem angegebenen Entwickler ohne Inhibitorzusatz

D_A, D_B

Farbdichte der Testmaterialien A bzw. B nach Entwicklung in dem angegebenen Entwickler, der den Inhibitor in einer solchen Konzentration enthält, daß folgende Gleichung gilt:

The diffusibility D _f is determined according to the following equation:

in which mean:

D _Ao , D _Bo

Color density of test materials A or after development in the specified developer without the addition of inhibitor

D _A , D _B

Color density of test materials A and B after development in the specified developer, which contains the inhibitor in such a concentration that the following equation applies:

The diffusibility D _{f is} given below for a large number of inhibitors.

The inhibitors are used in the layers of the color photographic recording material in the form of so-called DIR compounds, from which they are released imagewise during development in accordance with a previous exposure and then, if appropriate, develop their inhibiting effect after diffusion into other layers. The DIR compounds are essentially coupling compounds, ie compounds which are able to enter into a coupling reaction with the oxidation products of the color developer used. As a result of this coupling reaction, the inhibitor residue is then released set. The term DIR compound was chosen to clarify that the invention is not limited to the use of color coupling DIR couplers, but also includes those compounds which release inhibitor on reaction with the color developer oxidation products without at the same time contributing significantly to the development of a color image . Nevertheless, the use of DIR couplers is preferred.

Since it is desirable that the released inhibitors intervene in the development process as early as possible, it is of great advantage if the DIR compounds are very reactive, i.e. have a high reaction rate when reacting with developer oxidation products.

A method for determining the coupling reactivity is described in DE-A-27 04 797. DIR compounds preferred according to the invention have a reactivity k of greater than 5000 1 · mol ·¹ · s⁻¹, examples of suitable DIR compounds are listed below.

The sub-layer B of a laminate according to the invention as well as one, more or all of the sub-layers A, A ', A'',A''' ... can also contain further DIR compounds, the diffusibility D _f of the inhibitors released therefrom each may also be less than 0.4 depending on the application.

DIR couplers, the development inhibitors of the azole type, e.g. Release 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. Other advantages for color rendering, i.e. Color separation and color purity, and for detail reproduction, i.e. Sharpness and graininess can be achieved with such DIR couplers, which e.g. do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after a further subsequent reaction, which is achieved, for example, with a timing group. Examples of these are in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-0 157 146 and 0 204 175, in US-A-4 146 396 and 4 438 393 and in GB-A-2 072 363.

DIR couplers which release a development inhibitor which is decomposed into essentially photographically ineffective products in the developer bath are described, for example, in DE-A-32 09 486 and in EP-A-0 167 168 and 0 219 713. This measure ensures trouble-free development and processing consistency.

When using DIR couplers, in particular those which release a development diffuser which is readily diffusible, suitable measures for optical sensitization can be used to improve 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.

It has also proven to be advantageous if a polymer coupler or latex coupler instead of a low molecular weight color coupler is present as a color coupler in at least one of the sub-layers A, A ', A' ', A' ''. Sub-layer B can also contain such polymer couplers or latex couplers. When using polymer couplers or latex couplers instead of conventional low molecular weight couplers, it is possible to achieve a significantly improved image sharpness with the same silver application.

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, EP-A-0 341 089, US-A-4 612 278, US-A-4 578 346. 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.

Under suitable reaction conditions, e.g. in the production by emulsion polymerization, the polymer couplers are in the form of latices (latex couplers) and can be directly mixed in this form with the casting solutions for the photographic layers.

So-called loaded latices, in which latices are loaded with color couplers, are also suitable for the layer structures according to the invention. Such loaded latices are described for example in:
DE-OS 2 541 274, DE-A-2 835 856, DE-A-2 820 092, DE-A-2 541 230, DE-A-2 815 635, US-A-4 199 363, US-A -4,388,403, EP-A-0 069 671, EP-A-0 014 021.

When using latex couplers or latexes loaded with couplers, comparatively thin layers of low binder (A, A ', A'',A''' ...) can be produced, which has an advantageous effect in terms of a smaller thickness of the entire layer structure. In addition, one, several or all of the sub-layers A, A ', A'',A''' .... of a laminate can be completely free of silver halide. The ratio of coupler to silver halide (in equivalents) for the partial layers A, A ', A'',A''' ..... is generally greater than 0.2 and thus greater than the relevant ratio for the partial layer B .

All of these measures interact advantageously, so that it is possible by means of the invention to significantly reduce the total silver halide application of the recording material without impairing sensitivity and graininess. The recording material preferably has a total silver halide application of less than 8.0 g AgNO₃ / m².

Another advantage is that the intermediate layers or separating layers that are usually present between laminates of different spectral sensitivity can also be dispensed with without impairing the color separation.

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 portion of at least one layer can contain 0 to 15 mol% of iodide and 0 to 100 mol% of chloride and consist of 0 to 100 mol% of bromide. Silver bromide or silver bromide iodide emulsions are usually used, optionally with a small proportion of silver chloride. The crystals can be predominantly compact, which are, for example, regularly cubic or octahedral or can have transitional forms. However, platelet-shaped crystals (so-called T-grains) can also preferably be present, the average ratio of diameter to thickness (aspect ratio) of which is preferred 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, for example 12: 1 to 30: 1. Preferably, at least one of the sub-layers A, A ', A'',A''' ... and / or the sub-layer B contains a silver halide T-grain emulsion with an aspect ratio of not less than 7: 1. T-grain emulsions are described, for example, in DE-A-32 41 635, DE-A-32 41 647 and US-A-4 952 491.

The silver halide grains of at least one of the above-mentioned partial layers can preferably 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, for example. 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 both homodisperse and heterodisperse, homodisperse grain size distribution means that 95% of the grains do not exceed ± 30 % deviate from the average grain size. 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.

Gelatin is preferably used as a binder for the photographic layers. However, this can be replaced in whole or in part by other natural or synthetic binders.

The emulsions can be chemically and / or spectrally sensitized in the usual way, and the emulsion layers as well as other non-light-sensitive layers can be hardened in the usual way with known hardening agents.

Color photographic recording materials usually contain at least one silver halide emulsion layer each for recording light from the three spectral ranges blue, green and red. For this purpose, the light-sensitive layers are spectrally sensitized in a known manner by means of suitable sensitizing dyes. Blue-sensitive silver halide emulsion layers do not necessarily have to contain a spectral sensitizer, since in many cases the intrinsic sensitivity of the silver halide (e.g. silver bromide) is sufficient for the recording of blue light.

According to the invention, at least one of the silver halide emulsion layers is in the form of a laminate consisting of partial layers A, A ', A'',A''', ... B. Such a laminate is preferably present for each of the spectral ranges blue, green, red.

However, other arrangements are also conceivable. A layer which is not sensitive to light is generally arranged between layers of different spectral sensitivity and can contain means for preventing the incorrect diffusion of developer oxidation products. If there are several silver halide emulsion layers of the same spectral sensitivity, these can be immediately adjacent to one another or arranged in such a way that a light-sensitive layer with a different spectral sensitivity is located between them (DE-A-1 958 709, DE-A-2 530 645, DE-A -2 622 922).

Each of these laminates contains, in spatial and spectral association with the light-sensitive silver halide contained therein, one or more color couplers for producing the partial color image yellow, magenta or cyan which is complementary to the spectral sensitivity.

Spatial assignment is understood to mean that the color coupler is in such a spatial relationship to the silver halide of the same laminate that an interaction between them is possible that creates an image-like correspondence between the silver image formed during development and that produced from the color coupler Color picture allows. This is usually achieved by the fact that the color coupler is contained in the silver halide emulsion layer itself or in a possibly non-light-sensitive binder layer adjacent to it.

Spectral assignment is understood to mean that the spectral sensitivity of each of the light-sensitive silver halide emulsion layers and the color of the partial color image generated from the spatially assigned color coupler are complementary to one another.

Each of the different spectrally sensitized laminates can contain one or more color couplers. If there are several silver halide emulsion layers of the same spectral sensitivity, each of them can contain a color coupler, which color couplers need not necessarily be identical. They should only result in at least approximately the same color during color development.

worin bedeuten:

X

H oder eine unter den Bedingungen der Farbentwicklung freisetzbare Gruppe, die dem Kuppler keine Farbe verleiht;

R¹

Alkyl oder Aryl;

R²

H, Alkyl, Aralkyl, Acyl, wobei der Acylrest sich von aliphatischen oder aromatischen Carbon- oder Sulfonsäuren von N-substituierten Carbamin- oder Sulfinsäuren oder von Kohlensäurehalbestern ableitet, oder

oder

R³

Alkyl;

R⁴

eine heterocyclische Gruppe oder Aryl;

R⁵

einen Ballastrest;

R¹ bis R⁵

können vorzugsweise auch Teile einer Polymerkette sein.

Color couplers for producing the blue-green partial color image are usually couplers of the phenol or α-naphthol type; cyan couplers of the general formulas I and II are preferably used

in which mean:

X

H or a group that can be released under the conditions of color development that does not impart color to the coupler;

R¹

Alkyl or aryl;

R²

H, alkyl, aralkyl, acyl, where the acyl radical is derived from aliphatic or aromatic carboxylic or sulfonic acids from N-substituted carbamic or sulfinic acids or from carbonic acid semiesters, or

or

R³

Alkyl;

R⁴

a heterocyclic group or aryl;

R⁵

a ballast residue;

R¹ to R⁵

can preferably also be parts of a polymer chain.

Cyan couplers of the formula I are described, for example, in EP-A-0 161 626. Cyan couplers of the formula II are described, for example, in EP-A-0 067 689 and DE-A-39 33 899.

worin bedeuten

X

H oder eine unter den Bedingungen der Farbentwicklung freisetzbare Gruppe;

Y

einen oder mehrere Substituenten, z.B. Cl, Alkoxy, Alkylthio, Alkylsulfonyl, Acylamino;

R¹

Acylamino, gegebenenfalls mit einer Ballastgruppe;

R², R³

H, Alkyl, Aralkyl, Aryl, Alkoxy, Aroxy, Alkylthio, Arylthio, Amino, Anilino, Acylamino, Cyano, Alkoxycarbonyl, Carbamoyl, Sulfamoyl, wobei diese Reste weiter substituiert sein können.

R¹ bis R³

können auch vorzugsweise Teile einer Polymerkette sein.

Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; magenta couplers of the general formulas III, IV and V are preferably used

in what mean

X

H or a group releasable under the conditions of color development;

Y

one or more substituents, for example Cl, alkoxy, alkylthio, alkylsulfonyl, acylamino;

R¹

Acylamino, optionally with a ballast group;

R², R³

H, alkyl, aralkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, carbamoyl, sulfamoyl, where these radicals can be further substituted.

R¹ to R³

can also preferably be part of a polymer chain.

Magenta couplers of this type are described for example in US-A-3 725 067 and US-A-4 540 654.

Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the α-acylacetamide type; Suitable examples are α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers, preferably those that are bound to polymers.

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 site 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). The 2-equivalent couplers are also those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and which 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.

In addition to the constituents mentioned, the color photographic recording material of the present invention can contain further additives, for example antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties. In order to reduce or avoid the disadvantageous effect of UV light on the color images produced with the color photographic recording material according to the invention, it is advantageous to use one or more of those in the recording material contained layers, preferably in one of the upper layers, to use UV-absorbing compounds. Suitable UV absorbers are described for example in US-A-3 253 921, DE-C-2 036 719 and EP-A-0 057 160.

The usual layer supports can be used for the materials according to the invention, see Research Disclosure No. 17 643, Section XVII.

The usual hydrophilic film-forming agents are suitable as protective colloid or binder for the layers of the recording material, e.g. Proteins, especially gelatin. Casting aids and plasticizers can be used. Reference is made to the compounds specified in Research Disclosure No. 17,643 in Sections IX, XI and XII.

The layers of the photographic material can be hardened in the usual manner, for example with hardeners of the epoxy type, the heterocyclic ethylene imine and the acryloyl type. Furthermore, it is also possible to harden the layers according to the process of DE-A-22 18 009 in order to obtain color photographic materials which are suitable for high-temperature processing. It is also possible to harden the photographic layers with hardeners of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type. Further suitable hardening agents are known from DE-A-24 39 551, DE-A-22 25 230, DE-A-23 17 672 and from Research Disclosure 17 643, Section XI given above.

Further suitable additives are given in Research Disclosure 17 643 and in "Product Licensing INDEX" from December 1971, pages 107-110.

In order to produce color photographic images, the color photographic recording material according to the invention is developed with a color developer compound. All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine 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-methylsulfonamidoethyl) -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 , 3100 (1951) and in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, pages 545 ff.

After color development, the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together. The usual compounds can be used as bleaching agents, for example Fe³⁺ salts and Fe³⁺ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes etc. are particularly preferred Iron III complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediamine triacetic acid, alkyliminodicarboxylic acids and of corresponding phosphonic acids. Persulphates are also suitable as bleaching agents.

example 1

A color photographic recording material for the color negative color development was prepared (layer structures 1a to 1c by applying the following layers in the order given to a transparent cellulose triacetate support. The amounts given are based on 1 m². The corresponding amounts of AgNO₃ are given for the silver halide application. All silver halide emulsions were stabilized per 100 g of AgNO₃ with 0.1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

Wetting agents and other pouring aids were added as usual. The viscosity required for casting was set with the polymeric thickener VM-1.

Layer structure 1a (invention)

Layer 1

(Antihalation layer)
black colloidal silver sol with
0.2 g Ag
1.2 g gelatin

Layer 2

(red-sensitive layer A) red-sensitized silver bromide iodide emulsion
(3 mol% iodide;
average grain diameter 0.25 µm)
out
0.25 g AgNO₃, with
0.60 g gelatin
0.85 g cyan coupler C-1

Layer 3

(red-sensitive layer B) red-sensitized silver bromide iodide (core / shell) emulsion
Core: 11 mol% iodide,
average core diameter 0.5 µm;
Shell: 1.5 mol% iodide;
average total grain diameter 0.85 µm)
out
1.50 g AgNO₃, with
1.00 g gelatin
0.065 g cyan coupler C-2
0.035 g DIR coupler DIR-1
0.080 g tricresyl phosphate (CPM)

Layer 4

(red-sensitive layer A ') red-sensitized silver bromide iodide emulsion
(3 mol% iodide;
average grain diameter 0.25 µm)
out
0.20 g AgNO₃, with
0.65 g gelatin
0.70 g cyan coupler C-1
0.12 g RM-1 red mask

Layer 5

(green sensitive layer A) green sensitized silver bromide iodide emulsion
(4.5 mol% iodide;
average grain diameter 0.24 µm)
out
0.30 g AgNO₃, with
0.80 g gelatin
1.40 g magenta coupler M-1

Layer 6

(green-sensitive layer B) green-sensitized silver bromide iodide (core / shell) emulsion
Core: 8 mol% iodide,
average core diameter 0.45 µm;
Shell: 2 mol% iodide,
average total grain diameter 0.82 µm)
out
1.40 g AgNO₃, with
0.90 g gelatin
0.05 g yellow mask YM-1
0.020 g DIR coupler DIR-1
0.08 g CPM

Layer 7

(Green-sensitive layer A ') green-sensitized silver bromide iodide emulsion
(4.5 mol% iodide;
average grain diameter 0.24 µm)
out
0.20 g AgNO₃, with
0.50 g gelatin
0.70 g magenta coupler M-1
0.10 g yellow mask YM-1
0.10 g CPM

Layer 8

(Yellow filter layer)
yellow colloidal silver sol with
0.04 g Ag,
0.80 g gelatin
0.15 g of 2,5-di-t-pentadecyl hydroquinone
0.40 g CPM
0.60 g polyvinyl pyrrolidone (PVP)

Layer 9

(blue-sensitive layer A) blue-sensitized silver bromide iodide emulsion
(4 mol% iodide;
average grain diameter 0.27 µm)
0.20 g AgNO₃, with
0.45 g gelatin
0.65 g yellow coupler Y-1

Layer 10

(blue-sensitive layer B) blue-sensitized silver bromide iodide (core / shell) emulsion
Core: 12 mol% iodide
average core diameter 0.8 µm;
Shell: 7 mol% iodide,
average total grain diameter 1.05 µm
out
1.25 g AgNO₃, with
0.90 g gelatin
0.35 g yellow coupler Y-1
0.011 g DIR coupler DIR-1
0.015 g CPM

Layer 11

(blue-sensitive layer A ') blue-sensitized silver bromide iodide emulsion
(4 mol% iodide;
average grain diameter 0.27 µm)
out
0.35 g AgNO₃, with
1.25 g gelatin
1.35 g yellow coupler Y-1

Layer 12

(Protective and hardening layer)
out
0.30 g gelatin
0.50 g of curing agent H-1

Layer structure 1 b (comparison)

• Verlagerung der DIR-Kuppler aus den Schichten B in die Schichten A und A, d.h. Schichten B (Schichten 3, 6 und 6) ohne DIR-Kuppler, statt dessen
  in Schichten 2 und 4 je 17,5 mg DIR-1
  in Schichten 5 und 7 je 10 mg DIR-1
  in Schichten 9 und 11 je 5,5 mg DIR-1
• sowie Gradationsanpassung durch Änderung der Silberhalogenid-Aufträge gemäß Tabelle 1 A.

Like layer structure 1a, but with the following changes:

• Relocation of the DIR couplers from layers B to layers A and A, ie layers B (layers 3, 6 and 6) without DIR couplers instead
  in layers 2 and 4 each 17.5 mg DIR-1
  in layers 5 and 7 each 10 mg DIR-1
  in layers 9 and 11 each 5.5 mg DIR-1
• and gradation adjustment by changing the silver halide deposits according to Table 1A.

Layer structure 1c (comparison)

Like layer structure 1a, but all layers without DIR coupler and gradation adjustment by changing the silver halide deposits according to Table 1A. Table 1A Silver halide applications (in g AgNO₃ / m²) of the layer structures (1a - 1c) layer Structure 1a Structure 1b Structure 1c 2nd 0.25 0.28 0.25 3rd 1.50 1.30 1.33 4th 0.20 0.25 0.25 5 0.30 0.32 0.30 6 1.40 1.12 1.14 7 0.20 0.23 0.20 9 0.20 0.25 0.20 10th 1.25 1.08 1.12 11 0.35 0.38 0.35 total 5.65 5.21 5.14

One sample each of the layer structures 1a to 1c was exposed behind a gray step wedge with white light (exposure time: 0.01 s) and according to a color negative processing method, as in "The British Journal of Photography (1974), pages 597 and 598 described, processed.

In the case of white exposure, the gradations and maximum color densities (measured via fog) were the same for the three layer structures 1d to 1c within the experimental errors (± 2.5%), see Table 1B for photosensitivity.

As a measure of the color granularity, the RMS values (= mean fluctuation squares) were determined with a measuring aperture of 48 µm in diameter at different color densities. The measurement method is described in: T.H. James, The Theory of the Photographic Process, 4th ed., MacMillan Publ. Co., New York (1977) p. 619. Numerical values of the measured color granularities are also shown in Table 1B.

To determine the interimage effect, one sample each of the layer structures 1a to 1c was exposed behind a gray step wedge with red, one sample with green and one sample with blue light. The interimage effect then results as a percentage distribution of the color gradation when the color separation is exposed to light of the corresponding spectral range in relation to the color gradation that is obtained when exposed to white light (described for example by TH James, The Theory of the Photographic Process, 4th edition , McMillan Co. NY (1977) pp. 574 and 614).

The interimage effects of the three layer structures 1a to 1c are also shown in Table 1B.

It can be seen from Table 1B that color granularities and interimage effects compared to the DIR coupler-free comparison structure 1c are almost not improved by using the DIR coupler in the sub-layers A and A (see comparison structure 1b), but are probably improved by using the DIR Couplers in the layers B of the layer structure 1a according to the invention.

Example 2 Layer structure 2a (invention)

Layer 1

(Antihalation layer)
as with layer structure 1a to 1c (from example 1)

Layer 2

(red-sensitive layer A) red-sensitized silver chloride bromide iodide emulsion
(2.5 mol% chloride and 4.5 mol% iodide;
average grain diameter 0.18 µm)
out
0.15 g AgNO₃, with
0.30 g gelatin
0.45 g cyan coupler C-3

Layer 3

(red-sensitive layer A '') red-sensitized T-grain emulsion with the following parameters:

Layer 4 (red sensitive layer B)

Schicht 5  (rotempfindliche Schicht A') rotsensibilisierte Silberchloridbromidiodidemulsion
(2,5 mol-% Chlorid und 4,5 mol-% Iodid;
mittlerer Korndurchmesser 0,18 µm)
aus
0,20 g AgNO₃, mit
0,25 g Gelatine
0,60 g Cyankuppler C-3
0,15 g Rotmaske RM-2
Schicht 6  (grünempfindliche Schicht A) grünsensibilisierte Silberchloridbromidiodidemulsion
(2,0 mol-% Chlorid und 3,5 mol-% Iodid;
mittlerer Korndurchmesser 0,17 µm)
aus
0,20 g AgNO₃, mit
0,65 g Gelatine
0,60 g Magentakuppler M-2
Schicht 7  (grünempfindliche Schicht A''),
T-grain-Emulsion wie in Schicht 3, jedoch grünsensibilisiert
aus
0,25 g AgNO₃, mit
0,25 g Gelatine
0,60 g Magentakuppler M-2
Schicht 8  (grünempfindliche Schicht B) grünsensibilisierte T-grain-Emulsion mit folgenden Kenngrößen:

Schicht 9  (grünempfindliche Schicht A') grünsensibilisierte Silberchloridbromidiodidemulsion wie in Schicht 6
aus
0,15 g AgNO₃, mit
0,48 g Gelatine
0,45 g Magentakuppler M-2
0,10 g Gelbmaske YM-2
0,10 g TKP
Schicht 10  (Gelbfilterschicht)
gelbes kolloidales Silbersol mit
0,04 g Ag,
0,80 g Gelatine
0,15 g 2,5-Di-t-pentadecylhydrochinon
0,40 g TKP
Schicht 11  (blauempfindliche Schicht A) blausensibilisierte Silberchloridbromidiodidemulsion
(1,5 mol-% Chlorid und 3,5 mol-% Iodid;
mittlerer Korndurchmesser 0,30 µm)
aus
0,25 g AgNO₃, mit
0,50 g Gelatine
0,75 g Gelbkuppler Y-2
Schicht 12  (blauempfindliche Schicht B) blausensibilisierte Silberbromidiodidemulsion
(9,0 mol-% Iodid;
mittlerer Korndurchmesser 1,25 µm)
aus
1,20 g AgNO₃, mit
1,00 g Gelatine
0,40 g Gelbkuppler Y-3
0,009 g DIR-Kuppler DIR-4
0,01 g TKP
Schicht 13  (blauempfindliche Schicht A') blausensibilisierte Silberchloridbromidiodidemulsion wie in Schicht 11
aus
0,30 g AgNO₃, mit
0,40 g Gelatine
0,90 g Gelbkuppler Y-2
Schicht 14  (Schutz- und Härtungsschicht)
0,30 g Gelatine
0,45 g Härtungsmittel H-2

Layer 5 (red sensitive layer A ') red sensitized silver chloride bromide iodide emulsion
(2.5 mol% chloride and 4.5 mol% iodide;
average grain diameter 0.18 µm)
out
0.20 g AgNO₃, with
0.25 g gelatin
0.60 g cyan coupler C-3
0.15 g RM-2 red mask
Layer 6 (green sensitive layer A) green sensitized silver chloride bromide iodide emulsion
(2.0 mol% chloride and 3.5 mol% iodide;
average grain diameter 0.17 µm)
out
0.20 g AgNO₃, with
0.65 g gelatin
0.60 g magenta coupler M-2
Layer 7 (green sensitive layer A ''),
T-grain emulsion as in layer 3, but green-sensitized
out
0.25 g AgNO₃, with
0.25 g gelatin
0.60 g magenta coupler M-2
Layer 8 (green-sensitive layer B) green-sensitized T-grain emulsion with the following parameters:

Layer 9 (green sensitive layer A ') green sensitized silver chloride bromide iodide emulsion as in layer 6
out
0.15 g AgNO₃, with
0.48 g gelatin
0.45 g magenta coupler M-2
0.10 g yellow mask YM-2
0.10 g CPM
Layer 10 (yellow filter layer)
yellow colloidal silver sol with
0.04 g Ag,
0.80 g gelatin
0.15 g of 2,5-di-t-pentadecyl hydroquinone
0.40 g CPM
Layer 11 (blue sensitive layer A) blue sensitized silver chloride bromide iodide emulsion
(1.5 mol% chloride and 3.5 mol% iodide;
average grain diameter 0.30 µm)
out
0.25 g AgNO₃, with
0.50 g gelatin
0.75 g yellow coupler Y-2
Layer 12 (blue sensitive layer B) blue sensitized silver bromide iodide emulsion
(9.0 mol% iodide;
average grain diameter 1.25 µm)
out
1.20 g AgNO₃, with
1.00 g gelatin
0.40 g yellow coupler Y-3
0.009 g DIR coupler DIR-4
0.01 g CPM
Layer 13 (blue-sensitive layer A ') blue-sensitized silver chloride bromide iodide emulsion as in layer 11
out
0.30 g AgNO₃, with
0.40 g gelatin
0.90 g yellow coupler Y-2
Layer 14 (protective and hardening layer)
0.30 g gelatin
0.45 g of H-2 curing agent

Layer structure 2b (comparison)

• Verlagerung der DIR-Kuppler aus den Schichten B in die Schichten A und A'', d.h. Schichten B (Schichten 4, 8 und 12) ohne DIR-Kuppler,
  statt dessen
  in Schicht 2 : 2 mg DIR-3 und 4 mg DIR-2
  in Schicht 3 : 4 mg DIR-3 und 6 mg DIR-2
  in Schicht 6 : 6 mg DIR-4
  in Schicht 7 : 6 mg DIR-4
  in Schicht 11: 4 mg DIR-4
  in Schicht 13: 5 mg DIR-4
• sowie Gradationsanpassung durch Änderung der Silberhalogenid-Aufträge gemäß Tabelle 2A.

Like layer structure 2a, but with the following changes:

• Relocation of the DIR couplers from layers B to layers A and A ″, ie layers B (layers 4, 8 and 12) without DIR couplers,
  instead
  in layer 2: 2 mg DIR-3 and 4 mg DIR-2
  in layer 3: 4 mg DIR-3 and 6 mg DIR-2
  in layer 6: 6 mg DIR-4
  in layer 7: 6 mg DIR-4
  in layer 11: 4 mg DIR-4
  in layer 13: 5 mg DIR-4
• and gradation adjustment by changing the silver halide applications according to Table 2A.

Layer structure 2c (comparison)

Like layer structure 2a, but all layers without DIR coupler and gradation adjustment by changing the silver halide deposits according to Table 2A.

Processing and evaluation of the layer structures 2a to 2c as in example 1.

Results see Table 2B. It can be seen that even in Example 2, only using the DIR coupler in the layers B significantly improves the color granularity and the interimage effect (with layer structure 2a) and not, for example, using the DIR coupler (with layer structure 2b ) into the layers A and A '' which are adjacent to each other here. Table 2A Silver halide applications (in g AgNO₃ / m²) of the layer structures (2a to 2c) layer Structure 2a Structure 2b Setup 2c 2nd 0.15 0.18 0.16 3rd 0.30 0.35 0.32 4th 1.30 1.15 1.17 5 0.20 0.22 0.20 6 0.20 0.22 0.22 7 0.25 0.30 0.26 8th 1.20 1.04 1.04 9 0.15 0.18 0.16 11 0.25 0.29 0.27 12 1.20 1.03 1.04 13 0.30 0.37 0.32 total 5.50 5.33 5.16

Example 3 Layer structure 3a (invention)

Layer 1 (antihalo layer like layer 1 of layer structure 1a) layer 1
Layer 2 (blue-sensitive layer A) like layer structure 1a, layer 9 but 0.35 g AgNO₃ / m²
Layer 3 (blue-sensitive layer B) as layer structure 1a, layer 10 but 1.50 g AgNO₃ / m²
Layer 4 (blue-sensitive layer A ') like layer structure 1a, layer 11, however, 0.15 g AgNO₃ / m²
Layer 5 (red sensitive layer A) red sensitized silver chloride bromide emulsion
(3.2 mol% bromide;
average grain diameter 0.28 µm)
out
0.30 g AgNO₃, with
0.75 g gelatin
0.90 g cyan coupler C-1
Layer 6 (red-sensitive layer B) red-sensitized silver chloride bromide T-grain emulsion
(4.0 mol% bromide) with the following parameters:
medium grain diameter 1.65 µm) thickness 0.18 µm Aspect ratio 9: 1 mean sphere equivalents 0.77 µm out
1.20 g AgNO₃, with
1.20 g gelatin
0.15 g cyan coupler C-1
0.04 g DIR coupler DIR-1
0.03 g CPM
Layer 7 (red sensitive layer A ') red sensitized silver chloride bromide emulsion as in layer 5
out
0.15 g AgNO₃, with
0.75 g gelatin
0.95 g cyan coupler C-3
0.15 g red mask RM-1
Layer 8 (green sensitive layer A) green sensitized silver chloride bromide emulsion
(2.6 mol% bromide;
average grain diameter 0.24 µm)
out
0.28 g AgNO₃, with
0.65 g gelatin
1.20 g magenta coupler M-1
0.15 g yellow mask YM-1
0.20 g CPM
Layer 9 (green sensitive layer B) green sensitized silver chloride iodide T-grain emulsion
(2.0 mol% iodide;
medium grain diameter 1.33 µm) thickness 0.19 Aspect ratio 7: 1 average spherical grain size 0.78 µm out
1.10 g AgNO₃, with
0.80 g gelatin
0.10 g magenta coupler M-3
0.05 g DIR coupler DIR-4
0.02 g CPM
Layer 10 (green-sensitive layer A ') green-sensitized silver chloride bromide emulsion as in layer 8 (2.6 mol% bromide;
average grain diameter 0.24 µm)
out
0.10 g AgNO₃, with
0.70 g gelatin
1.40 g magenta coupler M-2
Layer 11 (protective and hardening layer) such as layer structure 2a, layer 14

Layer structure 3b (comparison)

• Verlagerung der DIR-Kuppler aus den Schichten B in die Schichten A und A', d.h. Schichten B (Schichten 3, 6 und 9) ohne DIR-Kuppler,
  statt dessen
  in Schichten 2 und 4: je 6 mg DIR-1
  in Schichten 5 und 7: je 20 mg DIR-1
  in Schichten 8 und 10: je 25 mg DIR-4
• sowie Gradationsanpassung der Silberhalogenid-Aufträge gemäß Tabelle 3A.

Tabelle 3A Silberhalogenid-Aufträge (in g AgNO₃/m²) der Schichtaufbauten (3a bis 3c) Schicht Aufbau 3a Aufbau 3b Aufbau 3c 2 0,35 0,38 0,36 3 1,50 1,40 1,43 4 0,15 0,20 0,15 5 0,30 0,35 0,30 6 1,20 1,15 1,18 7 0,15 0,20 0,16 8 0,28 0,30 0,28 9 1,10 1,00 1,04 10 0,10 0,12 0,10 Gesamt 5,13 5,10 5,00 Like layer structure 3a, but with the following changes:

• Relocation of the DIR couplers from layers B to layers A and A ', ie layers B (layers 3, 6 and 9) without DIR couplers,
  instead
  in layers 2 and 4: 6 mg DIR-1 each
  in layers 5 and 7: 20 mg DIR-1 each
  in layers 8 and 10: 25 mg DIR-4 each
• and gradation adjustment of the silver halide applications according to Table 3A.

Table 3A Silver halide applications (in g AgNO₃ / m²) of the layer structures (3a to 3c) layer Structure 3a Structure 3b Structure 3c 2nd 0.35 0.38 0.36 3rd 1.50 1.40 1.43 4th 0.15 0.20 0.15 5 0.30 0.35 0.30 6 1.20 1.15 1.18 7 0.15 0.20 0.16 8th 0.28 0.30 0.28 9 1.10 1.00 1.04 10th 0.10 0.12 0.10 total 5.13 5.10 5.00

Layer structure 3c (comparison)

Like layer structure 3a, but all layers without DIR coupler and gradation adjustment by changing the silver halide deposits according to Table 3A.

Processing and evaluation of the layer structures 3a to 3c as in example 1.

See Table 3B for results.

It can be seen that even in Example 3, only using the DIR coupler in layers B significantly improves the color and interimage (with layer structure 3a), whereas when using the DIR coupler in layers A and A '(with layer structure 3b ) these sizes, which are important for the image quality, can hardly be improved compared to the DIR coupler-free layer structure 3c.

Layer structure 3a is also characterized by particularly good image sharpness.

Formulas of the substances used in the layer structure examples 1 to 3:

Yellow masks :

Yellow coupler :

DIR coupler :

Hardening agent :

Claims (5)

Color photographic negative recording material with at least one color-coupler-containing photosensitive silver halide emulsion layer for each of the spectral ranges blue, green, red, which for at least one of the spectral ranges blue, green, red contains a silver halide and color coupler consisting of several sub-layers, consisting of at least one middle sub-layer B as well as above and below sub-layers A, A ', A' ', A' '', ...., whereby the middle sub-layer B has at least 3 DIN higher sensitivity than each of the sub-layers A, A ', A' ' , A '' ', ..., characterized in that the sub-layer B contains a DIR coupler which is able to release an inhibitor with a diffusibility of not less than 0.4. Recording material according to claim 1, characterized in that at least one of the sub-layers A, A ', A' ', A' '', ..... contains a polymer coupler. Recording material according to one of Claims 1 and 2, characterized in that at least one of the partial layers A, A ', A'',A''' ..... contains no light-sensitive silver halide. Recording material according to one of claims 1 to 3, characterized by a total silver halide application of not more than 8.0 g AgNO₃ / m². Recording material according to claim 1, characterized in that at least one of the sub-layers A, A ', A' ', A' '' ....., B contains a silver halide emulsion with tabular silver halide grains (aspect ratio at least 7: 1).