EP0377910B1 - Colour-photographic negative-recording material - Google Patents

Description

The invention relates to a color photographic negative recording material which has at least three color coupler-containing silver halide emulsion partial layers of different sensitivity for recording light from at least one of the spectral ranges red, green, blue, the color couplers contained in the most sensitive partial layer and in the least sensitive partial layer coupling faster than the color coupler in the medium-sensitive sub-layer.

It is known (for example from DE-A-1 958 703) that in double-layer color negative recording materials, that is to say recording materials which have two light-sensitive silver halide emulsion partial layers containing color coupler for the same spectral range, sensitivity and graininess can be improved if the color coupler in the sensitive sub-layer couples two to twenty times faster than the color coupler in the less sensitive sub-layer. They are also recording materials known that have three or more sub-layers of different sensitivity for the same spectral range. It is also known that the use of DIR couplers, even in materials with two or more partial layers, has a favorable effect on sharpness and granularity.

It should now be expected that recording materials with three sublayers for the same spectral range will achieve particularly favorable results if one looks for color couplers for the three sublayers according to their relative coupling speed and assigns them in such a way that the decreasing sensitivity of the individual sublayers leads to a decreasing one relative coupling speed of the color couplers contained therein.

It has now surprisingly been found that without granularity disadvantages, thinner layers and thus improved sharpness can be obtained if a color coupler is used in the least sensitive sub-layer as well as in the most sensitive sub-layer, which couples faster than the color coupler in the medium-sensitive sub-layer.

The invention relates to a color photographic negative recording material containing at least one red-sensitive, at least one green-sensitive and at least one blue-sensitive silver halide emulsion layer, each with assigned color couplers for the generation of spectral sensitivity of complementary colored image dyes, for recording light from at least one of the spectral ranges red, green, blue there are at least three color coupler-containing sub-layers of different sensitivity, namely a most sensitive, a medium-sensitive and a least sensitive sub-layer, at least one of which is used contains a DIR coupler in the more sensitive sub-layers, characterized in that the color coupler used solely for color production in the most sensitive sub-layer and the color coupler contained in the least sensitive sub-layer solely for color production serves by at least a factor of 1.5 (preferably by at least the factor 2) couple faster than the color coupler used only for color generation in the medium-sensitive sub-layer.

If color photographic recording materials for the recording of light from one or more of the three main spectral regions have three or more sub-layers of different sensitivity, then these are usually arranged in such a way that the further away they are from the common substrate, the greater their sensitivity. Color couplers can be assigned to each of the different spectrally related sub-layers, specifically these color couplers can be the same or different. The color couplers are usually selected with regard to their coupling reactivity so that faster coupling couplers are used in a more sensitive sub-layer and slower coupling couplers in a less sensitive sub-layer (DE-A-1 958 709). This rule is deviated from in the case of the recording material according to the invention insofar as the least sensitive sub-layer, a color coupler is used which, compared to the color coupler in the middle, medium-sensitive sub-layer, couples not faster, but faster. According to the present invention, the color coupler contained in the least sensitive sublayer, like the one contained in the most sensitive sublayer, couples faster than the color coupler contained in the middle, medium-sensitive sublayer by at least a factor of 1.5, preferably by at least a factor of 2.0 . When mentioning the clutch speed, reference is made to a relative clutch speed constant k, which can be determined by a method described in DE-A-27 04 797.

The terms "fast", "faster", "slow", "slower" used in the present context are to be understood in a relative sense, in each case with reference to corresponding couplers with the same function in another sub-layer with the same spectral sensitivity. A measure of the mentioned clutch speed is the mentioned relative clutch speed constant; it is given below in the unit 10⁴ · 1 · mol⁻¹ · s⁻¹.

The ratio of the coupling speeds of couplers in the different sub-layers of the same spectral sensitivity required according to the invention applies in any case to the color couplers and in particular to colorless color couplers. Advanced color photographic recording materials also contain Couplers with other functions, for example so-called mask couplers and so-called DIR couplers. In order to be able to cooperate optimally with the actual color couplers, these couplers, which are not limited to the color production alone, should differ from the latter in the relative coupling speed by no more than a factor of 5, preferably no more than a factor of 2, if possible. It is therefore advantageous and therefore preferred if not only the colorless color coupler in the least sensitive sub-layer, but also other couplers contained in this sub-layer, for example a mask coupler, have a higher coupling speed or in any case do not have a significantly lower coupling speed than the corresponding coupler in the middle medium sensitive sub-layer.

If faster couplers are used in the least sensitive partial layer, the sharpness can surprisingly be improved without impairing the granularity, and at the same time the amount of silver halide, especially in the least sensitive partial layer, can be reduced, which also has a favorable effect on the sharpness.

It is also advantageous if the color coupler contained in the least sensitive sub-layer not only couples faster than the color coupler contained in the middle medium-sensitive sub-layer, but also faster than the color coupler in the most sensitive sub-layer. To achieve good (Low) color granularity, especially in the image parts of lower color density (in the negative), it can also be advantageous if the same (fast) color coupler is used in the most sensitive sublayer and in the least sensitive sublayer or different color couplers with approximately the same (high) Coupling speed are used and if the color coupler in the most sensitive sub-layer is further mixed with a color coupler with a lower coupling speed in an amount of up to 90 mol%, based on the total coupler content in the most sensitive sub-layer.

The recording materials according to the invention contain at least one DIR coupler in the medium-sensitive partial layer and / or in the most sensitive partial layer of a layer structure consisting of at least three partial layers of the same spectral sensitivity. The use of DIR couplers and the advantages which can thus be achieved based on interimage effects and edge effects, such as improved color rendering and sharpness, are known. The inhibitors released from the DIR couplers can have low diffusibility (D <0.4) or high diffusibility (D ≥ 0.4). The DIR couplers can also be used as a mixture of two or more DIR couplers. Methods for measuring diffusibility are described, for example, in EP-A-0 101 621 and DE-A-37 36 048.

It is particularly advantageous if the least sensitive partial layer does not contain a DIR coupler.

Examples of color couplers, mask couplers and DIR couplers with which the invention can be implemented are given below with their coupling rate constant k [10⁴ · 1 · mol⁻¹ · s⁻¹]. The diffusibility of the released inhibitor is also indicated for the DIR couplers. However, the invention is not limited to the coupler examples given.

The recording material according to the invention has a large number of differently spectrally sensitized silver halide emulsion layers on a transparent layer support, including at least three silver halide emulsion layers of the same or approximately the same spectral sensitivity, which are referred to in the present context as partial layers. These three sub-layers can be directly adjacent to one another or can also be separated from one another by one or more layers of optionally other spectral sensitivity. At least one such layer structure consisting of three sub-layers of the same spectral sensitivity is equipped with the features according to the invention, which essentially consist in the least sensitive sub-layer as well as the most sensitive sub-layer containing a color coupler that couples at least 1.5 times faster than the color coupler in the medium-sensitive layer of the same spectral sensitivity, wherein at least one of the two more sensitive sub-layers of the same spectral sensitivity contains a DIR coupler and preferably no DIR coupler is contained in the least sensitive sub-layer. Such a multiplicity of partial layers, each consisting of a least sensitive partial layer, a medium-sensitive partial layer and a most sensitive partial layer with the features according to the invention, are advantageously present for each of the three spectral ranges blue, green and red.

With the help of the invention, it is possible to reduce the total silver halide content of the color photographic recording material, expressed by the equivalent amount of AgNO₃, to not more than 10g AgNO₃, preferably not more than 9 g AgNO₃ per m without impairing the color rendering and granularity, thereby improving the sharpness .

The silver halide present as a light-sensitive component in the photographic recording material can contain chloride, bromide or iodide or mixtures thereof as the halide. For example, the halide content of the silver halide in a light-sensitive layer can consist of 0 to 15 mol% of iodide, 0 to 10 mol% of chloride and 0 to 100 mol% of bromide. It can be predominantly compact silver halide crystals, e.g. are regular cubic or octahedral or can have transitional forms.

The silver halide grains can also have a multi-layered grain structure, in the simplest case homodisperse emulsions or mixtures thereof in at least one layer are preferred, with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as doping of the individual grain areas 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 homo- and also be heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ± 30%.

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

Gelatin is preferably used as the binder for the light-sensitive and non-light-sensitive layers. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers. Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, polysccharides, cellulose, sugar, starch or alginates. Semi-synthetic gelatin substitutes are usually modified natural products. Examples of these are cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthaloyl cellulose and gelatin derivatives which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers.

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

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

The silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached. The procedure is described, for example, by H. Frieser "The Basics of Photographic Processes with Silver Halides" page 675-734, Akademische Verlagsgesellschaft (1968).

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

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

Research Disclosure 17643/1978 in Department IV contains an overview of the polymethine dyes suitable as spectral sensitizers, their suitable combinations and combinations with a super-sensitizing effect.

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

The differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it. Usually, the red-sensitive layers are cyan couplers, the green-sensitive layers are magenta couplers and the blue-sensitive layers are yellow couplers.

Color couplers for producing the blue-green partial color image are usually couplers of the phenol or α-naphthol type. Derivatives of ureidophenols or 1,5-aminonaphthols are preferably used.

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

Color couplers for generating the yellow partial color image are usually couplers with an open-chain ketomethylene grouping; especially α-acylacetamide type couplers; suitable examples are α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers.

The color couplers can be 4-equivalent couplers, but also 2-equivalent couplers. The latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point, which is split off during the coupling. The 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products. The 2-equivalent couplers also include couplers that contain a detachable residue in the coupling point, the is set free when reacting with color developer oxidation products, either directly or after one or more further groups have been split off from the primarily split off residue (for example 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, for example as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.

DIR couplers, the mercaptotype development inhibitors, e.g. Release 1-phenyl-5-mercaptotetrazole are described, for example, in US-A-3,227,554 and US-A-3,632,345.

DIR couplers which release development inhibitors of the azole type, for example triazoles and benzotriazoles, are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 27 26 180, 36 26 219, 36 30 564, 36 36 824, 36 44 416, 28 42 063 and EP-A-0 272 573. Further advantages for color reproduction, ie color separation and color purity, and for detail reproduction, ie sharpness and granularity, can be achieved with those DIR couplers which, for example, do not split off the development inhibitor directly as a result of coupling with an oxidized color developer, but only after one further follow-up 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 as well in GB-A-2 072 363.

DIR couplers which release development inhibitors with a high diffusibility (D ≥ 0.4) are described, for example, in EP-A-0 101 621 and DE-A-37 36 048.

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

High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211. The high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.

The couplers or other compounds can be incorporated into silver halide emulsion layers and other layers in such a way that a solution, dispersion or emulsion is first prepared from the compound in question and then added to the casting solution for the layer in question. The selection of the suitable solvent or dispersing agent depends on the solubility of the compound.

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

Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-0 043 037.

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

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

Suitable oil formers are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters), benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.

Examples of suitable oil formers are dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, Tridecylphosphate, tributoxyethylphosphate, trichloropropylphosphate, di-2-ethylhexylphenylphosphate, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostyl-phenyl-tolate, isostearyl-tolyl-isolate, isostearyl-tol-a-tolate, isostyl-phenyl-t-a-tolate, Trioctyl citrate, N, N-dibutyl-2-butoxy-5-t-octylaniline, paraffin, dodecylbenzene and diisopropylnaphthalene.

The non-light-sensitive intermediate layers, which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.

Suitable agents, which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), chapters VII, 17 842 (Feb. 1979) and 18 716 (Nov. 1979), page 650 and in EP A-0 069 070, 0 098 072, 0 124 877 and 0 125 522.

The photographic recording 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.

Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film. Connections of different structures are usually used for the two tasks. Examples are aryl-substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3,707,375), butadiene compounds (US-A-4,045,229) or benzoxazole compounds (US-A-3,700,455).

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

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

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

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

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

Additives to improve the stability of dyes, couplers and whites and to reduce the color fog (Research Disclosure 17 643 (Dec. 1978), Chapter VII) can belong to the following chemical substance classes; Hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, spiroindanes, p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.

Compounds which have both a hindered amine partial structure and a hindered phenol partial structure in one molecule (US-A-4,268,593) are particularly effective in preventing the deterioration of yellow color images as a result of the development of heat, moisture and light. In order to prevent the deterioration of purple color images, in particular as a result of exposure to light, spiroindanes (JP-A-159 644/81) and chromanes which are substituted by hydroquinone diethers or monoethers (JP-A-89 835/80 ) particularly effective.

The layers of the photographic material can be hardened with the usual hardening agents. Suitable curing agents include formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen contain (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207) divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5 triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 732 316 and US-A-2 586 168); Isocyanates (US-A-3 103 437); Aziridine compounds (US-A-3 017 280 and US-A-2 983 611); Acid derivatives (US-A-2 725 294 and US-A-2 725 295); Carbodiimide type compounds (US-A-3 100 704); Carbamoylpyridinium salts (DE-A-22 25 230 and DE-A-24 39 551); Carbamoyloxypyridinium compounds (DE-A-24 08 814); Compounds with a phosphorus-halogen bond (JP-A-113 929/83); N-carbonyloximide compounds (JP-A-43353/81); N-sulfonyloximido compounds, (US-A-4 111 926), dihydroquinoline compounds (US-A-4 013 468), 2-sulfonyloxypyridinium salts (JP-A-110 762/81), formamidinium salts (EP-A-0 162 308 ), Compounds having two or more N-acyloximino groups (US-A-4 052 373), epoxy compounds (US-A-3 091 537), isoxazole-type compounds (US-A-3 321 313 and US-A-3 543 292); Halocarboxyaldehydes such as mucochloric acid; Dioxane derivatives such as dihydroxydioxane and di-chlorodioxane; and inorganic hardeners such as chrome alum and zirconium sulfate.

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

There are slow-acting and fast-acting hardeners and so-called instant hardeners, which are particularly advantageous, in the classes listed.

The last-mentioned hardening agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin with the formation of peptide bonds and crosslinking of the gelatin.

example 1

A color photographic recording material for color negative color development was produced (layer structure 1 A - comparison) by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities are based on 1 m. For the silver halide application, the corresponding amounts of AgNO₃ are given. 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.

Layer structure 1 A (comparison)

• Layer 1 (antihalo layer)
  • black colloidal silver sol with
  • 0.2 g Ag
  • 1.2 g gelatin
  • 0.1 g UV absorber UV-1
  • 0.2 g UV absorber UV-2
  • 0.02 g tricresyl phosphate (CPM)
  • 0.03 g dibutyl phthalate (DBP)
• Layer 2 (Mikrat intermediate layer)
  • Mikrat-silver bromide iodide emulsion (0.5 mol% iodide; average grain diameter 0.07 µm) from 0.25 g AgNO₃, with
  • 1.0 g gelatin
  • 0.05 g RM-2 red mask
  • 0.10 g CPM
• Layer 3 (1st red-sensitized layer, slightly sensitive) from red-sensitized silver bromide iodide emulsion (5.5 mol% iodide; average grain diameter 0.22 µm)
  • 1.20 g AgNO₃, with
  • 1.15 g gelatin
  • 0.52 g cyan coupler C-1
  • 0.03 g RM-1 red mask
  • 0.04 g DIR coupler DIR-3
  • 0.35 g CPM
  • 0.25 g DBP
• Layer 4 (2nd red-sensitized layer, medium-sensitive) from red-sensitized silver bromide iodide emulsion (4.5 mol% iodide; average grain diameter 0.52 µm)
  • 1.62 g AgNO₃, with
  • 1.40 g gelatin
  • 0.45 g cyan coupler C-2
  • 0.02 g RM-1 red mask
  • 0.05 g DIR coupler DIR-1
  • 0.30 g CPM
  • 0.25 g DBP
• Layer 5 (3rd red-sensitized layer, highly sensitive)
  • red-sensitized silver bromide iodide emulsion (8.5 mol% iodide; average grain diameter 0.85 µm) from 1.53 g AgNO₃, with
  • 1.24 g gelatin
  • 0.17 g 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)
  • green-sensitized silver bromide iodide emulsion (5 mol% iodide; average grain diameter 0.23 µm) from 1.06 g AgNO₃, with
  • 0.85 g gelatin
  • 0.36 g magenta coupler M-2
  • 0.04 g yellow mask YM-2
  • 0.04 g DIR coupler DIR-1
• Layer 8 (2nd green sensitized layer, medium sensitive)
  • Green-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.45 µm) from 1.25 g AgNO₃, with
  • 1.05 g gelatin
  • 0.38 g magenta coupler M-3
  • 0.05 g yellow mask YM-2
  • 0.04 g DIR coupler DIR-2
  • 0.35 g CPM
  • 0.15 g DBP
• Layer 9 (3rd green-sensitive layer, highly sensitive)
  • green-sensitized silver bromide iodide emulsion (9 mol% iodide; average grain diameter 0.82 µm)
  • 1.45 g AgNO₃, with
  • 1.1 g gelatin
  • 0.15 g magenta coupler M-4
  • 0.02 g yellow mask YM-3
  • 0.10 g CPM
  • 0.10 g DBP
• Layer 10 (yellow filter layer)
  • yellow colloidal silver sol with
  • 0.04 g Ag, passivated with 6 mg 1-phenyl-5-mercaptotetrazole per g Ag
  • 0.8 g gelatin
  • 0.15 g 2,5-di-t-pentadecyl hydroquinone
  • 0.40 g CPM
• Layer 11 (1st blue-sensitive layer, slightly sensitive)
  • blue-sensitized silver bromide iodide emulsion (4.5 mol% iodide; average grain diameter 0.28 µm)
  • 0.70 g AgNO₃, with
  • 1.2 g gelatin
  • 0.9 g yellow coupler Y-1
  • 0.20 g DIR coupler DIR-2
  • 0.70 g CPM
  • 0.20 g DBP
• Layer 12 (2nd blue-sensitive layer, medium-sensitive),
  • blue-sensitized silver bromide iodide emulsion (5 mol% iodide; average grain diameter 0.5 µm)
  • 0.4 g AgNO₃, with
  • 0.51 g yellow coupler Y-1
  • 0.85 g gelatin
  • 0.10 g DIR coupler DIR-2
  • 0.40 g CPM
  • 0.20 g DBP
• Layer 13 (3rd blue-sensitive layer, highly sensitive)
  • Blue-sensitized silver bromide iodide emulsion (9.5 mol% iodide; average grain diameter 0.94 µm) from 0.81 g AgNO₃, with
  • 0.25 g yellow coupler Y-4
  • 1.0 g gelatin
  • 0.20 g CPM
• Layer 14 (protective and hardening layer) of Mikrat-silver bromide iodide emulsion (0.5 mol% iodide; average grain diameter 0.04 µm)
  • 0.5 g AgNO₃, with
  • 1.2 g gelatin
  • 0.4 g of H-1 curing agent
  • 1.0 g formaldehyde scavenger FF

Gewichtsverhältnis: x : y = 7:3In Example 1, the following compounds are used in addition to the couplers already mentioned:
UV absorber UV-1

Weight ratio: x: y = 7: 3

UV absorber UV-2

Formaldehyde scavenger FF

Hardener H-1

Analog wurden auch die folgenden Schichtaufbauten 1B, 1C, 1D und 1E hergestellt.

The following layer structures 1B, 1C, 1D and 1E were also produced analogously.

Layer structure 1B (comparison):

Schicht 3:

ohne DIR-Kuppler,
AgNO₃-Auftrag 0,82 g
   (statt 1,20 g)

Schicht 7:

ohne DIR-Kuppler,
AgNO₃-Auftrag 0,66 g
   (statt 1,06 g)

Schicht 11:

ohne DIR-Kuppler,
AgNO₃-Auftrag 0,52 g
   (statt 0,70 g).

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

Layer 3:

without DIR coupler,
AgNO₃ order 0.82 g
(instead of 1.20 g)

Layer 7:

without DIR coupler,
AgNO₃ order 0.66 g
(instead of 1.06 g)

Layer 11:

without DIR coupler,
AgNO₃ order 0.52 g
(instead of 0.70 g).

Layer structure 1C (comparison):

Schicht 3:

0,32 g Kuppler C-4 (schnell) (statt 0,52 g Kuppler C-1 (langsam)) 0,028 g Rotmaske RM-2 (schnell) (statt 0,03 g Rotmaske RM-1 (langsam)) AgNO₃-Auftrag 0,93 g (statt 1,20 g)

Schicht 7:

0,24 g Kuppler M-6 (schnell) (statt 0,36 g Kuppler M-2 (langsam)) 0,04 g Gelbmaske YM-3 (schnell) (statt 0,04 g Gelbmaske YM-2 (langsam)) AgNO₃-Auftrag 0,73 g (statt 1,06 g)

Schicht 11:

0,46 g Kuppler Y-6 (schnell) (statt 0,51 g Kuppler Y-2 (langsam)) AgNO₃-Auftrag 0,59 g (statt 0,70 g)

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

Layer 3:

0.32 g coupler C-4 (fast) (instead of 0.52 g coupler C-1 (slow)) 0.028 g red mask RM-2 (fast) (instead of 0.03 g red mask RM-1 (slow)) AgNO₃- Order 0.93 g (instead of 1.20 g)

Layer 7:

0.24 g coupler M-6 (fast) (instead of 0.36 g coupler M-2 (slow)) 0.04 g yellow mask YM-3 (fast) (instead of 0.04 g yellow mask YM-2 (slow)) AgNO₃ order 0.73 g (instead of 1.06 g)

Layer 11:

0.46 g coupler Y-6 (fast) (instead of 0.51 g coupler Y-2 (slow)) AgNO₃ application 0.59 g (instead of 0.70 g)

Layer structure 1D (according to the invention):

Schicht 3:

ohne DIR-Kuppler, AgNO₃-Auftrag 0,50 g (statt 0,93 g)

Schicht 7:

ohne DIR-Kuppler AgNO₃-Auftrag 0,35 g (statt 0,73 g)

Schicht 11:

ohne DIR-Kuppler AgNO₃-Auftrag 0,32 g (statt 0,59 g)

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

Layer 3:

without DIR coupler, AgNO₃ application 0.50 g (instead of 0.93 g)

Layer 7:

without DIR coupler AgNO₃ application 0.35 g (instead of 0.73 g)

Layer 11:

without DIR coupler AgNO₃ application 0.32 g (instead of 0.59 g)

Layer structure 1E (according to the invention):

Schicht 5:

zusätzlich 0,022 g DIR-Kuppler DIR-6 AgNO₃-Auftrag 1,76 (statt 1,53 g)

Schicht 9:

zusätzlich 0,019 g DIR-Kuppler DIR-7 AgNO₃-Auftrag 1,63 g (statt 1,45 g)

Schicht 13:

zusätzlich 0,016 g DIR-Kuppler DIR-7 AgNO₃-Auftrag 1,06 g (statt 0,81 g)

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

Layer 5:

additionally 0.022 g DIR coupler DIR-6 AgNO₃ order 1.76 (instead of 1.53 g)

Layer 9:

additionally 0.019 g DIR coupler DIR-7 AgNO₃ application 1.63 g (instead of 1.45 g)

Layer 13:

additionally 0.016 g DIR coupler DIR-7 AgNO₃ application 1.06 g (instead of 0.81 g)

• 1. Der Kuppler in der hochempfindlichen Teilschicht kuppelt schnell.
• 2. Der Kuppler in der mittelempfindlichen Teilschicht kuppelt langsam.
• 3. Die mittelempfindliche Teilschicht enthält einen DIR-Kuppler.

Table 1a gives an overview of the most important features of layered structures 1A to 1E. All layer structures 1A to 1E correspond in the following points:

• 1. The coupler in the highly sensitive sub-layer couples quickly.
• 2. The coupler in the medium-sensitive sub-layer couples slowly.
• 3. The medium-sensitive sublayer contains a DIR coupler.

• 1. Die geringempfindliche Teilschicht enthält keinen DIR-Kuppler bei den Schichtaufbauten 1B, 1D und 1E.
• 2. Der in der geringempfindlichen Teilschicht enthaltene farblose Kuppler kuppelt langsam bei den Schichtaufbauten 1A und 1B, schnell bei den Schichtaufbauten 1C, 1D und 1E.
• 3. Die hochempfindliche Teilschicht enthält einen DIR-Kuppler nur bei Schichtaufbauten 1E.

However, there are differences in the following points:

• 1. The low-sensitive partial layer does not contain a DIR coupler in the layer structures 1B, 1D and 1E.
• 2. The colorless coupler contained in the low-sensitivity partial layer couples slowly in the layer structures 1A and 1B, quickly in the layer structures 1C, 1D and 1E.
• 3. The highly sensitive partial layer contains a DIR coupler only with layer structures 1E.

Tabelle 1c AgNO₃-Aufträge [g/m] Schichtaufbauten Schicht (Vergleich) (erfindungsgemäß) 1A 1B 1C 1D 1E 1 2 3 1,20 0,82 0,93 0,50 0,50 4 1,62 1,62 1,62 1,62 1,62 5 1,53 1,53 1,53 1,53 1,76 6 7 1,06 0,66 0,73 0,35 0,35 8 1,25 1,25 1,25 1,25 1,25 9 1,45 1,45 1,45 1,45 1,63 10 11 0,70 0,52 0,59 0,32 0,32 12 0,40 0,40 0,40 0,40 0,40 13 0,81 0,81 0,81 0,81 1,06 14 Gesamt 10,02 9,06 9,31 8,23 8,89 Table 1b provides an overview of the couplers, DIR couplers and mask couplers contained in the individual layers of the various layer structures. The relative coupling rate constant k is given in brackets in the unit 10⁴ · 1 · mol⁻¹ · s⁻¹. Table 1c gives an overview of the silver halide deposits contained in the individual layers of the various layer structures in the form of the equivalent amounts of AgNO₃. The total order AgNO₃ is also given.

Table 1c AgNO₃ orders [g / m] Layer structures layer (Comparison) (according to the invention) 1A 1B 1C 1D 1E 1 2nd 3rd 1.20 0.82 0.93 0.50 0.50 4th 1.62 1.62 1.62 1.62 1.62 5 1.53 1.53 1.53 1.53 1.76 6 7 1.06 0.66 0.73 0.35 0.35 8th 1.25 1.25 1.25 1.25 1.25 9 1.45 1.45 1.45 1.45 1.63 10th 11 0.70 0.52 0.59 0.32 0.32 12th 0.40 0.40 0.40 0.40 0.40 13 0.81 0.81 0.81 0.81 1.06 14 total 10.02 9.06 9.31 8.23 8.89

A sample of the layer structures 1A to 1E 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. 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: TH 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 given in Table 1d .

In addition, the modulation transfer function (MTF) on the five layer structures was determined as a measure of the sharpness. This method is described e.g. at T.H. James, p. 604.

As a measure of the sharpness, the spatial frequency (ν in [mm⁻¹] at which the MTF still has a value of 50% is given in Table 1d. The larger this value, the better the sharpness of the image.

It can be seen from this table that the structures 1D and 1E according to the invention have a significantly better sharpness compared to the comparative structures 1A to 1C without deterioration in the color granularity, in particular in the blue-green and purple-colored partial color image.

The sensitivity to light was the same for the setups 1A to 1E within the test fluctuations (± 0.2 DIN).

Example 2

With the same qualitative gradations in the coupling speeds as described in Table 1a (Example 1), but with a different layer sequence, layer structures 2A to 2E were produced with the couplers, DIR couplers and mask couplers shown in Table 2b (the relative coupling speed constant k is in brackets indicated) and the AgNO₃ orders evident from Table 2c. The red-sensitive layers 3, 4 and 11 correspond to the layers 3-5 in Example 1, the green-sensitive layers 6, 7 and 12 correspond to the layers 7-9 in Example 1, and instead of the blue-sensitive layers 11-13 present in Example 1 they contain Layer structures of example 2 only layers 9 and 15. Layers 5, 10 and 12 are intermediate layers and have the same composition as layer 6 in example 1. Layers 8 and 14 are yellow filter layers; each of them has the same composition as layer 10 in Example 1, but contains only half as much silver sol and CPM.

Table 2a provides an overview of the couplers, DIR couplers and mask couplers contained in the individual layers of the various layer structures. The relative coupling rate constant k is given in brackets in the unit 10⁴ · 1 · mol⁻¹ · s⁻¹. A

Tabelle 2b AgNO₃-Aufträge [g/m] Schichtaufbauten Schicht (Vergleich) (erfindungsgemäß) 2A 2B 2C 2D 2E 3 1,26 0,78 0,90 0,45 0,45 4 1,55 1,55 1,55 1,55 1,55 6 1,02 0,71 0,82 0,42 0,42 7 0,96 0,96 0,96 0,96 0,96 9 0,65 0,65 0,65 0,65 0,65 11 1,47 1,47 1,47 1,47 1,62 13 1,18 1,18 1,18 1,18 1,35 15 0,91 0,91 0,91 0,91 1,15 gesamt 9,00 8,21 8,44 7,59 8,15 Table 2b provides an overview of the silver halide deposits in the individual layers of the various layer structures in the form of the equivalent amounts of AgNO₃. The total order AgNO₃ is also given.

Table 2b AgNO₃ orders [g / m] Layer structures layer (Comparison) (according to the invention) 2A 2 B 2C 2D 2E 3rd 1.26 0.78 0.90 0.45 0.45 4th 1.55 1.55 1.55 1.55 1.55 6 1.02 0.71 0.82 0.42 0.42 7 0.96 0.96 0.96 0.96 0.96 9 0.65 0.65 0.65 0.65 0.65 11 1.47 1.47 1.47 1.47 1.62 13 1.18 1.18 1.18 1.18 1.35 15 0.91 0.91 0.91 0.91 1.15 total 9.00 8.21 8.44 7.59 8.15

Details of the layer structures 2A to 2E are given below:

Production of layer structures 2A to 2E

Layer support, amounts and stabilization of the emulsions, layers 1 and 2 as in Example 1.

Layer structure 2A (comparison)

• Layer 3 (1st red-sensitive layer, slightly sensitive)
  • red-sensitized silver chloride bromide iodide emulsion (1.3 mol% iodide; average grain diameter 0.26 µm)
  • 1.26 g AgNO₃, with
  • 1.42 g gelatin
  • 0.48 g cyan coupler C-3
  • 0.05 g DIR coupler DIR-3
  • 0.30 g CPM
  • 0.20 g DBP
• Layer 4 (2nd red-sensitive layer, medium-sensitive) red-sensitized silver chloride bromide iodide emulsion (1.0 mol% chloride, 2.5 mol% iodide; average grain diameter 0.55 µm)
  • 1.55 g AgNO₃, with
  • 1.35 g gelatin
  • 0.38 g cyan coupler C-3
  • 0.03 g RM-2 red mask
  • 0.045 g DIR coupler DIR-6
  • 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)
  • Green-sensitized silver chloride bromide iodide emulsion (1.8 mol% chloride, 3.0 mol% iodide; average grain diameter 0.26 µm) from 1.02 g AgNO₃, with
  • 1.00 g gelatin
  • 0.32 g magenta coupler M-1
  • 0.03 g yellow mask YM-1
  • 0.04 g DIR coupler DIR-1
  • 0.25 g CPM
  • 0.22 g DBP
• Layer 7 (2nd green sensitive layer, medium sensitive)
  • Green-sensitized silver chloride bromide iodide emulsion (0.5 mol% chloride, 2.8 mol% iodide; average grain diameter 0.52 µm) from 0.96 g AgNO₃, with
  • 0.82 g gelatin
  • 0.26 g magenta coupler M-1
  • 0.05 g yellow mask YM-1
  • 0.03 g DIR coupler DIR-4
  • 0.25 g CPM
  • 0.12 g DBP
• Layer 8 (yellow filter layer) yellow colloidal silver sol, passivated with
  • 6 mg 1-phenyl-5-mercaptotetrazole per 1 g Ag
  • 0.02 g Ag
  • 0.8 g gelatin
  • 0.15 g 2,5-di-t-pentadecyl hydroquinone
  • 0.20 g CPM
• Layer 9 (1st blue-sensitive layer, slightly sensitive)
  • blue-sensitized silver bromide iodide emulsion (4.5 mol% iodide; average grain diameter 0.45 µm)
  • 0.65 g AgNO₃, with
  • 1.20 g gelatin
  • 0.90 g yellow coupler Y-2
  • 0.15 g DIR coupler DIR-1
  • 0.80 g CPM
  • 0.50 g DBP
• Layer 10 (intermediate layer) like layer 5
• Layer 11 (3rd red-sensitive layer, highly sensitive)
  • red-sensitized silver bromide iodide emulsion (9.2 mol% iodide; average grain diameter 0.96 µm) from 1.47 g AgNO₃, with
  • 1.30 g gelatin
  • 0.12 g cyan coupler C-5
  • 0.01 g red mask RM-2
  • 0.10 g CPM
  • 0.05 g DBP
• Layer 12 (intermediate layer) like layer 5
• Layer 13 (3rd green-sensitive layer, highly sensitive),
  • green-sensitized silver bromide iodide emulsion (9.5 mol% iodide; average grain diameter 0.95 µm)
  • 1.18 g AgNO₃, with
  • 1.05 g gelatin
  • 0.14 g magenta coupler M-5
  • 0.01 g yellow mask YM-3
  • 0.12 g CPM
  • 0.05 g DBP
• Layer 14 (yellow filter layer) like layer 8
• Layer 15 (2nd blue-sensitive layer, highly sensitive),
  • blue-sensitized silver chloride bromio iodide emulsion (0.8 mol% chloride, 10.5 mol% iodide; average grain diameter 1.1 µm)
  • 0.91 g AgNO₃, with
  • 0.79 g gelatin
  • 0.12 g yellow coupler Y-3
  • 0.10 g CPM
• Layer 16 (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 [CAS Reg.-No. 65411-60-1]
  • 0.8 g formaldehyde scavenger FF

The following layer structures 2B, 2C, 2D and 2E were also produced analogously.

Layer structure 2B (comparison):

Schicht 3:

ohne DIR-Kuppler,
AgNO₃-AufLrag 0,78 g
   (statt 1,26 g)

Schicht 6:

ohne DIR-Kuppler,
AgNO₃-Auftrag 0,71 g
   (statt 1,02 g)

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

Layer 3:

without DIR coupler,
AgNO₃ order 0.78 g
(instead of 1.26 g)

Layer 6:

without DIR coupler,
AgNO₃ order 0.71 g
(instead of 1.02 g)

Layer structure 2C (comparison):

Schicht 3:

0,30 g Cyankuppler C-6 (schnell) (statt 0,48 g Cyankuppler C-3 (langsam)) AgNO₃-Auftrag 0,90 g (statt 1,26 g)

Schicht 6:

0,28 g Magentakuppler M-7 (schnell) (statt 0,32 g Magentakuppler M-1 (langsam))
0,03 g Gelbmaske YM-3 (schnell) (statt 0,03 g Gelbmaske YM-1 (langsam)) AgNO₃-Auftrag 0,82 g (statt 1,02 g)

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

Layer 3:

0.30 g cyan coupler C-6 (fast) (instead of 0.48 g cyan coupler C-3 (slow)) AgNO₃ application 0.90 g (instead of 1.26 g)

Layer 6:

0.28 g magenta coupler M-7 (fast) (instead of 0.32 g magenta coupler M-1 (slow))
0.03 g yellow mask YM-3 (fast) (instead of 0.03 g yellow mask YM-1 (slow)) AgNO₃ application 0.82 g (instead of 1.02 g)

Layer structure 2D (according to the invention):

Schicht 3:

ohne DIR-Kuppler,
AgNO₃-Auftrag 0,45 g (statt 0,90 g)

Schicht 6:

ohne DIR-Kuppler
AgNO₃-Auftrag 0,42 g (statt 0,82 g)

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

Layer 3:

without DIR coupler,
AgNO₃ order 0.45 g (instead of 0.90 g)

Layer 6:

without DIR coupler
AgNO₃ order 0.42 g (instead of 0.82 g)

Layer structure 2E (according to the invention):

Schicht 11:

zusätzlich 0,015 g DIR-Kuppler DIR-8 AgNO₃-Auftrag 1,62 g (statt 1,47 g)

Schicht 13:

zusätzlich 0,018 g DIR-Kuppler DIR-8 AgNO₃-Auftrag 1,35 g (statt 1,18 g)

Schicht 15:

zusätzlich 0,02 g DIR-Kuppler DIR-5 AgNO₃-Auftrag 1,15 g (statt 0,91 g)

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

Layer 11:

additionally 0.015 g DIR coupler DIR-8 AgNO₃ application 1.62 g (instead of 1.47 g)

Layer 13:

additionally 0.018 g DIR coupler DIR-8 AgNO₃ application 1.35 g (instead of 1.18 g)

Layer 15:

additionally 0.02 g DIR coupler DIR-5 AgNO₃ application 1.15 g (instead of 0.91 g)

Processing of the samples and determination of the color granularity and sharpness (i.e. the MTF values) was carried out as described in Example 1.

The values found for the color granularity and for the sharpness of the structures 2A to 2E are shown in Table 2c.

The measures according to the invention improve the sharpness, especially in blue-green and purple, without a deterioration in the color granularity.

The sensitivities for the setups 2A to 2E were the same within the test fluctuations (± 0.2 DIN).

Example 3

With the qualitative gradations of the coupling speeds shown in Table 3a, the layer structures 3A described below (comparison) as well as 3B and 3C (according to the invention) were produced.

Layer support, amounts and stabilization of the emulsions, layers 1, 2, 6 and 10 as in Example 1.

Layer structure 3A (comparison)

• Schicht 3 (1. rotsensibilisierte Schicht, gering empfindlich)
  • rotsensibilisierte Silberbromidiodidemulsion (6,5 mol-% Iodid; mittlerer Korndurchmesser 0,25 µm) aus
  • 0,38 g AgNO₃, mit
  • 0,90 g Gelatine
  • 0 20 g Cyankuppler C-7
  • 0,05 g Rotmaske RM-2
  • 0,20 g DBP
• Schicht 4 (2. rotsensibilisierte Schicht, mittelempfindlich) rotsensibilisierte Silberbromidiodidemulsion (4,8 mol-% Iodid; mittlerer Korndurchmesser 0,45 µm) aus
  • 1,50 g AgNO₃, mit
  • 1,40 g Gelatine
  • 0,45 g Cyankuppler C-2
  • 0,02 g Rotmaske RM-1
  • 0,05 g DIR-Kuppler DIR-1
  • 0,30 g TKP
  • 0,25 g DBP
• Schicht 5 (3. rotsensibilisierte Schicht, hochempfindlich)
  • rotsensibilisierte Silberbromidiodidemulsion (8,0 mol-% Iodid; mittlerer Korndurchmesser 0,90 µm) aus 1,45 g AgNO₃, mit
  • 0,95 g Gelatine
  • 0,15 g Cyankuppler C-2
  • 0,03 g Rotmaske RM-1
  • 0,10 g TKP
  • 0,08 g DBP
• Schicht 6 (Zwischenschicht) wie bei Aufbau 1A
• Schicht 7 (1. grünsensibilisierte Schicht, gering empfindlich)
  • grünsensibilisierte Silberbromidiodidemulsion (5 mol-% Iodid; mittlerer Korndurchmesser 0,23 µm) aus 0,25 g AgNO₃, mit
  • 0,85 g Gelatine
  • 0,36 g Magentakuppler M-5
  • 0,36 g TKP
• Schicht 8 (2. grünsensibilisierte Schicht, mittelempfindlich)
  • grünsensibilisierte Silberbromidiodidemulsion (4 mol-% Iodid; mittlerer Korndurchmesser 0,45 µm) aus 0,70 g AgNO₃, mit
  • 1,05 g Gelatine
  • 0,38 g Magentakuppler M-1
  • 0,05 g Gelbmaske YM-1
  • 0,04 g DIR-Kuppler DIR-2
  • 0,35 g TKP
  • 0,15 g DBP
• Schicht 9 (3. grünempfindliche Schicht, hochempfindlich)
  • grünsensibilisierte Silberbromidiodidemulsion (9 mol-% Iodid; mittlerer Korndurchmesser 0,82 µm) aus
  • 1,40 g AgNO₃, mit
  • 1,1 g Gelatine
  • 0,15 g Magentakuppler M-1
  • 0,02 g Gelbmaske YM-1
  • 0,10 g TKP
  • 0,10 g DBP
• Schicht 10 (Gelbfilterschicht) wie bei Schichtaufbau 1A
• Schicht 11 (blauempfindliche Schicht) Emulsionsabmischung aus
  • a.) einer blausensibilisierten Silberchloridbromidiodidemulsion (2,5 mol-% Chlorid, 4,5 mol-% Iodid; homodispers; Korndurchmesser 0,25 µm) aus 0,65 g AgNO₃, und
  • b.) einer blausensibilisierten Silberbromidemulsion (9,5 mol-% Iodid; homodispers; Korndurchmesser 0,82 µm) aus 0,55 g AgNO₃, mit
  • 1,0 g Gelatine
  • 1,95 g Gelbkuppler Y-6
  • 0,20 g DIR-Kuppler DIR-7
  • 0,70 g TKP
  • 0,20 g DBP
• Schicht 12 (Schutz- und Härtungsschicht) wie Schicht 14 von Schichtaufbau 1A

Layer support, layers 1 and 2 as for layer structure 1A.

• Layer 3 (1st red-sensitized layer, slightly sensitive)
  • red-sensitized silver bromide iodide emulsion (6.5 mol% iodide; average grain diameter 0.25 µm)
  • 0.38 g AgNO₃, with
  • 0.90 g gelatin
  • 0 20 g cyan coupler C-7
  • 0.05 g RM-2 red mask
  • 0.20 g DBP
• Layer 4 (2nd red-sensitized layer, medium-sensitive) red-sensitized silver bromide iodide emulsion (4.8 mol% iodide; average grain diameter 0.45 µm)
  • 1.50 g AgNO₃, with
  • 1.40 g gelatin
  • 0.45 g cyan coupler C-2
  • 0.02 g RM-1 red mask
  • 0.05 g DIR coupler DIR-1
  • 0.30 g CPM
  • 0.25 g DBP
• Layer 5 (3rd red-sensitized layer, highly sensitive)
  • red-sensitized silver bromide iodide emulsion (8.0 mol% iodide; average grain diameter 0.90 µm) from 1.45 g AgNO₃, with
  • 0.95 g gelatin
  • 0.15 g cyan coupler C-2
  • 0.03 g RM-1 red mask
  • 0.10 g CPM
  • 0.08 g DBP
• Layer 6 (intermediate layer) as in structure 1A
• Layer 7 (1st green-sensitized layer, slightly sensitive)
  • green-sensitized silver bromide iodide emulsion (5 mol% iodide; average grain diameter 0.23 µm) from 0.25 g AgNO₃, with
  • 0.85 g gelatin
  • 0.36 g M-5 magenta coupler
  • 0.36 g CPM
• Layer 8 (2nd green sensitized layer, medium sensitive)
  • green-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.45 µm) from 0.70 g AgNO₃, with
  • 1.05 g gelatin
  • 0.38 g magenta coupler M-1
  • 0.05 g yellow mask YM-1
  • 0.04 g DIR coupler DIR-2
  • 0.35 g CPM
  • 0.15 g DBP
• Layer 9 (3rd green-sensitive layer, highly sensitive)
  • green-sensitized silver bromide iodide emulsion (9 mol% iodide; average grain diameter 0.82 µm)
  • 1.40 g AgNO₃, with
  • 1.1 g gelatin
  • 0.15 g magenta coupler M-1
  • 0.02 g yellow mask YM-1
  • 0.10 g CPM
  • 0.10 g DBP
• Layer 10 (yellow filter layer) as with layer structure 1A
• Layer 11 (blue-sensitive layer) emulsion mixture
  • a.) a blue-sensitized silver chloride bromide iodide emulsion (2.5 mol% chloride, 4.5 mol% iodide; homodisperse; grain diameter 0.25 µm) from 0.65 g AgNO₃, and
  • b.) a blue-sensitized silver bromide emulsion (9.5 mol% iodide; homodisperse; grain diameter 0.82 µm) from 0.55 g AgNO₃, with
  • 1.0 g gelatin
  • 1.95 g yellow coupler Y-6
  • 0.20 g DIR coupler DIR-7
  • 0.70 g CPM
  • 0.20 g DBP
• Layer 12 (protective and hardening layer) as layer 14 of layer structure 1A

Layer structure 3B (according to the invention)

Schicht 5:

0,12 g Kuppler C-5
(statt 0,15 g Kuppler C-2)
0,03 g Rotmaske RM-2
(statt 0,03 g Rotmaske RM-1)

Schicht 9:

0,10 g Kuppler M-5
(statt 0,15 g Kuppler M-1)
0,02 g Gelbmaske YM-3
(statt 0,02 g Gelbmaske YM-1

like layer structure 3A but with the following changes:

Layer 5:

0.12 g coupler C-5
(instead of 0.15 g coupler C-2)
0.03 g RM-2 red mask
(instead of 0.03 g RM-1 red mask)

Layer 9:

0.10 g coupler M-5
(instead of 0.15 g coupler M-1)
0.02 g yellow mask YM-3
(instead of 0.02 g yellow mask YM-1

Layer structure 3C (according to the invention)

Schicht 5:

0,05 g Kuppler C-5 und
   0,10 g Kuppler C-2
   (statt 0,15 g Kuppler C-2)
   0,03 g Rotmaske RM-2
   (statt 0,03 g Rotmaske RM-1)

Schicht 9:

0,075 g Kuppler M-5 und
   0,075 g Kuppler M-1
   (statt 0,15 g Kuppler M-1)
   0,02 g Gelbmaske YM-3
   (statt 0,02 g Gelbmaske YM-1)

Like layer structure 3A but with the following changes:

Layer 5:

0.05 g coupler C-5 and
0.10 g coupler C-2
(instead of 0.15 g coupler C-2)
0.03 g RM-2 red mask
(instead of 0.03 g RM-1 red mask)

Layer 9:

0.075 g coupler M-5 and
0.075 g coupler M-1
(instead of 0.15 g coupler M-1)
0.02 g yellow mask YM-3
(instead of 0.02 g yellow mask YM-1)

Table 3b provides an overview of the couplers, DIR couplers and mask couplers contained in the individual layers of the layer structures 3A and 3B. The relative coupling rate constant k is given in brackets in the unit 10⁴ · 1 · mol⁻¹ · s⁻¹.

Processing of the samples of layer structures 3A, 3B and 3C and determination of the color granularity and sharpness (i.e. the MTF values) was carried out as described in Example 1.

The values found for the color granularity and for the sharpness of the structures 3A, 3B and 3C are shown in Table 3d, as are the photographic sensitivities.

It can be seen from Table 3c that, with the same sharpness, the color granularities and the sensitivities in blue-green and purple in the structures 3B and 3C according to the invention are improved compared to the comparison structure 3A.

Claims (4)

1. Colour photographic negative recording material containing at least one red-sensitive, at least one green-sensitive and at least one blue-sensitive silver halide emulsion layer, each with associated colour couplers for the production of image dyes of complementary colour to the spectral sensitivity, wherein, in order to record light from at least one of the spectral ranges red, green, blue, there are present at least three partial layers of differing sensitivities containing colour coupler, namely a most sensitive, an intermediately sensitive and a least sensitive partial layer, of which at least one of the two more sensitive partial layers contains a DIR coupler, characterised in that the colour coupler acting solely for colour production contained in the most sensitive partial layer and the corresponding colour coupler contained in the least sensitive partial layer couple faster than the corresponding colour coupler in the intermediately sensitive partial layer by a factor of at least 1.5.
2. Recording material according to claim 1, characterised in that the least sensitive partial layer contains no DIR coupler.
3. Recording material according to claim 1, characterised in that the DIR coupler contained in one of the two more sensitive partial layers differs in coupling rate from the colour coupler contained in the same partial layer by no more than a factor of 5.
4. Recording material according to claim 1, characterised by a total silver halide application of all the photosensitive layers, expressed as the equivalent quantity of AgNO₃, of no more than 10 g of AgNO₃ per m.