EP0205075B1 - Colour-photographic recording material and method for making colour-photographic images - Google Patents

Description

The invention relates to a photographic recording material with improved sensitometric properties.

Photographic recording materials are required to have high sensitivity, good sharpness and fine grain. For this purpose, it is already known to split emulsion layers into partial layers of different sensitivity, to use antihalation dyes and DIR compounds and e.g. reduce graininess by limited diffusion of dyes.

It is also known to use synthetic polymeric compounds instead of the gelatin predominantly used as binders. Synthetic polymers can also be used as peptizers or as carriers for hydrophobic substances, for example in the form of loaded latices, see US Pat. No. 4,199,363. In some cases excellent granularity is achieved, reference is made to DE-A 3 036 846 and EP-A 93 924.

The use of polymers is summarized in Research Disclosure 19 551, 20 502, 18 735, 18 549, 17 709, 17 329 and 15 638. Reference is also made to DE-A 2 745 287, US-A 3 411 911, US-A 3 536 491, US-A 2 852 386, US-A 2 772 163, DE-A 1 472 746, DE-A 1 522 387, EP-A 69 671, US-A 2 272 191 and US- A 2 772 163.

Such polymers can be loaded with color couplers, e.g. is known from DE-A 2 541 274, DE-A 2 541 230, DE-A 2 541 276, EP-A 0 014 921, US-A 4 133 687, EP-A 0 069 671, DD 144 129, EP -A 0 130 115, DD 138 831, DE-A 2 820 092, DE-A 1 597 467, US-A 4 291 113, GB-A 2 072 365, DE-A 2 835 856, GB-A 1 516 855, DE-A 30 36 846, DE-A 2 815 635.

However, the known measures still have disadvantages with regard to their sensitometric properties, in particular with regard to sharpness with good graininess and sensitivity.

The invention was therefore based on the object of specifying a color photographic recording material with improved properties, which in particular should have improved sharpness but also good graininess and sensitivity.

A color photographic recording material with at least one silver halide emulsion layer has now been found which is divided into a relatively insensitive sublayer L and at least one more sensitive sub-layer H is split, the sub-layers H and L being assigned at least one color coupler. According to the invention, at least one sub-layer H contains at least one synthetic polymer P and gelatin, in which sub-layer the weight ratio of all synthetic polymers P and gelatin is between 30:70 and 80:20 and in the sub-layer L the ratio of polymer to gelatin is less than Is 25:75.

In a particularly preferred embodiment, the weight ratio is at least 40:60 and in a further embodiment it is between 40:60 and 60:40.

In a particularly preferred embodiment, there is a low-molecular color coupler in the sub-layer H, while a low-molecular and / or polymeric coupler is assigned to the sub-layer L.

Furthermore, a method for producing color photographic images has been found in which the recording material according to the invention is exposed imagewise and developed in a color developer. The color developer preferably contains a p-phenylenediamine.

For the purposes of the present invention, synthetic polymers are preferably understood to mean synthetic high-molecular compounds from the group of the polymerization products, the polycondensation products and the polyaddition products.

Polymerization products are preferably polymers made from ethylenically unsaturated low-molecular compounds and polymers made from low-molecular compounds which have a ring structure.

Examples of ethylenically unsaturated compounds are ethylene, butadiene, isoprene, vinyl aromatics such as styrene, α-methylstyrene, divinylbenzene, chloromethylstyrene, vinyltoluene, (meth) acrylic acid derivatives such as optionally substituted (meth) acrylic acid esters, (meth) acrylic acid amides, (meth) acrylic acid , Vinyl esters, vinyl amides, vinyl ethers, vinyl heterocycles and others Vinyl pyridine, vinyl imidazole, vinyl sulfones, vinyl sulfonamides, vinyl ketones, maleic acid derivatives, fumaric acid derivatives, itaconic acid derivatives, (meth) allyl compounds, vinyl thioethers, vinyl silanes, vinyl chloride, vinylidene chloride, (meth) acrylonitrile.

Examples of the classes of compounds mentioned are listed in Research Disclosure 19 551 (1980) and Yocum, Nyquist "Functional Monomers", 2 vols., New York, Dekker 1973.

Low molecular weight compounds which have a ring structure are e.g. Ethylene oxide, propylene oxide, butylene oxide, aziridines, tetrahydrofuran, caprolactam, epichlorohydrin.

Polycondensation products and polyaddition products are e.g. Polyesters, polyamides, polycarbonates, polysulfones, polyurethanes, polysiloxanes, polyureas, phenol-formaldehyde resins, polyimides, polyphenylene oxide, epoxy resins, urea-formaldehyde resins. Examples of the compounds are described in Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, Verlag Chemie, Weinheim 1980.

Particularly preferred synthetic polymers are the nonionic polyurethanes known from German patent 1,522,387, those from German patent 1,522,393 known anionic polyurethanes which contain a group of phosphonic acid, phosphoric acid ester or phosphoric acid amide capable of salt formation and the anionic polyurethanes known from German patent 1,472,746.

Polymers are preferably used which are in dispersion form, i.e. have a particulate character. The mean particle size is in the range from 20 to 2000 nm, preferably in the range from 20 to 500 nm.

Polymers are also preferred whose glass transition temperature T _{g is} below + 25 ° C.

Polymer dispersions which are nonionic or have an anionic charge are also preferred.

Polymers are also preferred which show a certain solvency for the color coupler used. The color coupler is soluble in the polymer if a polymer / coupler mixture, produced by evaporating a solution of polymer and coupler, has no enthalpy of fusion of the coupler in a differential thermal analysis measurement. Polymers that can dissolve more than 5% color couplers are preferred.

The polymers are used in such a way that they enable a limited diffusion of the dye which is formed in the color coupling from the color coupler.

Latices that can be loaded are preferably suitable. The polymers described in DE-A 3 036 846, DE-A 1 522 387, DE-A 1 472 746 are particularly suitable. Preferred examples of polymers are L1 to L180 from Research Disclosure 19 551, polymer I to polymer V from DE-A 3 036 846, polyester p. 6 line 33 - p. 7 line 22 of EP 0 069 671.

Particularly preferred polymers are given below. Some of them are loaded with couplers.

Polymer P1:

Polymer II of DE-A 3 036 846 or US-A 4 388 403 is loaded with the color coupler C2 specified below. In the polymer: coupler ratio of 8: 1. The procedure is as described under Dispersion 1 of DE-A 3 036 846.

Polymer P2:

Polymer P2 is produced like polymer P1, except that instead of the coupler specified there, the purple coupler M1 specified below is used.

Polymer P3:

Polymer IV of DE-A 3 036 846 is loaded in the weight ratio 8: 1 with the yellow coupler Y1 indicated below in accordance with the preparation instructions of DE-A 3,036 846 specified under Dispersion IV.

Polymer P4:

Production according to polymer V of DE-A 3 036 846, which is loaded in a weight ratio of 1: 1 with the coupler specified below under the production specification of DE-A 3 036 846 specified under dispersion IV.

Polymer P5:

Production according to polymer II of DE-A 3 036 846, which is loaded in a weight ratio of 1: 1 with the following purple coupler M2, according to the production specification of DE-A 3 036 846 specified under dispersion IV.

Polymer P6:

Compound 4 of DE-PS 1 472 746, which is loaded in a weight ratio of 1: 1 with the yellow coupler Y1 specified below, the procedure according to the preparation specification of DE-A 3,036,846 specified under Dispersion IV being carried out during loading.

Polymer P7:

Compound 2 of DE-PS 1 472 746.

Polymer P8:

Compound 5 of DE-PS 1 472 746.

The above-mentioned polymers are added in particular to the highly sensitive partial layers of a color negative material. In addition to silver halide, the highly sensitive sub-layers may contain: color masks, White couplers, scavangers, DIR couplers as well as DAR couplers. A combination of the polymers mentioned here in the highly sensitive partial layers with DIR couplers is particularly advantageous because the sharpness is increased by means of edge effects. A combination of these polymers with DAR couplers (Development Accelerator Release) counteracts grain enlargement.

In addition, the highly sensitive partial layers can also contain casting aids such as wetting agents and thickeners etc.

In a particularly preferred embodiment, at least some of the polymers to be used according to the invention are used as carriers for a color coupler. In this case, there is a latex loaded with a coupler. It can be particularly advantageous to use a mixture of loaded and unloaded latex.

The sublayer L can contain the usual constituents, ie in addition to the silver halide emulsion, color couplers, masks, white couplers, scavangers, DIR couplers and / or DAR couplers. These components, in particular the color couplers, can also be applied to a latex in the low-sensitivity layer, which is then present as a loaded latex. It is also possible to fix the couplers in the form of polymeric couplers.

Usually the coupler / silver ratio in the low-sensitive layer L is larger than in the more sensitive sub-layer H.

In a preferred embodiment, the recording material according to the invention has at least one blue, green and red sensitive layer. Of these, at least one layer is split into two sub-layers L and H according to the invention. It is particularly preferred to divide all spectrally sensitized layers into at least two sub-layers of different sensitivity.

The sub-layers of the same spectral sensitivity can be combined to form double or multiple-layer packets, but the sub-layers of one spectral sensitivity can alternate with the layers of another spectral sensitivity, but also in any order that achieves the most advantageous constellation.

Preferably, at least one blue-sensitive layer lies above the green- and red-sensitive layers and is separated from them by a yellow filter layer. In addition to the photosensitive layers, additional protective and intermediate layers can be used.

Layer structures in which at least one emulsion layer in partial layers of different sensitivity are split, are known for example from DE-A 1 958 709 (Pankow).

Typical structures that can be used are given below, the usual intermediate layers being omitted for the sake of clarity.

Here mean:

r

 red-sensitive sub-layer, low sensitivity

R

 red-sensitive sub-layer, medium sensitivity

RR

red-sensitive sub-layer, highest sensitivity

G

 green-sensitive sub-layer, low sensitivity

G

green-sensitive sub-layer, medium sensitivity

GG

green-sensitive sub-layer, highest sensitivity

b

blue-sensitive sub-layer, low sensitivity

B

blue-sensitive sub-layer, medium sensitivity

BB

blue-sensitive sub-layer, highest sensitivity

GF

Yellow filter

Tr

 Layer support

When assessing the sensitivity of the individual sub-layers, it is not the absolute sensitivity that is important, but the effective sensitivity, taking into account the respective position within the color photographic multilayer material. The difference in the effective sensitivity is expediently between 0.1 and 1.0 relative log Ixt units. In individual cases, the difference in sensitivity is chosen so that a balanced gradation curve results without perceptible distortion during color photographic processing.

In addition to the layers already mentioned, further non-light-sensitive auxiliary layers can be present in the color photographic recording material according to the invention, e.g. Adhesive layers, antihalation layers or cover layers, in particular intermediate layers between the light-sensitive layers, as a result of which the diffusion of developer oxidation products from one layer into another is to be effectively prevented. For this purpose, intermediate layers of this type can furthermore contain certain compounds which are able to react with developer oxidation products. Such layers are preferably arranged between adjacent light-sensitive layers of different spectral sensitivity. A less sensitive silver halide emulsion with an average grain diameter of about 0.1 μm or smaller, which contains chloride, bromide and optionally iodide, can also be embedded in these intermediate layers. Such a layer has a particularly beneficial effect on the sensitivity of the adjacent layers. The less sensitive silver halide emulsion can, however, also be introduced directly into the light-sensitive layers.

Color couplers, which can react with color developer oxidation products to form a dye, are preferably assigned to the light-sensitive silver halide emulsion layers. The color couplers are preferably directly adjacent to and in particular contained in the silver halide emulsion layer.

For example, the red-sensitive layer can use a color coupler to generate the blue-green partial color image included, usually a coupler of the phenol or α-naphthol type. The green-sensitive layer can contain, for example, at least one color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone type usually being used.

The blue-sensitive layer can contain, for example, at least one color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping. The color couplers can be, for example, 6, 4 and 2 equivalent couplers. Suitable couplers are known, for example, from the publications "Color Coupler" by W. Pelz in "Messages from the Research Laboratories of Agfa, Leverkusen / Munich", Volume III, page 111 (1961), K. Venkataraman in "The Chemistry of Synthetic Dyes", Vol. 4, 341 to 387, Academic Press (1971) and TH James, "The Theory of the Photographic Process", 4th Ed., Pp. 353-362, as well as from Research Disclosure No. 17643 of December 1978, Section VII, published by Industrial Opportunities Ltd., Homewell Havant, Hampshire, PO9 1 EF in the UK. The usual mask couplers can be used to improve the color rendering. The recording material can also contain DIR compounds and white couplers which do not give any dye when reacted with color developer oxidation products. The inhibitors which can be split off from the DIR compounds can be split off directly or via non-inhibiting intermediate compounds.

Reference is made to GB 953 454, US 3,632,345, US 4,248,962 and GB 2,072,363 and Research Disclosure No. 10226 dated October 1972.

Examples of particularly suitable yellow couplers are given in the following table:

Examples of particularly suitable cyan couplers are given in the following table:

Typical purple couplers are given below:

The light-sensitive silver halide emulsions used can contain chloride, bromide and iodide or mixtures thereof as the halide. In a preferred embodiment, the halide content of at least one layer consists of 0 to 12 mol% of AgI, 0 to 50 mol% of AgCl and 50 to 100% of AgBr. In a preferred embodiment, the crystals are predominantly compact, e.g. are cubic or octahedral or have transitional forms. They can be characterized in that they essentially have a thickness of more than 0.2 μm. The average ratio of diameter to thickness is preferably less than 8: 1, it being true that the diameter of a grain is defined as the diameter of a circle with a circle content corresponding to the projected area of the grain. In another preferred embodiment, all or individual emulsions can also have essentially tabular silver halide crystals in which the ratio of diameter to thickness is greater than 8: 1. The emulsions can be monodisperse emulsions, which preferably have an average grain size of 0.3 μm to 1.2 μm. The silver halide grains can have a layered grain structure.

The emulsions can be chemically sensitized. For chemical sensitization of the silver halide grains the usual sensitizers are suitable. Sulfur-containing compounds, for example allyl isothiocyanate, allyl thiourea and thiosulfates, are particularly preferred. Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky, Z.Wiss.Phot. 46 , 65-72 (1951). It is also possible to sensitize the emulsions with polyalkylene oxide derivatives. Reference is also made to Research Disclosure No. 17 643, section III.

The emulsions can be optically sensitized in a manner known per se, e.g. with the usual polymethine dyes, such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like. Such sensitizers are from F.M. Hamer in "The Cyanine Dyes and related Compounds", (1964). In this regard, reference is made in particular to Ullman's Encyclopedia of Industrial Chemistry, 4th edition, volume 18, pages 431 ff and to Research Disclosure No. 17 643, section IV, given above.

The usual antifoggants and stabilizers can be used. Particularly suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are, for example, in the article by Birr, Z.Wiss.Phot. 47, 1952), pp. 2-58. More suitable Stabilizers and antifoggants are given in Research Disclosure No. 17,643 above in Section IV. Suitable compounds for improving the resistance to formalin are given in US-A 464 463.

The recording material can contain stabilizers against visible and UV light and to improve the storage stability, which may optionally be in polymeric form. Particularly good stabilizers in this sense are e.g. Amino allyl malonitriles.

The additional components of the photographic material can be incorporated by customary, known methods. If the compounds are soluble in water or alkali, they can be added in the form of aqueous solutions, optionally with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide. If they are water or. are insoluble in alkali, they can be incorporated into the recording materials in a known manner in dispersed form. For example, a solution of these compounds in a low-boiling organic solvent can be mixed directly with the silver halide emulsion or initially with an aqueous gelatin solution and the organic solvent can then be removed. The dispersion of the respective compound thus obtained can then be mixed with the silver halide emulsion. If necessary, so-called oil formers are also used, generally higher-boiling organic compounds, which include the compounds to be dispersed in the form of oily droplets.

In this connection, reference is made, for example, to U.S. Patents 2,322,027, 2,533,514, 3,689,271, 3,764,336 and 3,765,897. It is also possible, e.g. To install couplers in the form of loaded latices, see DE-OS 2 541 274 and EP-A 14 921. Furthermore, the constituents can also be defined as polymers in the material, see e.g. DE-OS 2 044 992, US 3 370 952 and US 4 080 211.

The usual substrates can be used for the materials according to the invention, e.g. Cellulose ester supports, e.g. Cellulose acetate and polyester. Also suitable are paper supports, which can optionally be coated, e.g. with polyolefins, especially with polyethylene or polypropylene. In this regard, reference is made to 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 indicated in Research Disclosure 17,643 above 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. It is also possible to use the Harden layers according to the method of German Offenlegungsschrift 2 218 009 in order to obtain color photographic materials which are suitable for high-temperature processing. It is also possible to harden the photographic layers or the color photographic multilayer materials with hardeners of the diazine-triazine or 1,2-dihydroquinoline series or with hardeners of the vinylsulfone type. Further suitable hardening agents are known from German laid-open documents 2 439 551, 2 225 230, 2 317 672 and from Research Disclosure 17 643, section XI, specified above.

The curing is preferably adjusted so that the swelling of the layers in water (10 ° DH) at 38 ° C (5 min) does not drop below 2.3-2.6 and there is sufficient wet scratch resistance for processing.

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

Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, for example 4-amino-N, N-diethyl-aniline hydrochloride: 4-amino-3-methyl-N-ethyl-N-β- (methanesulfonamido) ethyl-aniline sulfate hydrate ; 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate; 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid and N-ethyl-N-β-hydroxyethyl-p-phenylenediamine. Further 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, e.g. Fe³⁺ salts and Fe³⁺ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes etc. Particularly preferred are iron III complexes of aminopolycarboxylic acids, especially e.g. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulphates are also suitable as bleaching agents.

In the following examples, the following compounds are used in addition to the polymers and couplers already given:

example 1

1A

ist der Vergleichstyp ohne Polymerenzusatz,

1B

ist ein Vergleichstyp, bei dem Polymere nicht nur den hoch-, sondern auch den niedrigempfindlichen Teilschichten zugesetzt sind.

1C

enthält erfindungsgemäß in den hochempfindlichen Teilschichten:

• RR = Schicht Nr. 4
• GG = Schicht Nr. 7
• BB = Schicht Nr. 11

das Polymere P8 im Gewichtsverhältnis von Polymeres: Gelatine = 1:1.
Der Farbkuppler liegt hier wie bei 1A und 1B in emulgierter Form vor.

1D

enthält erfindungsgemäß in den hochempfindlichen Teilschichten folgende mit Farbkuppler beladene Polymere:

• RR = Schicht 4: P1
• GG = Schicht 7: P2
• BB = Schicht 11: P3

The layer structure variants 1A, 1B, 1C and 1D are produced.

1A

is the comparison type with no added polymer,

1B

is a comparison type in which polymers are added not only to the high-sensitive but also to the low-sensitive sub-layers.

1C

contains according to the invention in the highly sensitive partial layers:

• RR = layer no.4
• GG = layer no.7
• BB = layer no.11

the polymer P8 in the weight ratio of polymer: gelatin = 1: 1.
The color coupler is here in emulsified form as in 1A and 1B.

1D

contains according to the invention in the highly sensitive partial layers the following polymers loaded with color couplers:

• RR = Layer 4: P1
• GG = layer 7: P2
• BB = layer 11: P3

To produce these four layer structures, the following layers were applied to a transparent layer support made of cellulose triacetate in the order given here.

The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given.

1. Schicht:

(Antihaloschicht) Schwarzes kolloidales Silbersol mit 1,5 g Gelatine und 0,33 g Ag

2. Schicht:

(Zwischenschicht) 0,6 g Gelatine

3. Schicht:

(niedrigempfindliche, rotsensibilisierte Schicht)
Die drei Schichtaufbau-Varianten 1A, 1C und 1D enthielten in dieser 3. Schicht jeweils 3,0 g einer Ag(Br,J)-Emulsion mit 4 Mol-% Iodid, mittlerer Korndurchmesser = 0,45 µm, spektral sensibilisiert für den roten Spektralbereich, und 2,0 g Gelatine. Ferner enthielt diese 3. Schicht 0,6 g Blaugrünkuppler C1, emulgiert (1 Gewichtsteil Kuppler mit 0,5 Gewichtsteilen Ölbildner), außerdem 50 mg Rotmaske CC1 sowie 25 mg DIR1.
Bei der Schichtaufbau-Variante 1B enthielt die 3. Schicht die hier genannten Bestandteile zur Erzielung gleicher Gradation in einer um den Faktor 0,8 verminderten Menge, außerdem enthielt hier diese Schicht 1,6 g P8.

4. Schicht:

(hochempfindliche, rotsensibilisierte Schicht)
Aufbau-Variante 1A:
2,8 g einer Ag(Br,J)-Emulsion mit 8,5 Mol-% Iodid, mittlerer Korndurchmesser = 0,8 µm, Spektral rot sensibilisiert, 1,8 g Gelatine und 0,15 g des Blaugrün-Kupplers C2, emulgiert (1 Gewichtsteil des Farbkupplers mit 1 Gewichtsteil Dibutylphthalat).
Die Aufbau-Varianten 1B, 1C und 1D enthielten diese Bestandteile in der 4. Schicht zur Erzielung gleicher Gradation in einer um den Faktor 0,6 verminderten Menge, außerdem enthielt beim Aufbau 1B und 1C diese 4. Schicht 0,9 g P8. Die Aufbau-Variante 1D enthielt statt des Blaugrün-Kuppler-Emulgats 0,9 g des Polymeren P1, welches im Gewichtsverhältnis von 1 Teil Kuppler:8 Teilen Polymeres mit dem Blaugrün-Kuppler C2 beladen war.

5. Schicht:

(Zwischenschicht) 0,7 g Gelatine und 0,2 g 2,5-Diisooctylhydrochinon

6. Schicht:

(niedrigempfindliche, grünsensibilisierte Schicht)
Die drei Schichtaufbau-Varianten 1A, 1C und 1D enthielten in dieser 6. Schicht jeweils 2,5 g AgNO₃ einer Ag(Br,J)-Emulsion mit 4,5 Mol-% Iodid, mittlerer Korndurchmesser = 0,4 µm, Spektral grün sensibilisiert, und 1,5 g Gelatine. Außerdem enthielt diese 6. Schicht 0,6 g des Purpurkupplers M1 als Emulgat (1 Gewichtsteil Farbkuppler emulgiert mit 1 Gewichtsteil Trikresylphosphat), 20 mg der Gelbmaske CC2 und 7,5 mg des DIR-Kupplers DIR2.
Bei der Aufbau-Variante 1B enthielt die 6. Schicht die hier genannten Bestandteile zur Erzielung gleicher Gradation in einer um den Faktor 0,85 verminderten Menge, außerdem enthielt hier diese Schicht 1,3 g P8.

7. Schicht:

(hochempfindliche, grünsensibilisierte Schicht) Aufbau-Variante 1A;
2,5 g einer Ag(Br,J)-Eulsion mit 7,0 Mol-% Iodid, mittlerer Korndurchmesser = 0,70 µm, Spektral grün sensibilisiert, 1,4 g Gelatine, 0,15 g des gleichen Purpur-Kupplers M1 wie in Schicht Nr. 6, emulgiert wie dort angegeben, sowie 0,02 g des gleichen Gelbmasken-Kupplers CC2.
Die Aufbau-Varianten 1B, 1C und 1D enthielten diese Bestandteile in der 7. Schicht zur Erzielung gleicher Gradation in einer um den Faktor 0,8 verminderten Menge, außerdem enthielt diese 7. Schicht beim Aufbau 1B und 1C 1,1 g P8.
Die Aufbau-Variante 1D enthielt statt des Purpur-Kuppler-Emulgats 1,1 g des Polymeren P2, welches im Gewichtsverhältnis von 1 Teil Kuppler:8 Teile Polymeres mit dem Purpur-Kuppler M1 beladen war.

8. Schicht:

(Zwischenschicht) 0,5 g Gelatine und 0,15 g 2,5-Diisooctylhydrochinon

9. Schicht:

(Gelbfilterschicht) gelbes kollidales Silbersol mit 0,2 g Ag und 0,9 g Gelatine

10. Schicht:

(niedrigempfindliche, blauempfindliche Schicht)
Die drei Schichtaufbau-Varianten 1A, 1C und 1D enthielten in dieser 10. Schicht jeweils 0,75 g einer spektral blau-sensibilisierten Ag(Br,J)-Emulsion mit 4,9 Mol-% Iodid, mittlerer Korndurchmesser = 0,45 µm, und 0,85 g Gelatine.
Außerdem enthielt hier diese 10. Schicht 0,7 g Gelbkuppler Y1, emulgiert im Gewichtsverhältnis 1:1 mit Trikresylphosphat, sowie 0,15 g des DIR-Kupplers DIR3.
Bei der Schichtaufbau-Variante 1B enthielt die 10. Schicht zur Erzielung gleicher Gradation diese Bestandteile in einer um den Faktor 0,75 verminderten Menge, zusätzlich aber noch 0,6 g P8.

11. Schicht:

(hochempfindliche, blauempfindliche Schicht)
Aufbau-Variante 1A:
1,0 g einer Spektral blau sensibilisierten Ag(Br,J)-Emulsion mit 9,0 Mol-% AgJ, mittlerer Korndurchmesser = 0,9 µm, 0,85 g Gelatine und 0,3 g des gleichen Gelbkupplers Y1 wie in Schicht 10, emulgiert wie dort beschrieben.
Bei den Aufbau-Varianten 1B, 1C und 1D enthielt die 11. Schicht diese Bausteine zur Erzielung gleicher Gradation in einer um den Faktor 0,7 verminderten Menge, außerdem enthielt diese 11. Schicht beim Aufbau 1B und 1C 0,6 g P8.
Die Aufbau-Variante 1D enthielt anstelle des Gelbkuppler-Emulgats 0,65 g des Polymeren P3, welches im Gewichtsverhältnis von 1 Teil Kuppler:8 Teilen Polymeres mit dem Gelbkuppler Y1 beladen war.

12. Schicht:

(Schutzschicht) 1,2 g Gelatine 0,5 g eines üblichen UV-Absorbers.

13. Schicht:

(Härtungsschicht) 1,5 g Gelatine und 0,7 g eines üblichen Härtungsmittels.

All silver halide emulsions of this material were stabilized with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per 100 g of AgNO₃.

1st layer:

(Antihalation layer) Black colloidal silver sol with 1.5 g gelatin and 0.33 g Ag

2 layer:

(Intermediate layer) 0.6 g gelatin

3 layer:

(low-sensitivity, red-sensitive layer)
The three layer structure variants 1A, 1C and 1D each contained 3.0 g of an Ag (Br, J) emulsion with 4 mol% iodide, average grain diameter = 0.45 µm, spectrally sensitized to the red layer in this third layer Spectral range, and 2.0 g of gelatin. This third layer also contained 0.6 g of cyan coupler C1, emulsified (1 part by weight of coupler with 0.5 part by weight of oil former), also 50 mg of red mask CC1 and 25 mg of DIR1.
In the layer structure variant 1B, the third layer contained the components mentioned here in order to achieve the same gradation in a quantity reduced by a factor of 0.8, and this layer also contained 1.6 g of P8.

4th layer:

(highly sensitive, red-sensitive layer)
Construction variant 1A:
2.8 g of an Ag (Br, J) emulsion with 8.5 mol% iodide, average grain diameter = 0.8 µm, spectrally red sensitized, 1.8 g gelatin and 0.15 g of the cyan coupler C2, emulsified (1 part by weight of the color coupler with 1 part by weight of dibutyl phthalate).
The construction variants 1B, 1C and 1D contained these components in the 4th layer in order to achieve the same gradation in a quantity reduced by a factor of 0.6, and in the construction 1B and 1C this 4th layer also contained 0.9 g of P8. The construction variant 1D contained, instead of the cyan coupler emulsifier, 0.9 g of the polymer P1, which was loaded with the cyan coupler C2 in the weight ratio of 1 part coupler: 8 parts polymer.

5th layer:

(Interlayer) 0.7 g gelatin and 0.2 g 2,5-diisooctylhydroquinone

6th layer:

(low-sensitivity, green-sensitized layer)
The three layer structure variants 1A, 1C and 1D each contained 2.5 g of AgNO₃ an Ag (Br, J) emulsion with 4.5 mol% iodide, average grain diameter = 0.4 µm, spectrally green in this 6th layer sensitized, and 1.5 g of gelatin. This 6th layer also contained 0.6 g of the purple coupler M1 as an emulsifier (1 part by weight of color coupler emulsified with 1 part by weight of tricresyl phosphate), 20 mg of the yellow mask CC2 and 7.5 mg of the DIR coupler DIR2.
In the construction variant 1B, the 6th layer contained the constituents mentioned here in order to achieve the same gradation in a quantity reduced by a factor of 0.85, and this layer also contained 1.3 g of P8.

7th layer:

(highly sensitive, green-sensitized layer) Construction variant 1A;
2.5 g of an Ag (Br, J) emulsion with 7.0 mol% iodide, average grain diameter = 0.70 µm, spectrally green sensitized, 1.4 g gelatin, 0.15 g of the same purple coupler M1 as in layer # 6, emulsified as indicated there, and 0.02 g of the same yellow mask coupler CC2.
Construction variants 1B, 1C and 1D contained these components in the 7th layer in order to achieve the same gradation in a quantity reduced by a factor of 0.8, and in addition, this 7th layer contained 1.1 g of P8 in construction 1B and 1C.
The construction variant 1D contained 1.1 g of polymer P2 instead of the purple coupler emulsifier, which was loaded with the purple coupler M1 in the weight ratio of 1 part coupler: 8 parts polymer.

8th layer:

(Interlayer) 0.5 g gelatin and 0.15 g 2,5-diisooctyl hydroquinone

9th layer:

(Yellow filter layer) yellow colloidal silver sol with 0.2 g Ag and 0.9 g gelatin

10th layer:

(low-sensitivity, blue-sensitive layer)
The three layer structure variants 1A, 1C and 1D each contained 0.75 g of a spectrally blue-sensitized Ag (Br, J) emulsion with 4.9 mol% iodide, average grain diameter = 0.45 µm in this 10th layer , and 0.85 g of gelatin.
In addition, this 10th layer contained 0.7 g of yellow coupler Y1, emulsified in a weight ratio of 1: 1 with tricresyl phosphate, and 0.15 g of the DIR coupler DIR3.
In the layer structure variant 1B, the 10th layer contained these components in a quantity reduced by a factor of 0.75 in order to achieve the same gradation, but additionally 0.6 g of P8.

11th layer:

(highly sensitive, blue sensitive layer)
Construction variant 1A:
1.0 g of a spectrally blue sensitized Ag (Br, J) emulsion with 9.0 mol% AgJ, average grain diameter = 0.9 μm, 0.85 g gelatin and 0.3 g of the same yellow coupler Y1 as in the layer 10, emulsified as described there.
In the construction variants 1B, 1C and 1D, the 11th layer contained these building blocks in order to achieve the same gradation in a quantity reduced by a factor of 0.7, and in addition, this 11th layer in the construction 1B and 1C contained 0.6 g of P8.
The construction variant 1D contained, instead of the yellow coupler emulsifier, 0.65 g of the polymer P3, which was loaded with the yellow coupler Y1 in the weight ratio of 1 part coupler: 8 parts polymer.

12th layer:

(Protective layer) 1.2 g of gelatin 0.5 g of a conventional UV absorber.

13th layer:

(Hardening layer) 1.5 g of gelatin and 0.7 g of a conventional hardening agent.

These four layer structures 1A, 1B, 1C and 1D are only intended to demonstrate how effective it is for the sharpness and granularity of color negative material if you only load these polymers (with or without photographically active components such as color couplers) incorporated highly sensitive sub-layers.

The materials were exposed to white light behind a gradient wedge and then using a color negative processing process as described in "The British Journal of Photography", (1974), pages 597 u. 598 is processed. The color granularity (σ _D ) was then measured at various color densities according to that described by TH James, "The Theory of the Photographic Process", 4th edition, Macmillan Publ. Co Inc., New York / London (1977) p. 618 - 621 procedures described.

Table B1 / I shows the color granularity of the layer structure variants measured at 0.5, 1.0 and 1.5 via fog.

Determination of sharpness

This is done with the help of the modulation transfer function (MTF) according to the procedure described by T.H. James, "The Theory of the Photographic Process", 4th ed., Macmillan Publ. Co Inc., New York / London (1977) p. 605.

The spatial frequencies (in lines per mm) at which the MTF has a value of 75%, 50% and 25% are specified here. The higher sharpness of the structures according to the invention can be seen from the higher spatial frequencies at which the MTF reaches these percentages.

Table B1 / II shows the sharpness data for the layer structure variants of Example 1.

Example 2

The eight layer structure variants 2A to 2H described here are produced.

2A:

weder DIR- noch DAR-Kuppler,

2B:

DIR-Kuppler,

2C:

DAR-Kuppler,

2D:

DAR- und DIR-Kuppler.

Of these, the layer structure variants 2A to 2D are comparison structures without the addition of polymers according to the invention. The highly sensitive sub-layers of these comparative structures contain

2A:

neither DIR nor DAR couplers,

2 B:

DIR coupler,

2C:

DAR coupler,

2D:

DAR and DIR couplers.

The four layer construction variants 2E to 2H correspond to these four variants 2A to 2D, but according to the invention they contain, in the highly sensitive partial layers, addition of the above-mentioned polymers, specifically mixtures of unloaded ones with those which were loaded with color couplers.

The medium and low-sensitive partial layers as well as the separation and filter layers are the same for all eight variants. There are differences only from the 13th shift.

Eight layers were built onto a transparent cellulose triacetate support The following layers are applied in the order given here.

The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given.

1. Schicht:

(Antihaloschicht) Schwarzes kolloidales Silbersol mit 1,5 g Gelatine und 0,33 g Ag

2. Schicht:

(Mikrat-Zwischenschicht) 0,6 g Gelatine und 0,2 g einer Ag(Br,J)krat-Emulsion mit 1,5 Mol-% Iodid, mittlerer Korndurchmesser = 0,05 µm.

3. Schicht:

(niedrigempfindliche, rotsensibilisierte Schicht) Zusammensetzung wie die dritte Schicht von Beispiel 1, Schichtaufbau-Varianten 1A, 1C und 1D.

4. Schicht:

Zwischenschicht, enthaltend 0,6 g Gelatine und 0,2 g des gleichen Blaugrünkupplers C1 wie in der 3. Schicht.

5. Schicht:

(mittelempfindliche, rotsensibilisierte Schicht)
2,0 g rotsensibilisierte Ag(Br,J)-Emulsion, 6 Mol-% Iodid, mittlerer Korndurchmesser = 0,7 µm, 1,2 g Gelatine, 0,3 g des Blaugrünkupplers C1, 40 mg der Rotmaske CC1 und 20 mg des gleichen DIR-Kupplers DIR1.

6. Schicht:

Zwischenschicht 0,6 g Gelatine und
0,2 g Diisooctylhydrochinon.

7. Schicht:

(niedrigempfindliche, grünsensibilisierte Schicht)
Zusammensetzung wie die 6. Schicht die Beispiel 1, Schichtvarianten 1A, 1C und 1D.

8. Schicht:

Zwischenschicht, enthaltend 0,6 g Gelatine, 0,2 g des Purpurkupplers M1 und 0,05 g der Gelbmaske CC2.

9. Schicht:

(mittelempfindliche, grünsensibilisierte Schicht)
1,2 g einer spektral grünsensibilisierten Ag(Br,J)-Emulsion mit 4,0 Mol-% Jodid, mittlerer Korndurchmesser 0,8 µm, 0,75 g Gelatine, 0,18 g des gleichen Purpur-Kupplers, 0,04 g der gleichen Gelbmaske und 0,02 g des gleichen DIR-Kupplers wie in der 7. Schicht.

10. Schicht:

(Gelbfilterschicht)
Gelbes kolloidales Silbersol mit 0,1 g Ag, 0,5 g Gelatine und 0,1 g 2,5-Diisooctyl-Hydrochinon.
Das gelbe Silbersol war mit einem Phenylmercaptotetrazol stabilisiert.

11. Schicht:

niedrigempfindliche, blauempfindliche Schicht
0,8 g blausensibilisierte Ag(Br,J)-Emulsion (5 Mol-% Iodid), mittlerer Korndurchmesser = 0,5 µm, 0,9 g Gelatine und 0,7 g Gelbkuppler Y1 emulgiert im Gewichtsverhältnis 1:1 mit Trikresylphosphat, sowie 150 mg des DIR-Kupplers DIR3.

12. Schicht:

Zwischenschicht
Gleiche Zusammensetzung wie die 4. Schicht.

13. Schicht:

hochempfindliche rotsensibilisierte Schicht
Variante 2A:
Rotsensibilisierte Ag(Br,J)-Emulsion, 8 Mol-% Iodid, mittlerer Korndurchmesser = 1,0 µm mit 2,8 g AgNO₃, 1,6 g Gelatine und 0,15 g des Bg-Kupplers C10.
Variante 2B:
Gleiche Emulsion wie bei 2A, aber Silberauftrag 3,2 g, 2,0 g Gelatine und 0,15 g des Bg-Kupplers C2, zusätzlich 0,06 g des DIR-Kupplers DIR4.
Variante 2C:
Gleiche Zusammensetzung wie Variante 2A, zusätzlich 0,01 g des DAR-Kupplers DAR1.
Variante 2D:
Gleiche Zusammensetzung wie die DIR-Kupplerhaltige Variante 2B, aber zusätzlich noch 0,01 g des gleichen DAR-Kupplers DAR1.
Bei den Varianten 2E - 2H enthielt die hochempfindliche Bg-Schicht (= 13. Schicht) die gleichen Bestandteile wie die Varianten 2A - 2D, jedoch zur Erzielung gleicher Gradation in einer um den Faktor 0,65 verminderten Menge. Außerdem war hier das Blaugrünkuppler-Emulgat ersetzt durch 0,2 g des mit Blaugrünkuppler im Gewichtsverhältnis 1:1 beladenen Polymeren P4, abgemischt mit 1,5 g des unbeladenen Polymeren P7.

14. Schicht:

Zwischenschicht Gleiche Zusammensetzung wie die 4. Schicht.

15. Schicht:

hochempfindliche grünsensibilisierte Schicht
Variante 2A:
3,0 g grünsensibilisierte Ag(Br,J)-Emulsion, 7,5 Mol-% Iodid, mittlerer Korndurchmesser = 1,1 µm, 1,8 g Gelatine und 0,16 g des Purpur-Kupplers M2 emulgiert im Gewichtsverhältnis 1:1 mit Trikresylphosphat.
Variante 2B:
Gleiche Emulsion wie bei 2A, aber Silberauftrag 3,4 g, 2,2 g Gelatine und 0,16 g des gleichen Purpur-Kupplers wie bei 2A, emulgiert wie dort und zusätzlich 0,05 g des DIR-Kuppers DIR5.
Variante 2C:
Gleiche Zusammensetzung wie Variante 2A, zusätzlich 0,01 g des DAR-Kupplers DAR1.
Variante 2D:
Gleiche Zusammensetzung wie Variante 2B, aber zusätzlich noch 0,01 g des DAR-Kupplers DAR1.
Bei den Varianten 2E - 2H enthielt die hochempfindliche Purpurschicht (= 15. Schicht) die gleichen Bestandteile wie die Varianten 2A - 2D, jedoch zur Erzielung gleicher Gradation in einer um den Faktor 0,85 verminderten Menge. Außerdem war hier das Purpurkuppler-Emulgat ersetzt durch 0,2 g des mit dem Purpurkuppler M2 im Gewichtsverhältnis 1:1 beladenen Polymeren P5, abgemischt mit 1,6 g P7.

16. Schicht:

(Gelbfilterschicht)
Gleiche Zusammensetzung wie die 10. Schicht.

17. Schicht:

hochempfindliche, blausensibiliserte Schicht
Variante 2A:
0,8 g einer Spektral blau sensibilisierten Ag(Br,J)-Emulsion mit 10,5 Mol-% Iodid, mittlerer Korndurchmesser 1,2 µm, 0,9 g Gelatine und 0,25 g des Gelbkupplers Y1 wie in der 11. Schicht, emulgiert wie dort.
Variante 2B:
1,2 g der gleichen Emulsion wie bei 2A, 1,0 g Gelatine, 0,25 g des Gelbkupplers Y1, emulgiert wie bei 2A, zusätzlich 0,1 g des DIR-Kupplers DIR3.
Variante 2C:
Gleiche Zusammensetzung wie Variante 2A, zusätzlich 0,01 g des DAR-Kupplers DAR1.
Variante 2D:
Gleiche Zusammensetzung wie Variante 2B, aber zusätzlich noch 0,01 g des DAR-Kupplers DAR1.
Bei den Varianten 2E - 2H enthielt die hochempfindliche Gelbschicht (= 17. Schicht) die gleichen Bestandteile wie die Varianten 2A - 2D, jedoch zur Erzielung gleicher Gradation in einer um den Faktor 0,75 verminderten Menge. Außerdem war hier das Gelbkuppler-Emulgat ersetzt durch 0,4 g des mit dem Gelbkuppler Y1 im Gewichtsverhältnis 1:1 beladenen Polymeren P6, abgemischt mit 0,8 g P7.

18. Schicht:

(Härtungsschicht)
1,5 g Gelatine, 0,9 g eines üblichen Härtungsmittels, 0,5 g eines üblichen UV-Absorbers.

All silver halide emulsions of this material were stabilized with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per 100 g of AgNO₃.

1st layer:

(Antihalation layer) Black colloidal silver sol with 1.5 g gelatin and 0.33 g Ag

2 layer:

(Mikrat intermediate layer) 0.6 g of gelatin and 0.2 g of an Ag (Br, J) krat emulsion with 1.5 mol% iodide, average grain diameter = 0.05 µm.

3 layer:

(Low-sensitivity, red-sensitized layer) Composition as the third layer of Example 1, layer structure variants 1A, 1C and 1D.

4th layer:

Intermediate layer, containing 0.6 g of gelatin and 0.2 g of the same cyan coupler C1 as in the 3rd layer.

5th layer:

(medium-sensitive, red-sensitive layer)
2.0 g of red-sensitized Ag (Br, J) emulsion, 6 mol% iodide, average grain diameter = 0.7 µm, 1.2 g of gelatin, 0.3 g of the cyan coupler C1, 40 mg of the red mask CC1 and 20 mg the same DIR coupler DIR1.

6th layer:

Interlayer 0.6 g of gelatin and
0.2 g diisooctyl hydroquinone.

7th layer:

(low-sensitivity, green-sensitized layer)
Composition like the 6th layer, example 1, layer variants 1A, 1C and 1D.

8th layer:

Intermediate layer containing 0.6 g of gelatin, 0.2 g of the purple coupler M1 and 0.05 g of the yellow mask CC2.

9th layer:

(medium sensitive, green sensitized layer)
1.2 g of a spectrally green-sensitized Ag (Br, J) emulsion with 4.0 mol% iodide, average grain diameter 0.8 μm, 0.75 g gelatin, 0.18 g of the same magenta coupler, 0.04 g of the same yellow mask and 0.02 g of the same DIR coupler as in the 7th layer.

10th layer:

(Yellow filter layer)
Yellow colloidal silver sol with 0.1 g Ag, 0.5 g gelatin and 0.1 g 2,5-diisooctyl hydroquinone.
The yellow silver sol was stabilized with a phenyl mercaptotetrazole.

11th layer:

low-sensitivity, blue-sensitive layer
0.8 g blue-sensitized Ag (Br, J) emulsion (5 mol% iodide), average grain diameter = 0.5 µm, 0.9 g gelatin and 0.7 g yellow coupler Y1 emulsified in a weight ratio of 1: 1 with tricresyl phosphate, and 150 mg of the DIR coupler DIR3.

12th layer:

Intermediate layer
Same composition as the 4th layer.

13th layer:

highly sensitive red-sensitive layer
Variant 2A:
Red-sensitized Ag (Br, J) emulsion, 8 mol% iodide, average grain diameter = 1.0 µm with 2.8 g AgNO₃, 1.6 g gelatin and 0.15 g of the Bg coupler C10.
Variant 2B:
The same emulsion as for 2A, but silver coating 3.2 g, 2.0 g gelatin and 0.15 g of the Bg coupler C2, additionally 0.06 g of the DIR coupler DIR4.
Variant 2C:
Same composition as variant 2A, additionally 0.01 g of the DAR coupler DAR1.
Variant 2D:
Same composition as the DIR coupler variant 2B, but additionally 0.01 g of the same DAR coupler DAR1.
In variants 2E - 2H, the highly sensitive Bg layer (= 13th layer) contained the same components as variants 2A - 2D, but to achieve the same gradation in a quantity reduced by a factor of 0.65. In addition, the cyan coupler emulsifier was replaced by 0.2 g of the polymer P4 loaded with cyan coupler in a weight ratio of 1: 1, mixed with 1.5 g of the unloaded polymer P7.

14th layer:

Intermediate layer Same composition as the 4th layer.

15th layer:

highly sensitive green-sensitive layer
Variant 2A:
3.0 g green-sensitized Ag (Br, J) emulsion, 7.5 mol% iodide, average grain diameter = 1.1 µm, 1.8 g gelatin and 0.16 g of the purple coupler M2 emulsified in a weight ratio of 1: 1 with tricresyl phosphate.
Variant 2B:
The same emulsion as in 2A, but silver application 3.4 g, 2.2 g gelatin and 0.16 g of the same magenta coupler as in 2A, emulsified as there and additionally 0.05 g of the DIR coupler DIR5.
Variant 2C:
Same composition as variant 2A, additionally 0.01 g of the DAR coupler DAR1.
Variant 2D:
Same composition as variant 2B, but additionally 0.01 g of the DAR coupler DAR1.
In the variants 2E - 2H, the highly sensitive purple layer (= 15th layer) contained the same components as the variants 2A - 2D, but reduced in order to achieve the same gradation in a factor of 0.85 Amount. In addition, the purple coupler emulsifier was replaced by 0.2 g of the polymer P5 loaded with the purple coupler M2 in a weight ratio of 1: 1, mixed with 1.6 g of P7.

16th layer:

(Yellow filter layer)
Same composition as the 10th layer.

17th layer:

highly sensitive, blue-sensitive layer
Variant 2A:
0.8 g of a spectrally blue-sensitized Ag (Br, J) emulsion with 10.5 mol% iodide, average grain diameter 1.2 μm, 0.9 g gelatin and 0.25 g of the yellow coupler Y1 as in FIG. 11. Layer, emulsified like there.
Variant 2B:
1.2 g of the same emulsion as in 2A, 1.0 g of gelatin, 0.25 g of yellow coupler Y1, emulsified as in 2A, additionally 0.1 g of DIR coupler DIR3.
Variant 2C:
Same composition as variant 2A, additionally 0.01 g of the DAR coupler DAR1.
Variant 2D:
Same composition as variant 2B, but additionally 0.01 g of the DAR coupler DAR1.
In the variants 2E - 2H, the highly sensitive yellow layer (= 17th layer) contained the same components as the variants 2A - 2D, but in order to achieve the same gradation in a quantity reduced by a factor of 0.75. In addition, the yellow coupler emulsifier was replaced by 0.4 g of the polymer P6 loaded with the yellow coupler Y1 in a weight ratio of 1: 1, mixed with 0.8 g of P7.

18th layer:

(Hardening layer)
1.5 g of gelatin, 0.9 g of a conventional hardening agent, 0.5 g of a conventional UV absorber.

Color granularity and sharpness were determined as in Example 1 and are given in the following tables.

When specifying the sensitivity, increasing the value by 3 units corresponds to doubling the sensitivity.

Claims (9)

1. A colour photographic recording material comprising at least one silver halide emulsion layer which is divided into a relatively non-sensitive partial layer L and at at least one more sensitive partial layer H, at least one colour coupler being associated with the partial layers H and L, characterized in that at least one partial layer H contains at least one synthetic polymer P and gelatin, the ratio by weight of all the polymers P and gelatin in this layer being from 40:60 to 80:20 and the ratio of polymer to gelatin in the partial layer L being less 25:75.
2. A colour photographic recording material as claimed in claim 1, characterized in that the layer H contains at least one low molecular weight colour coupler.
3. A colour photographic recording material as claimed in claim 1, characterized in that at least one emulsion layer sensitized to another spectral region is present between at least one partial layer H and at least one partial layer L.
4. A colour photographic recording material as claimed in claim 1, characterized in that the polymer is a high molecular weight polymerization, polycondensation or polyaddition product.
5. A colour photographic recording material as claimed in claim 1, characterized in that the polymer is completely or predominantly a nonionic or anionic polyurethane.
6. A colour photographic recording material as claimed in claim 1, characterized in that the polymer is at least partly charged with a colour coupler.
7. A colour photographic recording material as claimed in claim 1, characterized in that the glass transition temperature of the polymer is below 25°C.
8. A colour photographic recording material as claimed in claim 1, characterized in that the polymer P is present in dispersion form with an average particle size of 20 to 2,000 nm.
9. A process for producing colour photographic images by imagewise exposure of the material claimed in claim 1 and development in a developer bath containing at least one p-phenylene diamine.