EP0318799A2 - Color photographic recording material with a cyan phenolic coupler - Google Patents

Abstract

In a colour-photographic recording material, which contains a phenolic cyan coupler and whose proteinatious binder (gelatine) has been hardened with a fragmenting hardener, the mechanical load-bearing capacity can be improved by additionally using a plasticising acrylate polymer latex.

Description

The invention relates to a color photographic recording material which contains at least one layer of a phenolic cyan coupler and a plasticizing acrylate polymer latex.

It is known to produce colored photographic images by chromogenic development, that is to say by developing imagewise exposed silver halide emulsion layers in the presence of suitable color couplers by means of suitable color-forming developer substances - so-called color developers - the oxidation product of the developer substances with the color coupler which is formed in accordance with the silver image being formed of a dye image reacts. Aromatic compounds containing primary amino groups, in particular those of the p-phenylenediamine type, are usually used as color couplers.

It is known that a high proportion of ballast in photographic layers causes poor mechanical properties of the respective photographic material. The volume filling level of the gelatin should not be less than 45%, so that the known mechanical properties such as elongation at break, breaking strength etc. are acceptable. In recent times, wherever time, where ever higher demands are placed on sharpness, granularity and shorter processing times, the proportion of the binder must be reduced. This deteriorates the mechanical properties, among other things. also sensitivity to pressure and tension, which are ultimately also reflected in the sensitometry. Even more rational manufacturing processes, which include result in higher material temperatures when watering, affect pressure and tensile sensitivity.

• 1. Härtungsmittel, die die Gelatineketten durch Wasserabspaltung verknüpfen und bei der Härtungsreaktion als fotografisch inaktive Fragmente in der Schicht freigesetzt werden.
• 2. Härtungsmittel, von denen ein Teil bei der Ver­knüpfung der Gelatineketten mit eingebaut wird, während ein anderer Teil freigesetzt wird.

In addition to the light-sensitive silver halide, all organic additives of an electroneutral or ionic nature also act as dietary fibers, in particular if they are used from aqueous solution and cannot be emulsified. These fibers also include fragments of hardening agents that are released as by-products in the hardening reaction and remain in the layer. Such hardeners are referred to below as fragmenting hardeners. They are divided into two groups:

• 1. Hardening agents which link the gelatin chains by splitting off water and are released as photographically inactive fragments in the layer during the hardening reaction.
• 2. Hardening agents, part of which is incorporated when the gelatin chains are linked, while another part is released.

It has been shown that recording materials which have been hardened with such fragmenting hardeners, in particular in connection with the phenolic cyan couplers which have recently been used because of higher dye stability, have an increased sensitivity to mechanical stress. Such recording materials, for example, after bending, as e.g. is sometimes unavoidable when transporting film inside the camera with the emulsion layer being wound on the outside, a density drop in the bending area after development (winding error).

Numerous possibilities are described in the literature which improve the mechanical properties of film materials. For example, US-A-2 960 404 describes a method of adding polyhydric alcohols, e.g. Ethylene glycol, glycerin and trimethylolpropane for the gelatin layer. The addition of these compounds counteracts the winding error, but such compounds cause the surface of photographic recording materials to stick strongly.

Other possibilities, for example the incorporation of polyurethanes as described in DE-C-1 472 746 and DE-A-1 522 387, contribute to the formation of fog and, due to particle coarsening, cause embedded color coupler dispersions to be particularly moist warm climate, an increase in color grain and although the breaking strength is greatly improved, the above-mentioned error is significantly increased.

The invention has for its object to provide a color photographic recording material which contains a phenolic cyan coupler and is hardened with a fragmenting hardener and which has a reduced sensitivity to mechanical stress.

The invention relates to a color photographic recording material having at least one layer which contains light-sensitive silver halide and a cyan coupler in a proteinaceous binder and has been hardened with a hardening agent for the proteinaceous binder which forms inert fibers remaining in the layer when hardened that at least one photosensitive silver halide emulsion layer contains a phenolic cyan coupler and a plasticizing acrylate polymer latex.

worin bedeuten
R¹ Acyl,
R² Alkyl oder Acylamino
R³ H oder Halogen, z.B. Chlor;
oder R² und R³ zusammen einen ankondensierten, gegebenenfalls stickstoffhaltigen heterocyclischen Ring;
X H, Halogen oder eine bei Farbkupplung abspaltbare Gruppe.The recording material according to the invention contains, for example, a phenolic cyan coupler of the formula I in at least one light-sensitive silver halide emulsion layer

in what mean
R1 acyl,
R² alkyl or acylamino
R³ H or halogen, for example chlorine;
or R² and R³ together form a condensed, optionally nitrogen-containing heterocyclic ring;
XH, halogen or a group that can be split off with a color coupling.

An acyl radical represented by R 1 is in particular an acyl radical which is derived from aliphatic or aromatic carboxylic acids, in particular halogen-, alkyl-, alkoxy- or aroxy-substituted carboxylic acids, or from N-alkyl- or N-aryl-substituted carbamic acids.

worin bedeuten:
Z O oder S;
R⁴ eine Alkylengruppe mit 1 bis 20 C-Atomen, insbesondere eine Methylengruppe oder eine Alkylidengruppe der Formel

H oder Alkyl bedeutet und wobei Alkyl geradkettig oder verzweigt sein kann;
R⁵ Halogen, Hydroxy, Carboxy, Alkyl, Cycloalkyl, Aryl, Aralkyl, Alkoxy, Aryloxy, Alkylsulfamoyl, Aryl sulfamoyl, Alkylsulfonamido, Arylsulfonamido, Al­kylsulfonyl, Arylsulfonyl, Alkoxycarbonyl oder Acyloxy, worin Alkyl 1 bis 20 C-Atome enthält, wo­rin Aryl vorzugsweise eine gegebenenfalls substi­tuierte Phenylgruppe ist und worin Alkyl, Aryl und Aralkyl auch beliebig mit Alkyl, Hydroxy, Carboxy, Alkoxycarbonyl oder Acyloxy substituiert sein kön­nen; und
m 1- 3.An alkyl radical represented by R 2 preferably has 1 to 4 carbon atoms and can be unsubstituted or substituted. An acylamino residue represented by R² contains, for example, an acyl residue derived from a carboxylic acid containing a ballast group. Such an acyl radical corresponds, for example, to the following formula

in which mean:
ZO or S;
R⁴ is an alkylene group with 1 to 20 carbon atoms, in particular a methylene group or an alkylidene group of the formula

Is H or alkyl and where alkyl can be straight-chain or branched;
R⁵ halogen, hydroxy, carboxy, alkyl, cycloalkyl, aryl, aralkyl, alkoxy, aryloxy, alkylsulfamoyl, arylsulfamoyl, alkylsulfonamido, arylsulfonamido, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl or acyloxy, in which alkyl contains 1 to 20 carbon atoms, in which aryl preferably one is optionally substituted phenyl group and in which alkyl, aryl and aralkyl can also be substituted as desired with alkyl, hydroxy, carboxy, alkoxycarbonyl or acyloxy; and
m 1-3.

Couplers of the formula I in which R 2 is an acylamino group are preferred, and those in turn in which those in formula I the acyl radicals represented by R 1 are derived from an N-phenylcarbamic acid, the phenyl ring preferably being substituted, for example by halogen, cyano, -CF₃, alkylsulfonyl, sulfamoyl or -SO₂F.

Examples of phenolic cyan couplers used according to the invention are listed below:

The acrylate polymer latex used according to the invention is a dispersion of water-insoluble particles of a polymer which mainly consists of polymerized structural units of a monomer of the following formula II:
CH₂ = CH-COO-R (II)
where R is an alkyl radical having 1 to 8 carbon atoms. Examples of R are ethyl, propyl, butyl, 2-ethylhexyl.

The acrylate polymer used can be a homopolymer or a copolymer which has a lower proportion of one or more monomers (comonomers) copolymerizable with alkyl acrylate, for which, for example, the following are possible: acrylamide, acrylic acid, sulfonic acid group-containing acrylic monomers, e.g. ω-acrylamido-ω-methylpropanesulfonic acid (AMPS), hydroxyalkyl acrylate, glycidyl acrylate, alkoxyalkyl acrylate.

The composition must be selected so that the proportion of the comonomer may have to be kept so low that a copolymer which is insoluble in water is always obtained as a latex during the copolymerization.

Also suitable as polymer latex are graft polymers of polyalkyl acrylate on suitable polymeric graft bases, e.g. on polyurethanes as described, for example, in US Pat. No. 3,791,857, or on gelatin or on polyvinylpyrrolidone.

Also suitable are alkyl acrylate copolymers with a small proportion of a copolymerized copolymerizable wetting agent, as described, for example, in EP-A-0 010 335.

The glass transition temperature Tg is decisive for the suitability as a softening acrylate polymer latex.

The glass transition temperature is determined using differential thermal analysis (G. W. MILLER, Applied Polymer Symposia No. 10, (1969), pp. 35-72). Plasticizing polymers in the sense of the present invention are particularly those with a glass transition temperature of below -10 ° C.

To estimate the T _g values of copolymers, the equation from Gordon-Taylor, J. Appl. Chem. 2, 492 (1952) can be used. It enables in shape
(T _g -T _A ) W _A + K (T _g -T _B ) W _B = O
the calculation of the glass transition temperature T _{g of} a particular copolymer when the glass transition temperatures of the corresponding homopolymers T _A and T _B and the proportions by weight W _A and W _{B of} the comonomers in question in the copolymer are known. In this way, a suitable selection of monomers which are suitable for building up the acrylate polymer latex according to the invention can thus be made. The T _g values of conventional homopolymers are described in the "Polymer Handbook" by Brandrup et. al., Interscience Publishers, Wiley & Sons, New York, 1966.

The particles of the acrylate polymer latex used according to the invention can also be surrounded by a thin shell of a harder polymer and can be present as a so-called core / shell polymer, as described, for example, in DE-A-3 516 466. Such a harder polymer can, for example, have a glass transition temperature of above 35 ° C.

Examples of polymers according to the invention are given below:

Gelatin is preferably used as the proteinaceous binder in the recording material according to the invention.

The hardening agent used to harden the proteinaceous binder, in particular the gelatin, corresponds to the following formula III
A - B (III)
wherein A and B denote parts of the curing agent which are bonded together by a reactive bond which is released in the course of the curing reaction, at least one of the A and B parts of the molecule remaining in the hardened binder matrix in modified form as a result of reaction with the binder as inert fiber . The curing agents used according to the invention can be one of the two above assign designated groups. The fragmenting hardeners of the first group split off water from the gelatin chains, which they add. As a result, they escape balance and then remain in the layer as inert fiber. The so-called carboxyl group-activating hardeners are to be counted for this. Of the fragmenting hardeners of the second group, one part of the molecule is firmly incorporated into the crosslinked binder matrix when the gelatin chains are linked, while another part of the molecule forms a low-molecular inert fiber during the hardening reaction with the gelatin, which at least partially remains in the binder matrix.

worin bedeuten
R¹ Alkyl, Aryl oder Aralkyl;
R² einen Rest wie R¹ oder einen Alkyl-, Aryl-, Aral­kyl- oder Alkaralkylrest, der mit einer Gruppe der Formel

verknüpft ist, oder
R¹ und R² zusammen die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Pipe­razin- oder Morpholinringes erforderlichen Atome, wobei dieser Ring z.B. durch C₁-C₃-­Alkyl oder Halogen substituiert sein kann;
R³ Wasserstoff, Alkyl, Aryl, Alkoxy, Acylamino, eine über eine Alkylengruppe angeknüpfte Hydroxy-, Alkoxy-, Acyloxy, Amino- oder Acylaminogruppe, eine gegebenenfalls über eine Alkylengruppe angeknüpfte Ureidogruppe oder ein Brückenglied oder eine direkte Bindung an eine Polymerkette;
Z die zur Vervollständigung eines 5- oder 6-gliedri­gen aromatischen heterocyclischen Ringes, gegebe­nenfalls mit anelliertem Benzolring, erforderlichen C-Atome und
X^⊖ ein Anion, das entfällt, wenn bereits eine anioni­sche Gruppe mit dem übrigen Molekül verknüpft ist;

worin
R¹, R², R³ und X^⊖ die für Formel IV angegebene Bedeutung haben;

worin bedeuten
R⁴ bis R⁷ C₁-C₂₀-Alkyl, C₇-C₂₀-Aralkyl, C₆-C₂₀-Aryl, jeweils unsubstituiert oder durch Halogen, Sulfo, Alkoxy, Di-C₁-C₄-alkyl-substituiertes Carbamoyl und, im Falle von Aralkyl und Aryl durch C₁-C₂₀-­Alkyl substituiert;
R⁸ eine durch ein nucleophiles Agens abspaltbare Gruppe bedeuten und
X^⊖ die in Formel IV angegebene Bedeutung hat, wobei jeweils
2 der substituenten R⁴ bis R⁷ zusammen mit einem Stickstoffatom oder der Gruppe

gegebenenfalls unter Einschluß weiterer Heteroatome wie O oder N auch einen gesättigten, 5- bis 7-glie­drigen Ring bilden können;
R⁹―N=C=N―R¹⁰      (VII)
worin
R⁹ C₁-C₁₀-Alkyl, C₅-C₈-Cycloalkyl, C₃-C₁₀-Alkoxyalkyl oder C₇-C₁₅-Aralkyl bedeutet,
R¹⁰ die Bedeutung von R⁹ hat oder für einen Rest der Formel

steht, wobei
R¹¹ C₁-C₄-Alkylen und
R¹², R¹³ und R¹⁴ C₁-C₆-Alkyl bedeuten, wobei einer der Reste R¹², R¹³ und R¹⁴ durch eine Carbamoylgruppe oder eine Sulfogruppe substituiert sein kann und/oder zwei dieser Reste zusammen mit dem Stick­stoffatom zu einem gegebenenfalls substituierten heterocyclischen Ring, beispielsweise einem Pyrro­lidin-, Piperazin- oder Morpholinring verknüpft sein können;
X^⊖ die in Formel IV angegebene Bedeutung hat;

worin
X^⊖ die in Formel IV angegebene Bedeutung hat,
R⁸ die in Formel VI angegebene Bedeutung hat;
R¹⁵ C₁-C₁₀-Alkyl, C₆-C₁₅-Aryl oder C₇-C₁₅-Aralkyl, jeweils unsubstituiert oder durch Carbamoyl, Sulfamoyl oder Sulfo substituiert, bedeutet; und
R¹⁶ und R¹⁷ Wasserstoff, Halogen, Acylamino, Nitro, Carbamoyl, Ureido, Alkoxy, Alkyl, Alkenyl, Aryl oder Aralkyl oder gemeinsam die restlichen Glieder eines mit dem Pyridiniumring kondensierten Ringes, insbesondere eines Benzoringes, bedeuten,
wobei
R⁸ und R¹⁵ miteinander verknüpft sein können, wenn R⁸ eine Sulfonyloxygruppe ist;

worin
R¹, R² und X^⊖ die in Formel IV angegebene Bedeutung haben und
R¹⁸ C₁-C₁₀-Alkyl, C₆-C₁₄-Aryl oder C₇-C₁₅-Aralkyl bedeutet;

worin
R¹, R² und X^⊖ die in Formel IV angegebene Bedeutung haben,
R¹⁹ Wasserstoff, Alkyl, Aralkyl, Aryl, Alkenyl, Alkoxy, Alkylthio oder Amino bedeutet,
R²⁰ und R²¹ Alkyl,Aralkyl, Aryl, Alkenyl, Acyl oder zusammen gemeinsam mit dem Stickstoffatom die rest­lichen Glieder eines heterocyclischen Ringes bedeuten,

worin bedeuten
R²² Wasserstoff, Alkyl oder Aryl
R²³ Acyl, Alkoxycarbonyl, Aryloxycarbonyl oder Carbamoyl;
R²⁴ Wasserstoff oder R²³;
R²⁵ und R²⁶ Alkyl, Aryl, Aralkyl oder gemeinsam mit dem Stickstoffatom die restlichen Glieder eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes bedeuten, und
X^⊖ die in Formel IV angegebene Bedeutung hat.Examples of the curing agents used according to the invention correspond, for example, to one of the following general formulas IV to XI:

in what mean
R1 alkyl, aryl or aralkyl;
R² is a radical such as R¹ or an alkyl, aryl, aralkyl or alkaralkyl radical which is a group of the formula

is linked, or
R¹ and R² together are the atoms necessary to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring can be substituted, for example, by C₁-C₃-alkyl or halogen;
R³ is hydrogen, alkyl, aryl, alkoxy, acylamino, a hydroxy, alkoxy, acyloxy, amino or acylamino group attached via an alkylene group, an ureido group optionally attached via an alkylene group or a bridge link or a direct link to a polymer chain;
Z the C atoms and required to complete a 5- or 6-membered aromatic heterocyclic ring, optionally with a fused benzene ring
X ^⊖ an anion which is omitted if an anionic group is already linked to the rest of the molecule;

wherein
R¹, R², R³ and X ^{⊖ have} the meaning given for formula IV;

in what mean
R⁴ to R⁷ C₁-C₂₀-alkyl, C₇-C₂₀-aralkyl, C₆-C₂₀-aryl, in each case unsubstituted or by halogen, sulfo, alkoxy, di-C₁-C₄-alkyl-substituted carbamoyl and, in the case of aralkyl and aryl C₁-C₂₀ alkyl substituted;
R⁸ is a group which can be split off by a nucleophilic agent and
X ^{⊖ has} the meaning given in formula IV, where in each case
2 of the substituted R⁴ to R⁷ together with a nitrogen atom or the group

optionally including a further 5- to 7-membered ring, including other heteroatoms such as O or N;
R⁹ ― N = C = N ― R¹⁰ (VII)
wherein
R⁹ is C₁-C₁₀-alkyl, C₅-C₈-cycloalkyl, C₃-C₁₀-alkoxyalkyl or C₇-C₁₅-aralkyl,
R¹⁰ has the meaning of R⁹ or for a radical of the formula

stands, where
R¹¹ C₁-C₄ alkylene and
R¹², R¹³ and R¹⁴ are C₁-C₆-alkyl, where one of the radicals R¹², R¹³ and R¹⁴ can be substituted by a carbamoyl group or a sulfo group and / or two of these radicals together with the nitrogen atom to form an optionally substituted heterocyclic ring, for example a pyrrolidine -, piperazine or morpholine ring can be linked;
X ^{⊖ has} the meaning given in formula IV;

wherein
X ^{⊖ has} the meaning given in formula IV,
R⁸ has the meaning given in formula VI;
R¹⁵ is C₁-C₁₀ alkyl, C₆-C₁₅ aryl or C₇-C₁₅ aralkyl, each unsubstituted or substituted by carbamoyl, sulfamoyl or sulfo; and
R¹⁶ and R¹⁷ represent hydrogen, halogen, acylamino, nitro, carbamoyl, ureido, alkoxy, alkyl, alkenyl, aryl or aralkyl or together the remaining members of a ring condensed with the pyridinium ring, in particular a benzo ring,
in which
R⁸ and R¹⁵ may be linked when R⁸ is a sulfonyloxy group;

wherein
R¹, R² and X ^{⊖ have} the meaning given in formula IV and
R¹⁸ is C₁-C₁₀ alkyl, C₆-C₁₄ aryl or C₇-C₁₅ aralkyl;

wherein
R¹, R² and X ^{⊖ have} the meaning given in formula IV,
R¹⁹ represents hydrogen, alkyl, aralkyl, aryl, alkenyl, alkoxy, alkylthio or amino,
R²⁰ and R²¹ represent alkyl, aralkyl, aryl, alkenyl, acyl or together with the nitrogen atom the remaining members of a heterocyclic ring,

in what mean
R²² is hydrogen, alkyl or aryl
R²³ acyl, alkoxycarbonyl, aryloxycarbonyl or carbamoyl;
R²⁴ is hydrogen or R²³;
R²⁵ and R²⁶ are alkyl, aryl, aralkyl or together with the nitrogen atom the remaining members of an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, and
X ^{⊖ has} the meaning given in formula IV.

Compounds of formula IV are preferred. Other suitable fragmenting hardeners are, for example, water-soluble sulfates from a heteroaromatic bis- or polysulfone as described in DE-A-3 708 541 or water-soluble addition compounds from tertiary amine and a heteroaromatic bis- or polysulfone as described in DE-A-3 628 717.

Examples of fragmenting hardeners used according to the invention are given below:

In making the color photographic light-sensitive material of the present invention, the diffusion-resistant phenolic cyan coupler is incorporated into the coating solution of the red-sensitive silver halide emulsion layer together with the plasticizing acrylate polymer latex. For example, the preferably oil-soluble or hydrophobic couplers can be added to a hydrophilic colloid solution from a solution in a suitable coupler solvent (oil former), if appropriate in the presence of a wetting or dispersing agent. The hydrophilic casting solution can of course contain other conventional additives in addition to the binder. The solution of the couplers need not be directly dispersed in the casting solution for the silver halide emulsion layer or other water permeable layer; rather, it can also advantageously be first dispersed in an aqueous non-photosensitive solution of a hydrophilic colloid, whereupon the mixture obtained, if appropriate after the removal of the low-boiling organic solvents used, is mixed with the casting solution for the photosensitive silver halide emulsion layer or another water-permeable layer before application.

Suitable light-sensitive silver halide emulsions are emulsions of silver chloride, silver bromide or mixtures thereof, possibly with a low silver iodide content of up to 10 mol% in one of the commonly used hydrophilic binders. Gelatin is preferably used as a binder for the photographic layers. However, this can be replaced in whole or in part by other natural or synthetic binders.

The emulsions can be chemically and spectrally sensitized in the usual way and the emulsion layers as well as other non-photosensitive layers are hardened in the usual way, for which purpose a fragmenting hardener is used according to the present invention.

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

Each of the light-sensitive layers mentioned can consist of a single layer or, in a known manner, for example in the case of the so-called double-layer arrangement, also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470). Red-sensitive silver halide emulsion layers are usually arranged closer to the support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, a yellow filter layer which is not sensitive to light generally being located between green-sensitive layers and blue-sensitive layers. However, other arrangements are also conceivable. A layer which is not sensitive to light is generally arranged between layers of different spectral sensitivity and can contain means for preventing the incorrect diffusion of developer oxidation products. If there are several silver halide emulsion layers of the same spectral sensitivity, these can be immediately adjacent to one another or arranged in such a way that a light-sensitive layer with a different spectral sensitivity is located between them (DE-A-1 958 709, DE-A-2 530 645, DE-A -2 622 922).

Color photographic recording materials for producing multicolored images usually contain, in spatial and spectral assignment to the silver halide emulsion layers of different spectral sensitivity, coloring compounds, here in particular color couplers, for producing the different partial color images cyan, purple and yellow.

Spatial assignment is understood to mean that the color coupler is in such a spatial relationship to the silver halide emulsion layer that an interaction between them is possible which permits an image-wise match between the silver image formed during development and the color image generated from the color coupler. This is generally achieved by the fact that the color coupler is contained in the silver halide emulsion layer itself or in a possibly non-light-sensitive binder layer adjacent to it.

A spectral assignment is to be understood to mean that the spectral sensitivity of each of the light-sensitive silver halide emulsion layers and the color of the partial color image generated from the spatially assigned color coupler are in a specific relationship, each of the spectral sensitivities (red, green, blue) having a different color of the relevant partial color image (e.g. teal, purple, yellow) is assigned.

One or more color couplers can be assigned to each of the differently spectrally sensitized silver halide emulsion layers. If there are several silver halide emulsion layers of the same spectral sensitivity, each of them can contain a color coupler, which color couplers need not necessarily be identical. They should only result in at least approximately the same color during color development, normally a color that is complementary to the color of the light, for which the silver halide emulsion layers in question are predominantly sensitive.

According to the present invention, red-sensitive silver halide emulsion layers are assigned at least one non-diffusing phenolic cyan coupler. Green-sensitive silver halide emulsion layers are assigned at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone, indazolone or pyrazoloazole type usually being used. Finally, blue-sensitive silver halide emulsion layers are assigned at least one non-diffusing color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping. Color couplers of this type are known in large numbers and are described in a large number of patents. One example is the publications "Color Coupler" by W. PELZ in "Messages from the research laboratories of Agfa, Leverkusen / Munich", Volume III, page 111 (1961) and by K. VENKATARAMAN in "The Chemistry of Synthetic Dyes", Vol. 4, 341 to 387, Academic Press (1971).

The color couplers can be both conventional 4-equivalent couplers and 2-equivalent couplers in which a smaller amount of silver halide is required to produce the color. As is well known, 2-equivalent couplers are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site, which is split off during the coupling. The 2-equivalent couplers include both those that are practically colorless and 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. The latter couplers can also be present in the light-sensitive silver halide emulsion layers and serve there as mask couplers to compensate for the undesired secondary densities of the image dyes. However, the known white couplers are also to be counted among the 2-equivalent couplers, but they do not give any dye when reacted with color developer oxidation products. Among the 2-equivalent couplers are also the known DIR couplers, which are couplers which contain a detachable residue in the coupling point, which is released as a diffusing development inhibitor when reacted with color developer oxidation products. Other photographically active compounds, for example development accelerators or fogging agents, can also be released during the development from such couplers.

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

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

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

For the production of color photographic images, the color photographic recording material according to the invention is developed with a color developer compound. All developer compounds which have the ability in the form of their oxidation product with color couplers can be used as the color developer compound React azomethine dyes. Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines, such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl-3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.

Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3100 (1951) and in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, pages 545 ff.

After color development, the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together. The usual compounds can be used as bleaching agents, for example Fe³⁺ salts and FE³⁺ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes etc. Iron-III complexes of aminopolycarboxylic acids are particularly preferred, in particular, for example, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediamine triacetic acid, alkyliminodicarboxylic acids and alkyliminodicarboxylic acids and Phosphonic acids. Persulphates are also suitable as bleaching agents.

example 1

A color photographic recording material for color negative development was produced by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given. All silver halide emulsions were stabilized per 100 g of AgNO₃ with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

Layer 1 (antihalo layer)

Black colloidal silver sol with
0.3 g Ag and 1.4 g gelatin.

Layer 2 (intermediate layer)

0.3 g gelatin.

Layer 3 (1st red-sensitized layer)

red-sensitized silver chloride bromide iodide emulsion (5 mol% iodide; average grain diameter 0.5 µm) from 2.4 g AgNO₃, with
0.9 mmol cyan coupler (as indicated in Table 1)
0.06 g red mask CR-1
0.037 g DIR coupler D-1
1.2 g gelatin
0.2 g polymer (as indicated in Table 1)

Layer 4 (2nd red-sensitized layer)

Red-sensitized silver bromide iodide emulsion (10 mol% iodide; average grain diameter 0.8 µm) from 2.9 g AgNO₃, with
0.25 mmol cyan coupler (as in layer 3)
0.02 g red mask CR-1
0.04 g DIR coupler D-2
2.0 g gelatin
0.2 g polymer (as in layer 3)

Layer 5 (intermediate layer)

0.9 g gelatin

Layer 6 (1st green-sensitized layer)

green-sensitized silver bromide iodide emulsion (5 mol% iodide; average grain diameter 0.4 µm) from 2.2 g AgNO₃, with
0.65 g purple coupler M-1
0.02 g yellow mask MY-1
0.043 g DIR coupler D-1
1.4 g gelatin

Layer 7 (2nd green-sensitized layer)

green-sensitized silver bromide iodide emulsion (10 mol% iodide; average grain diameter 0.8 µm) from 2.7 g AgNO₃, with
0.17 g purple coupler M-1
0.04 g yellow mask MY-1
1.6 g gelatin

Layer 8 (yellow filter layer)

yellow colloidal silver sol with
70 mg Ag and 0.32 g gelatin

Layer 9 (1st blue sensitive layer)

Silver bromide iodide emulsion (3 mol% iodide; average grain diameter 0.3 µm) from 0.95 g AgNO₃, with
0.96 g yellow coupler Y-1
1.4 g gelatin

Layer 10 (2nd blue sensitive layer)

Silver bromide iodide emulsion (8 mol% iodide; average grain diameter 0.8 µm) from 1.0 g AgNO₃, with
0.22 g yellow coupler Y-1
1.6 g gelatin

Layer 11 (protective layer)

0.8 g UV absorber UV-1
1.1 g gelatin

Layer 12 (protective layer)

0.8 g gelatin

Layer 13 (hardening layer)

0.3 g of gelatin and hardener as indicated in Table 1.

The formulas of the compounds used in Example 1 are listed below:

Various versions of the specified recording material were produced, which differed only in the cyan coupler contained in layers 3 and 4 and the curing agent used, and in the presence or absence of a polymer according to the present invention.

The following cyan couplers were used for comparison:

General dispersion instructions for the cyan couplers:

100 g of coupler are dissolved together with 80 g of dibutyl phthalate in 300 ml of ethyl acetate and at 50 ° C. with a high-speed mixing siren in 1.3 l of 7.5% gelatin, likewise heated to 50 ° C., which is additionally mixed with 10 g of sodium dodecylbenzenesulfonate. emulsified. The low-boiling solvent is then removed in vacuo and the remaining dispersion is allowed to solidify at 6 ° C.

The various materials were cut into 35 mm wide test strips.

The test strips were then individually stored with the emulsion side inside (egg) in opaque cans (r = 1.5 cm) for one day in a room climate.

Following the egg pre-storage, the strips that were stitched together in loops were hung with the emulsion side facing outwards (Ea) over a rod (radius = 2.5 mm) and, loaded with a weight of 250 g, 3 days in a room climate (dark room) stored (23 ± 1 ° C, 50 to 60% RH).

Following this storage, the strips were exposed on D _max with a flash unit with a diffuser and processed according to EC Gehret, British Journal of Photography 1974, p. 594.

The strips were evaluated using a Joyce-Gevaert densitometer. The difference in density of the cyan dye ΔD _max / cyan visible on the test strips as a crossbar was measured.

From Table 1 it can clearly be seen that there was practically no transverse stripe (D _max difference) on the strip which contained the triple (phenolic cyan coupler / fragmenting hardener / polymer) of the compounds according to the invention, while in the presence of phenolic couplers in Absence of acrylates an error occurred as horizontal stripes. Table 1 Coupler Polymer in layers 3 and 4 Hardening agent [mg / m²] ΔD _max / cyan VC-1 ./. 0.6 g H-7 Cf. 0 I-2 ./. 0.6 g H-7 Cf. 0.38 I-2 P-1 0.6 g H-7 erf. 0.02 I-5 ./. 0.6 g H-7 Cf. 0.31 I-5 P-2 0.6 g H-7 erf. 0.00 I-8 ./. 0.4 g H-10 Cf. 0.26 I-8 P-4 0.4 g H-10 erf. 0.02 VC-2 ./. 0.4 g H-24 Cf. 0.03 I-10 ./. 0.4 g H-24 Cf. 0.36 I-10 P-9 0.4 g H-24 erf. 0.01

Example 2

Various color photographic recording materials were produced as in Example 1, with the difference that a non-inventive polymer was also used as a plasticizer for comparison. The different combinations can be seen in Table 2. Table 2 Coupler Polymer in layers 3 and 4 Hardening agent ΔD _max / cyan I-14 ./. 0.5 g H-2 Cf. 0.32 I-14 0.1 g VP-1 * 0.5 g H-2 Cf. 0.34 I-14 0.2 g VP-1 0.5 g H-2 Cf. 0.37 I-14 0.3 g VP-1 0.5 g H-2 Cf. 0.39 I-14 0.1 g P-2 0.5 g H-2 erf. 0.17 I-14 0.2 g P-2 0.5 g H-2 erf. 0.08 I-14 0.3 g P-2 0.5 g H-2 erf. 0.02 * VP-1 is compound 12 from DE-C-1 472 746.

It can easily be seen from the table that the combination according to the invention, depending on the amount of polymer added, has a considerably lower maximum density loss when tested using the test method in Example 1.

Example 3

The maximum density loss shown as a crossbar in Examples 1 and 2 can also be shown as a complete gradation as follows. For this purpose, 2 sensitometer strips are individually stored as in the 1st test method.

Following the egg pre-storage, a strip with the emulsion side on the outside and the other with the emulsion side on the inside is wound on a rod (r = 4 mm) and stored in black bags for 3 days in a room climate. The winding takes place with a counterweight of 100 g. The strips are attached using extremely thin polyester adhesive tape (60 µm).

The strips are then exposed with a graduated gray wedge and processed as described in Example 1. The blue-green gradations obtained are then measured. In the event of damage, the Ea-wrapped strip has a flatter bg gradation than the egg-wrapped strip.

Table 3 shows the values of the combination tested.

It can clearly be seen that the combinations according to the invention have practically no γ differences in egg and Ea winding. Table 3 Coupler 0.2 g each of polymer in layers 3 and 4 Hardening agent γEi γEa I-1 ./. 0.6 g H-44 Cf. 0.58 0.50 I-1 P-6 0.6 g H-44 erf. 0.55 0.55 I-11 ./. 0.9 g H-13 Cf. 0.65 0.54 I-11 P-10 0.9 g H-13 erf. 0.64 0.62 I-16 ./. 0.6 g H-7 Cf. 0.67 0.54 I-16 P-2 0.6 g H-7 erf. 0.66 0.65

Claims (9)

1. Color photographic recording material with at least one layer which contains light-sensitive silver halide and a cyan coupler in a proteinaceous binder and has been hardened with a hardening agent for the proteinaceous binder which forms inert fibers remaining in the layer when hardened, characterized in that at least a photosensitive silver halide emulsion layer contains a phenolic cyan coupler and a plasticizing acrylate polymer latex. 2. Recording material according to claim 1, characterized in that the phenolic cyan coupler corresponds to the following formula I.

in what mean
R1 acyl;
R² is alkyl or acylamino;
R³ H or halogen;
or R² and R³ together form a condensed, optionally nitrogen-containing heterocyclic ring;
XH, halogen or a group that can be split off with a color coupling. 3. Recording material according to claim 2, characterized in that in formula I R² is acylamino, wherein the acyl radical corresponds to the following formula

in which mean:
ZO or S;
R⁴ is an alkylene group with 1 to 20 C atoms;
R⁵ halogen, hydroxy, carboxy, alkyl, cycloalkyl, aryl, aralkyl, alkoxy, aryloxy, alkylsulfamoyl, arylsulfamoyl, alkylsulfonamido, arylsulfonamido, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl or acyloxy;
m 1-3. 4. Recording material according to claim 2, characterized in that in formula I the acyl radical represented by R¹ is derived from an N-phenylcarbamic acid. 5. Recording material according to one of claims 1 to 4, characterized in that the layer containing the phenolic cyan coupler contains a dispersion of water-insoluble particles of a polymer which consists predominantly of polymerized structural units of a monomer of the following formula II
CH₂ = CH - COO - R (II)
where R is alkyl having 1 to 8 carbon atoms. 6. Recording material according to claim 5, characterized in that the polymer has a glass transition temperature Tg of below -10 ° C. 7. Recording material according to one of claims 5 or 6, characterized in that the polymer particles are surrounded by a thin shell of a harder polymer. 8. Recording material according to one of claims 1 to 7, characterized in that the proteinaceous binder is gelatin which is hardened with a hardening agent of the formula III, A - B (III)
wherein A and B represent molecular parts of the hardening agent which are connected to one another by a reactive bond which is released in the course of the hardening reaction, at least one of the molecular parts A and B in a form modified by reaction with the gelatin as inert fiber in the hardened gelatin matrix remains. 9. Recording material according to claim 8, characterized in that the curing agent is a carboxyl group-activating curing agent.