EP0401610B1 - Silver halide colour photographic material - Google Patents

Description

The invention relates to a color photographic silver halide material with high sensitivity and high color density, which has good spectral absorption properties, especially in the purple range.

In color photography based on light-sensitive silver halides, the colors yellow, purple and blue-green are created by reaction of the developer oxidation product with the corresponding couplers. Pyrazolone compounds are usually used as purple couplers, but they pose numerous problems. Firstly, they have an undesired absorption in the wavelength range from 400 to 500 nm in addition to the desired and predominant absorption in the range from 540 to 560 nm. Secondly, the dyes produced with these couplers show a low maximum color density, thirdly, the long-term stability of these couplers is unsatisfactory because it is not Exposed photographic material shows when stored for a long time, especially in the presence minimal amounts of formaldehyde, a change in color and a decrease in color formation during color development.

A large number of proposals have been made to overcome these drawbacks, with the most promising approach being to use purple couplers of a different structure. It has been shown that pyrazolotriazole magenta couplers show no undesired absorption, are essentially resistant to formaldehyde and have a high color constancy. On the other hand, these couplers have the disadvantage that they can only be used to produce unstable dispersions which are to be incorporated into the silver halide emulsions. In addition, the absorption wavelengths of the dyes produced with these couplers are shorter than the desired value.

In order to remedy these difficulties as well, EP-A-145 342, which contains a number of further references, proposes to disperse pyrazolotriazole magenta couplers of a certain structure in certain phenolic compounds (so-called oil formers) and thus into them Silver halide emulsion to incorporate.

In this way, it is possible to overcome the aforementioned difficulties to a certain degree, but the proposed solutions either fall ill too low sensitivity, too large fog, too low formaldehyde resistance and inadequate stability of the coupler dispersgate made from it.

It has now been found that these difficulties can also be overcome if special oil formers are used for pyrazolotriazole magenta couplers.

worin

R₁

Alkyl, Aryl oder ein Ballastrest,

R²

ein Ballastrest, Alkyl oder Aryl,

Z

Wasserstoff oder eine Gruppe die bei Reaktion mit dem Entwickleroxidationsprodukt abgespalten werden kann, bedeuten,

und eine Verbindung der Formel (III)

enthält, worin

R₃

Alkyl, Alkoxy, Aryl, gegebenenfalls substituiertes Amino oder den Rest eines Heterocyclus,

R₄

Alkyl, Aryl oder einen Heterocyclus,

bedeuten, mit Ausnahme der Verbindung der Formel

The invention therefore relates to a color photographic silver halide material which comprises a purple coupler of the formulas (I) or (II) in at least one silver halide emulsion layer.

wherein

R₁

Alkyl, aryl or a ballast residue,

R²

a ballast residue, alkyl or aryl,

Z.

Is hydrogen or a group which can be split off on reaction with the developer oxidation product,

and a compound of formula (III)

contains what

R₃

Alkyl, alkoxy, aryl, optionally substituted amino or the residue of a heterocycle,

R₄

Alkyl, aryl or a heterocycle,

mean, except for the compound of the formula

The alkyl radicals R₁ and R₂ have in particular 1 to 16 carbon atoms, e.g. Methyl, ethyl, butyl, dodecyl, iso-propyl, tert-butyl, iso-amyl, and can be substituted by halogen atoms, C₁-C₄ alkylsulfonyl groups or phenoxy groups, e.g. CF₃, C₃F₇, CH₃-SO₂-CH₂-CH₂-CH₂-.

The aryl radicals R₁ and R₂ are in particular optionally substituted by C₁-C₄-alkyl, halogen, C₁-C₄-alkoxi, C₁-C₄-alkylcarbonylamino, C₁-C₄-alkylsulfonylamino, C₁-C₄-alkylsulfonyl, C₁-C₄-alkoxycarbonyl, phenyl or naphthyl radicals .

Preferably either R₁ or R₂ is a ballast group.

The leaving group Z is preferably halogen, for example chlorine, bromine, iodine or fluorine, an aryloxy group, for example phenoxy) p-methoxyphenoxy, p-butanesulfonamidophenoxy or p-tert.-butylcarboamidophenoxy, an arylthio group, for example phenylthio or a heterocyclic thio group, e.g. 1-ethyltetrazole-5-thiolyl. Z is preferably a halogen atom, in particular chlorine.

worin

Z′

eine Gruppe ist, die durch Reaktion mit dem Entwickleroxidationsprodukt abgespalten wird,

R₉ und R₁₀

Wasserstoff oder Alkyl,

R₁₁

Alkyl, Halogen oder Hydroxy

l, p und q

eine Zahl 0 bis 4 und

r

0 oder 1 bedeuten.

Such residues are to be regarded as ballast residues, which make it possible to store the compounds according to the invention in a diffusion-resistant manner in the hydrophilic colloids usually used in photographic materials. Organic radicals which generally contain straight-chain or branched aliphatic groups and optionally also isocyclic or heterocyclic aromatic groups having generally 8-20 C atoms are preferably suitable for this purpose. With the rest of the molecule, these radicals are either directly or indirectly, for example connected via one of the following groups: -NHCO-, -NHSO₂-, -NR-, where R is hydrogen or alkyl, -O- or -S-, In addition, the diffusion-proofing residue also contain water-solubilizing groups, such as sulfo groups or carboxyl groups, which may also be in anionic form. Since the diffusion properties depend on the molecular size of the total compound used, it is sufficient in certain cases, for example if the total molecule used is large enough, to use shorter-chain residues as ballast residues. The pyrazolotriazole coupler preferably corresponds to the formula (IV)

wherein

Z ′

is a group which is split off by reaction with the developer oxidation product,

R₉ and R₁₀

Hydrogen or alkyl,

R₁₁

Alkyl, halogen or hydroxy

l, p and q

a number 0 to 4 and

r

0 or 1 mean.

L is preferably a number 0 to 3, p is a number 1 to 3 and q is 1 or 2.

Alkyl R₃ is especially C₁-C₆ alkyl; Alkoxy R₃ is in particular C₁-C₄ alkoxy; Aryl R₃ and R₄ is in particular phenyl and phenyl substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen.

Optionally substituted amino R₃ is in particular amino, C₁-C₁ Alkyl-alkylamino, di-C₁-C₁₂-alkylamino, -NHCO- R₅, NHCO-heterocycle, -NH-CO-NHR₅ and -NHSO₂-R₅, where R₅ is alkyl or aryl and Heterocycle has the following meaning.

Suitable heterocycle residues are in particular pyridyl and morpholinyl.

wobei R₆ und R₇ geradkettige oder verzweigte Alkylreste mit zusammen 6 bis 28 C-Atomen sind.Alkyl R₄ is in particular C₈-C₃₀-alkyl, preferably C₈-C₃₀-alkyl with at least one branch, in particular alkyl of the formula

where R₆ and R₇ are straight-chain or branched alkyl radicals with a total of 6 to 28 carbon atoms.

The group -SO₂R₃ in p- and the group -NHCOORCO in the o-position to the OH group are preferably linked to the phenyl radical.

Typical examples of pyrazolotriazole magenta couplers according to the invention are listed below.

Typical examples of the phenol compounds of formula III according to the invention are listed below.

The production of the purple couplers is known for example from EP-A-145 342. The phenolic compounds of the formula (III) are prepared by known methods. A typical method is described in the examples.

The silver halide can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms. However, platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain. However, the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is greater than 5: 1, e.g. 12: 1 to 30: 1.

The silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as doping of the individual grain areas, being different. The average grain size of the emulsions is preferably between 0.2 »m and 2.0» m, the grain size distribution can be both homo- and heterodisperse. In addition to the silver halide, the emulsions can also contain organic silver salts, for example silver benzotriazolate or silver behenate.

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

The photographic emulsions can be prepared by various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966)) VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.

The silver halide is preferably precipitated in the presence of the binder, for example the gelatin, and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used. The latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide. The water-soluble silver salts and the halides are combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded. The pAg range can vary within wide limits during the precipitation, the so-called pAg-controlled method is preferably used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation. In addition to the preferred precipitation with an excess of halide, so-called inverse precipitation with an excess of silver ions is also possible. In addition to precipitation, the silver halide crystals can also grow by physical ripening (Ostwald ripening) in the presence of excess halide and / or silver halide complexing agent. The growth of the emulsion grains can even take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.

Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe may also be present during the precipitation and / or physical ripening of the silver halide grains.

The precipitation can also be carried out in the presence of sensitizing dyes. Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.

The silver halides can be, for example, silver bromide, silver bromide iodide with iodide contents from 0.1 to 40 mol%, silver chloride, silver chloride bromide with bromide contents from 1 to 80 mol% and silver bromide iodide chloride with a predominant proportion of bromide.

Gelatin is preferably used as the binder. 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-vinylpyrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates. Semi-synthetic gelatin substitutes are usually modified natural products. Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives, which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers, are examples of this.

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. The production of such gelatins is published, for example, in The Science and Technology of Gelatine AG 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 gelatin can be partially or completely oxidized.

After crystal formation has been completed or at an earlier point in time, the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchangers.

The photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss Phot. 47 (1952), pp. 2-58. Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, (subst.) Benzotriazoles or benzothiazolium salts can also be used as antifoggants. Heterocycles containing mercapto groups are particularly suitable, for example mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, these mercaptoazoles can also contain a water-solubilizing group, for example a carboxyl group or sulfo group. Other suitable compounds are published in Research Disclosure No. 17643 (1978), Section VI.

The stabilizers can be added to the silver halide emulsions before, during or after their ripening. Of course, the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.

Mixtures of two or more of the compounds mentioned can also be used.

The silver halide emulsions are usually chemically ripened, for example by the action of gold compounds or compounds of divalent sulfur.

The photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics ( eg acceleration of development, high contrast, sensitization etc.).

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

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 bromide.

Color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive emulsion layer. These 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 cyan couplers are assigned to the red-sensitive layers, magenta couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers, wherein according to the invention magenta couplers of the formula (I) or (II) are used exclusively or in a mixture with other magenta couplers described below.

Color couplers for producing the blue-green partial color image are usually couplers of the phenol or α-naphthol type; suitable examples of this are known in the literature.

Color couplers for producing the yellow partial color field are usually couplers with an open-chain ketomethylene grouping, in particular couplers of the type α-acylacetamids; Suitable examples are α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers, which are also known from the literature.

Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; Suitable examples of this are described in large numbers in the literature.

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), the white couplers that react with Color developer oxidation products result in essentially colorless products. The 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling point, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue ( eg DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428,) develops a certain desired photographic activity, 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.

Since with DIR, DAR or FAR couplers mainly the effectiveness of the residue released during coupling is desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-1 547 640).

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 incorporation of the couplers or other compounds in silver halide emulsion layers can be done in this way take place that a solution, a dispersion or an 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 by grinding processes are described, for example, in DE-A-2 609 741 and DE-A-2 609 742.

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, so-called polymeric oil formers, can be used.

The compounds can also be introduced into the casting solution in the form of loaded latices. Reference is made, for example, to DE-A-2 541 230, DE-A-2 541 274, DE-A-2 835 856, EP-A-0 014 921, EP-A-0 069 671, EP-A-0 130 115, U.S.-A-4,291,113.

It should be noted, however, that couplers of the formula (I) or (II) according to the invention using compounds of the formula (III) are introduced into a casting solution and thus into an emulsion layer.

The diffusion-resistant incorporation of anionic water-soluble compounds (e.g. dyes) can also be carried out with the help of cationic polymers, so-called pickling polymers.

Suitable oil formers for other couplers and other compounds are e.g. Alkyl phthalates, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters and trimesic acid esters.

Color photographic material typically comprises at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support. The order of these layers can be varied as desired. Couplers that form blue-green, purple and yellow dyes are usually incorporated into the red, green or blue-sensitive emulsion layers. However, different combinations can also be used.

Each of the light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470). Here, red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers, which in turn are closer than blue-sensitive layers, with green-sensitive layers generally being different Layers and blue-sensitive layers there is a non-light-sensitive yellow filter layer.

With a suitably low intrinsic sensitivity of the green or Red-sensitive layers can be chosen without the yellow filter layer, other layer arrangements in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.

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

If there are several sub-layers of the same spectral sensitization, these can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains. In general, the sublayer with higher sensitivity will be located further away from the support than the sublayer with lower sensitivity. Partial layers of the same spectral sensitization can be adjacent to one another or separated by other layers, for example by layers of different spectral sensitization. For example, all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A 1 958 709, DE-A-2 530 645, DE-A 2 622 922).

The photographic material may further contain UV light absorbing compounds, whites, spacers, filter dyes, formalin scavengers and others.

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, styrene 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 e.g. in Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter V.

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 3 331 542, DE-A 3 424 893, Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter XVI).

The average particle diameter of the spacers is in particular in the range from 0.2 to 10 »m. 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.

The binders of the material according to the invention, in particular if gelatin is used as the binder, are hardened with suitable hardeners, for example with hardeners of the epoxy type, the ethyleneimine type, the acryloyl type or the vinylsulfone type. Diazine, triazine or 1,2-dihydroquinoline series hardeners are also suitable.

The binders of the material according to the invention are preferably hardened with instant hardeners.

Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry and the swelling of the layer structure occurs as a result of the crosslinking reaction . Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).

These hardening agents that react very quickly with gelatin are e.g. to 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 to form peptide bonds and crosslink the gelatin.

• a)
  
     worin

  R₁

  Alkyl, Aryl oder Aralkyl bedeutet,

  R₂

  die gleiche Bedeutung wie R₁ hat oder Alkylen, Arylen, Aralkylen oder Alkaralkylen bedeutet, wobei die zweite Bindung 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 bedeuten, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,

  R₃

  für Wasserstoff, Alkyl, Aryl, Alkoxy, -NR₄-COR₅, -(CH₂)_m-NR₈R₉, -(CH₂)_n-CONR₁₃R₁₄ oder

  

  oder ein Brückenglied oder eine direkte Bindung an eine Polymerkette steht, wobei

  R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈, und R₁₉

  Wasserstoff oder C₁-C₄-Alkyl,

  R₅

  Wasserstoff, C₁-C₄-Alkyl oder NR₆R₇,

  R₈

  -COR₁₀

  R₁₀

  NR₁₁R₁₂

  R₁₁

  C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

  R₁₂

  Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

  R₁₃

  Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

  R₁₆

  Wasserstoff, C₁-C₄-Alkyl, COR₁₈ oder CONHR₁₉,

  m

  eine Zahl 1 bis 3

  n

  eine Zahl 0 bis 3

  p

  eine Zahl 2 bis 3 und

  Y

  O oder NR₁₇ bedeuten oder

  R₁₃ und R₁₄

  gemeinsam die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes erforderlichen Atome darstellen, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,

  Z

  die zur Vervollständigung eines 5- oder 6-gliedrigen aromatischen heterocyclischen Ringes, gegebenenfalls mit anelliertem Benzolring, erforderlichen C-Atome und

  X^⊖

  ein Anion bedeuten, das entfällt, wenn bereits eine anionische Gruppe mit dem übrigen Molekül verknüpft ist;

• b)
  
     worin

  R₁, R₂, R₃

  und X^⊖ die für Formel (a) angegebene Bedeutung besitzen.

Suitable examples of instant hardeners are, for example, compounds of the general formulas

• a)
  
  wherein

  R₁

  Means alkyl, aryl or aralkyl,

  R₂

  has the same meaning as R₁ or means alkylene, arylene, aralkylene or alkaralkylene, the second bond having a group of the formula

  

  is linked, or

  R₁ and R₂

  together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, the ring being able to be substituted, for example, by C₁-C₃alkyl or halogen,

  R₃

  for hydrogen, alkyl, aryl, alkoxy, -NR₄-COR₅, - (CH₂) _m -NR₈R₉, - (CH₂) _n -CONR₁₃R₁₄ or

  

  or a bridge link or a direct bond to a polymer chain, wherein

  R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈, and R₁₉

  Hydrogen or C₁-C₄ alkyl,

  R₅

  Hydrogen, C₁-C₄-alkyl or NR₆R₇,

  R₈

  -COR₁₀

  R₁₀

  NR₁₁R₁₂

  R₁₁

  C₁-C₄ alkyl or aryl, especially phenyl,

  R₁₂

  Hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,

  R₁₃

  Hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,

  R₁₆

  Hydrogen, C₁-C₄-alkyl, COR₁₈ or CONHR₁₉,

  m

  a number 1 to 3

  n

  a number 0 to 3

  p

  a number 2 to 3 and

  Y

  O or NR₁₇ mean or

  R₁₃ and R₁₄

  together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring may be substituted, for example, by C₁-C₃alkyl or halogen,

  Z.

  the carbon atoms required to complete a 5- or 6-membered aromatic heterocyclic ring, optionally with a fused benzene ring, and

  X ^⊖

  mean an anion which is omitted if an anionic group is already linked to the rest of the molecule;

• b)
  
  wherein

  R₁, R₂, R₃

  and X ^{⊖ have} the meaning given for formula (a).

The materials according to the invention, be it color negative or color reversal films, color negative or color reversal paper or direct positive materials, are processed in the usual manner according to the processes recommended for this.

Example 1 (comparison)

In each case 8 mmol pp coupler (see Table 1) were dissolved in ethyl acetate (EA) at about 50 ° C. and oil formers (ÖF; see Table 1) and di-n-octyl sulfosuccinate (emulsifier) were added, so that a weight ratio
Coupler: ÖF: EA: Emulsifier = 1: 1: 3: 0.1
resulted. The mixture was then emulsified in 7.5% by weight gelatin solution. A ratio results depending on the molecular weight
Coupler: approx. 1: 2 gelatin.

The emulsifier was 6 min. stirred at 1000 U / min, where it heated to about 50 ° C and EA was suctioned off in a water jet vacuum (200-300 mbar).

• a) Teilchengröße
  • 1: sehr fein (< 0,5 »m)
  • 2: fein (< 1,0 »m)
  • 3: fein mit einigen größeren Teilchen
  • 4: mittel
  • 5: grob
• b) Homogenität
  • 1: keine Kristalle erkennbar
  • 2: vereinzelt Kristalle erkennbar
  • 3: viele Kristalle erkennbar
  • 4: stark auskristallisiert

The quality of the fresh coupler emulgate was assessed as follows using a phase contrast or polarization microscope:

• a) Particle size
  • 1: very fine (<0.5 »m)
  • 2: fine (<1.0 »m)
  • 3: fine with some larger particles
  • 4: medium
  • 5: rough
• b) homogeneity
  • 1: no crystals recognizable
  • 2: isolated crystals
  • 3: many crystals can be seen
  • 4: strongly crystallized

The same assessment was made after the Emulgate had been stirred intensively for 3 h and 6 h at 50 ° C.

Comparison coupler

Reference oil former

Example 2

enthielt. Nach dem Trocknen und Aufschneiden wurden die so hergestellten Proben hinter einem Stufenkeil belichtet und im Negativ-AP 70 Prozeß (38°C) verarbeitet.

The Emulgate prepared according to the example were mixed with a silver bromide iodide emulsion (0.7 mol% iodide) in a ratio of 1 mol coupler: 5.2 mol AgNO₃, applied to a layer of cellulose acetate and with a protective layer made of a 3% by weight gelatin solution overlays the compound of the formula as a curing agent

contained. After drying and slicing, the samples thus produced were exposed behind a step wedge and processed in the negative AP 70 process (38 ° C.).

The following baths were used:

Color developer

Bleach bath

Fixer

E

Empfindlichkeit in DIN-Einheiten

γ

Steigung der charakteristischen Kurve im linearen Teil

FA

Farbausbeute in D_max/aufgetragenes Ag

S

Schleier

It means:

E

Sensitivity in DIN units

γ

Slope of the characteristic curve in the linear part

FA

Color yield in D _max / applied Ag

S

veil

Table 2 shows that the combination according to the invention, in comparison with the couplers or oil formers of the prior art, is distinguished by high sensitivity, steep gradation and high color yield with comparable fresh fog values.

Example 3

Individual layers produced according to Example 2 of the couplers and oil formers listed in Table 3 were exposed to a formalin concentration of 10 ppm at 70% rel. Before exposure and processing according to Example 2 for 0, 3, 7, 14 and 21 days. Exposed to humidity.

The following color density values resulted after processing:

Example 4

Schicht 1

(Antihalogschicht)
Schwarzes kolloidales Silbersol mit
0,18 g Ag
0,30 g UV-Absorber UV-1
1,5 g Gelatine

Schicht 2

(Zwischenschicht)
Silberbromidiodidemulsion (0,8 mol-% Iodid) aus 0,15 g AgNO₃, mit
0,15 g 2,5-Dioctylhydrochinon
0,11 g Kuppler BG 1
0,3 g Gelatine

Schicht 3

(1. rotsensibilisierte Schicht)
rotsensibilisierte Silberbromidiodidemulsion (5 mol-% Iodid) aus 0,7 g AgNO₃, mit
0,1 g Kuppler BG 2
0,3 g Kuppler BG 3
0,01 g Kuppler BG 4
1,2 g Gelatine

Schicht 4

(2. rotsensibilisierte Schicht)
rotsensibilisierte Silberbromidiodidemulsion (10 mol-% Iodid) aus 1,2 g AgNO₃, mit
0,1 g Kuppler BG 2
0,05 g Kuppler BG 3
0,05 g Kuppler BG 5
0,9 g Gelatine

Schicht 5

(3. rotsensibilisierte Schicht)
rotsensibilisierte Silberbromidiodidemulsion (10 mol-% Iodid) aus 2,0 g AgNO₃, mit
0,05 g Kuppler BG 3
0,15 g Kuppler BG 5
0,003 g Kuppler DIR 1
0,8 g Gelatine

Schicht 6

(Zwischenschicht)
0,5 g Gelatine

Schicht 7

(1. grünsensibilisierte Schicht)
grünsensibilisierte Silberbromidiodidemulsion (5 mol-% Iodid) aus 0,5 g AgNO₃, mit
0,3 g Kuppler V1 in VÖ 1
0,4 g Kuppler MG 1
0,5 g Kuppler MG 2
0,5 g Kuppler DIR 2
1,2 g Gelatine

Schicht 8

(2. grünsensibilisierte Schicht)
grünsensibilisierte Silberbromidiodidemulsion (6 mol-% Iodid) aus 1,0 g AgNO₃, mit
0,25 g Kuppler V1 in VÖ1
0,01 g Kuppler MG 1
0,01 g Kuppler MG 2
0,01 g Kuppler DIR 2
1,7 g Gelatine

Schicht 9

(3. grünempfindliche Schicht)
grünsensibilisierte Silberbromidiodidemulsion (10 mol-% Iodid) aus 1,5 g AgNO₃, mit
0,015 g Kuppler MG 1
0,07 g Kuppler V1 in VÖ 1
0,002 g Kuppler DAR 1
1,0 g Gelatine

Schicht 10

(Gelbfilterschicht)
gelbes kollidales Silbersol aus 0,05 g Ag, mit
0,03 g 3,5-Ditert.-octylhydrochinon und
0,6 g Gelatine

Schicht 11

(1. blauempfindliche Schicht)
Silberbromidiodidemulsion (5 mol-% Iodid) aus 0,3 g AgNO₃, mit
0,7 g Kuppler Y1
0,03 g Kuppler DIR 3
1,4 g Gelatine

Schicht 12

(2. blauempfindliche Schicht)
Silberbromidiodidemulsion (5 mol-% Iodid) aus 0,3 g AgNO₃, mit
0,25 g Kuppler Y1
0,6 g Gelatine

Schicht 13

(Mikratschicht)
Silberbromidiodidemulsion (2 mol-% Iodid) aus 0,4 g AgNO₃, mit
0,1 g Gelatine

Schicht 14

(3. blauempfindliche Schicht)
Silberbromidiodidemulsion (10 mol-% Iodid) aus 0,8 g AgNO₃, mit
0,2 g Kuppler Y1
0,5 g Gelatine

Schicht 15

(1. Schutzschicht)
0,14 g UV-Absorber UV-1
0,20 g UV-Absorber UV-2
0,4 g Gelatine

Schicht 16

(2. Schutzschicht)
0,95 g Härtungsmittel gemäß Beispiel 2
0,23 g Gelatine

A color photographic recording material for negative color 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

(Anti-halogen layer)
Black colloidal silver sol with
0.18 g Ag
0.30 g UV absorber UV-1
1.5 g gelatin

Layer 2

(Intermediate layer)
Silver bromide iodide emulsion (0.8 mol% iodide) from 0.15 g AgNO₃, with
0.15 g 2,5-dioctyl hydroquinone
0.11 g Coupler BG 1
0.3 g gelatin

Layer 3

(1st red-sensitized layer)
red-sensitized silver bromide iodide emulsion (5 mol% iodide) from 0.7 g AgNO₃, with
0.1 g BG 2 coupler
0.3 g BG 3 coupler
0.01 g Coupler BG 4
1.2 g gelatin

Layer 4

(2nd red-sensitized layer)
red-sensitized silver bromide iodide emulsion (10 mol% iodide) from 1.2 g AgNO₃, with
0.1 g BG 2 coupler
0.05 g Coupler BG 3
0.05 g Coupler BG 5
0.9 g gelatin

Layer 5

(3rd red-sensitized layer)
red-sensitized silver bromide iodide emulsion (10 mol% iodide) from 2.0 g AgNO₃, with
0.05 g Coupler BG 3
0.15 g coupler size 5
0.003 g coupler DIR 1
0.8 g gelatin

Layer 6

(Intermediate layer)
0.5 g gelatin

Layer 7

(1st green-sensitized layer)
green-sensitized silver bromide iodide emulsion (5 mol% iodide) from 0.5 g AgNO₃, with
0.3 g coupler V1 in release 1
0.4 g MG 1 coupler
0.5 g MG 2 coupler
0.5 g coupler DIR 2
1.2 g gelatin

Layer 8

(2nd green-sensitized layer)
green-sensitized silver bromide iodide emulsion (6 mol% iodide) from 1.0 g AgNO₃, with
0.25 g coupler V1 in release 1
0.01 g MG 1 coupler
0.01 g MG 2 coupler
0.01 g coupler DIR 2
1.7 g gelatin

Layer 9

(3rd green-sensitive layer)
green-sensitized silver bromide iodide emulsion (10 mol% iodide) from 1.5 g AgNO₃, with
0.015 g MG 1 coupler
0.07 g coupler V1 in release 1
0.002 g coupler DAR 1
1.0 g gelatin

Layer 10

(Yellow filter layer)
yellow colloidal silver sol from 0.05 g Ag, with
0.03 g of 3,5-di-tert-octylhydroquinone and
0.6 g gelatin

Layer 11

(1st blue sensitive layer)
Silver bromide iodide emulsion (5 mol% iodide) from 0.3 g AgNO₃, with
0.7 g coupler Y1
0.03 g coupler DIR 3
1.4 g gelatin

Layer 12

(2nd blue sensitive layer)
Silver bromide iodide emulsion (5 mol% iodide) from 0.3 g AgNO₃, with
0.25 g coupler Y1
0.6 g gelatin

Layer 13

(Micrate layer)
Silver bromide iodide emulsion (2 mol% iodide) from 0.4 g AgNO₃, with
0.1 g gelatin

Layer 14

(3rd blue sensitive layer)
Silver bromide iodide emulsion (10 mol% iodide) from 0.8 g AgNO₃, with
0.2 g coupler Y1
0.5 g gelatin

Layer 15

(1st protective layer)
0.14 g UV absorber UV-1
0.20 g UV absorber UV-2
0.4 g gelatin

Layer 16

(2nd protective layer)
0.95 g of curing agent according to Example 2
0.23 g gelatin

The recording material thus produced is referred to as material A (not according to the invention). In the same way, a material B was produced according to the present invention, which differs from material A only in that in layers 7, 8 and 9 the coupler C2 in ÖF 5 was used instead of V1 in VÖ 1.

After exposure and processing as described in Example 2, the following sensitometric data were obtained. The values obtained when materials A and B had been stored in the drying cabinet (35 ° C.; 85% relative humidity) for 1 week before exposure are given in brackets.

After exposure to 10 ppm formalin at 70% rel.

Moisture for 21 days before exposure u. Processing, D _max decreased from material A to 0.95 from material B to only 2.70.

The following connections were used:

Claims (5)

1. Colour photographic silver halide material which contains in at least one silver halide emulsion layer a magenta coupler of the formulae (I) or (II)

   

   in which

   R₁   means alkyl, aryl or a ballast residue,

   R₂   means a ballast residue, alkyl or aryl

   Z   means hydrogen or a group which may be eliminated on reaction with the developer oxidation product,

   and a compound of the formula (III)

   

   in which

   R₃   means alkyl, alkoxy, aryl, optionally substituted amino or the residue of a heterocycle,

   R₄   means alkyl, aryl or a heterocycle

   with the exception of the compound of the formula

   
2. Colour photographic silver halide material according to claim 1, in which Z means halogen, an aryloxy group, an arylthio group or a heterocyclic thio group.
3. Colour photographic silver halide material according to claim 1, in which the magenta coupler is of the formula (IV)

   

   in which

   Z′   is a group which is eliminated by reaction with the developer oxidation product,

   R₉ and R₁₀   mean hydrogen or alkyl,

   R₁₁   means alkyl, halogen or hydroxy,

   l, p and q   mean a number from 0 to 4 and r means 0 or 1.
4. Colour photographic silver halide material according to claim 3, in which

   l   means a number from 0 to 3,

   p   means a number from 1 to 3 and

   q   means a number 1 or 2.
5. Colour photographic silver halide material according to claim 1 in which the phenol is of the formula

   

   and R₃ and R₄ have the stated meaning.