EP0447657B1 - Photographic recording material - Google Patents

Description

The invention relates to a photographic recording material with a layer support and at least one photosensitive silver halide emulsion layer arranged thereon.

According to the invention, the material contains special triazoles as antifoggants and special heterocyclic mercapto compounds as stabilizers.

Recording materials with light-sensitive silver halide emulsions, in particular chemically sensitized ones, are known to tend to form fog, caused by germs which can be developed without exposure.

It is known to add so-called antifoggants or stabilizers to photographic silver halide emulsions to reduce the formation of fog, e.g. B. heterocyclic compounds containing sulfur, for example in the form of a mercapto group.

For example, reference should be made to the German interpretation documents 1 183 371 (GB 1 067 066), 1 189 380 (US 3 364 028 and 3 365 294), 1 597 503 (US 3 615 617), DE 1 979 027, to the German published documents 1 522 363 (GB 1 186 441), 2 042 533 (US 3 761 278), 2 130 031 and 2 308 530.

Furthermore, these compounds are used to adapt the sensitivity of the emulsions to the specified standard.

When using the above-mentioned conventional antifoggants to lower the sensitivity, the flattening of the gradation curve of the respective silver halide emulsion occurs as an undesirable side effect.

The object of the invention was to develop a photographic recording material in which the sensitivity and the gradation of the silver halide emulsions can be controlled independently of one another.

sowie einen Stabilisator der Formel (II) in einer Menge von 10⁻⁵ - 10⁻² Mol pro Mol Silberhalogenid

enthält, worin

X

H, ein Kation eines Metallatoms oder eines Nichtmetallrestes, eine Gruppe mit kovalenter Bindung zu dem Stickstoffatom des Triazols, die erst bei der Verarbeitung des Materials unter Freisetzung des Triazols gespalten wird,

R₁

H, gegebenenfalls substituiertes C₁-C₉-Alkyl, C₂-C₈-Alkenyl, C₆-C₁₀-Aryl, SR₃

R₂

H, gegebenenfalls substituiertes C₁-C₉-Alkyl, C₂-C₈-Alkenyl, C₆-C₁₀-Aryl, C₅-C₁₀-Heteroaryl, Cl, Br, -COOR₃, -COR₃, -OCOR₃,

R₃

gegebenenfalls substituiertes C₁-C₉-Alkyl, C₂-C₈-Alkenyl, C₆-C₁₀-Aryl, C₅-C₁₀-Heteroaryl,

Me

H, NH₄, Alkalimetalle wie Na, K, ein zweiwertiges Kation wie Zn oder Ca oder ein Kation eines Nichtmetallrestes wie Triethylammonium

Z

die zur Vervollständigung eines 5- oder 6-gliedrigen heterocyclischen Ringes benötigten Glieder, beispielsweise zur Vervollständigung der folgenden Ringe:
Imidazol, Oxazol, Thiazol, Selenazol, Triazol, Thiadiazol, Oxadiazol, Tetrazol, Pyridin, Pyrimidin, Triazin sowie deren Benzo- und Naphthoderivate.

The invention relates to a photographic recording material with a layer support and at least one photosensitive silver halide emulsion layer arranged thereon, characterized in that indicates that the silver halide emulsion layer is an antifoggant of formula (I)

and a stabilizer of the formula (II) in an amount of 10⁻⁵ - 10⁻² mol per mol of silver halide

contains what

X

H, a cation of a metal atom or a non-metal radical, a group with a covalent bond to the nitrogen atom of the triazole, which is only cleaved when the material is processed to release the triazole,

R₁

H, optionally substituted C₁-C₉-alkyl, C₂-C₈-alkenyl, C₆-C₁₀-aryl, SR₃

R₂

H, optionally substituted C₁-C₉-alkyl, C₂-C₈-alkenyl, C₆-C₁₀-aryl, C₅-C₁₀-heteroaryl, Cl, Br, -COOR₃, -COR₃, -OCOR₃,

R₃

optionally substituted C₁-C₉ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, C₅-C₁₀ heteroaryl,

Me

H, NH₄, alkali metals such as Na, K, a divalent cation such as Zn or Ca or a cation of a non-metal radical such as triethylammonium

Z.

the members required to complete a 5- or 6-membered heterocyclic ring, for example to complete the following rings:
Imidazole, oxazole, thiazole, selenazole, triazole, thiadiazole, oxadiazole, tetrazole, pyridine, pyrimidine, triazine and their benzo and naphtho derivatives.

The heterocyclic compounds can be further substituted, for example by fluorine, chlorine, bromine, optionally also by substituted alkyl groups having preferably up to 8 carbon atoms such as methyl, ethyl, isopropyl, alkenyl such as allyl, cycloalkyl such as cyclohexyl, optionally substituted aryl such as phenyl or Naphthyl, hydroxy, alkoxy with preferably up to 6 carbon atoms such as methoxy or butoxy, mercapto, alkylthio with preferably up to 6 carbon atoms such as methylthio, butylthio, carboxyl, alkoxycarbonyl, sulfo, optionally substituted sulfonamide, nitro, amino, with alkyl , Aryl or acyl substituted amino, such as butylamino or acetylamino.

Examples of cations of a metal atom according to group X are Na ^⊕ , K ^⊕ , Mg ^2⊕ and Zn ^2⊕ ; a cation of a non-metal radical represents, for example, NH₄ ^⊕ .

Suitable heteroaryl radicals are, for example: thiophene, furan, 1,2,4-triazole and pyridine.

-CO-N(CH₃)₂, -CO-CH₃, -SO₂-N(CH₃)₂ und SO₂-CH₃.The following examples serve for groups which are covalently bonded to the nitrogen atom and can be split off during processing of the photographic material:

-CO-N (CH₃) ₂, -CO-CH₃, -SO₂-N (CH₃) ₂ and SO₂-CH₃.

Suitable substituents of the radicals R₁, R₂ and R₃ are conventional substituents in the field of photographic antifoggants, such as halogen, in particular chlorine or bromine, C₁-C₄-alkoxy groups, C₁-C₄-alkoxycarbonyl, C₆-C₁₀-aryloxycarbonyl and C₁-C₄-alkylcarbonyloxy.

Aryl and heteroaryl can also be substituted with C₁-C₈ alkyl.

The state of the art under Article 54 (3) EPC is EP-A-0 369 235. Antifoggants of the formula (I) and stabilizers of the formula (II) have already been described here.

Suitable examples of the compounds (I) according to the invention in which the group X is each hydrogen are listed below:

The antifoggants according to the invention are used in an amount of 10⁻⁵ to 10⁻², preferably 0.5 to 5 x 10⁻³ mol per mol of silver halide.

The compounds are prepared by known methods, as described, for example, in the literature:

For R₁ = alkyl, aryl and R₂ = carboxylic acid ester group in Klein et al .; J. Heterocyclic Chem. 13 , 589 (1976). The alcohol component of the ester can be exchanged by transesterification with sodium alcoholate catalysis at 60 to 100 ° C.

For R₁ = alkylthio and R₂ = carboxylic acid ester group in Nemeryuk et al., Coll. Czech. Chem. Commun. 51: 215 (1981) and Goerdeler et al., Ber. 99 , 1618 (1966).

For R₁ = alkylthio and R₂ = alkanoyl or aroyl in RT Chakrasuli et al., Synthesis 1988 , 453.

5-Mercapto-1,2,3-triazole can be used, for example, to obtain alkylthio-1,2,3-triazoles by alkylation with alkyl bromides. 1,2,4-triazole-substituted 1,2,3-triazoles can be prepared in a conventional manner by ring-closing reaction of a 1,2,3-triazolecarboxylic acid ester with thiosemicarbazide.

Suitable examples of the stabilizers (II) according to the invention are the following compounds:

Examples of photographic materials are black and white films, black and white paper, black and white reversal photographic paper, color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the silver color bleaching process.

Color photographic recording materials with a layer support and at least three light-sensitive silver halide emulsion layers of different spectral sensitivity arranged thereon, to which a yellow coupler, a magenta coupler and a cyan coupler are each spectrally assigned, in particular color reversal materials, are preferred.

Suitable supports for the production of color photographic materials are, for example, films and foils of semisynthetic and synthetic polymers, such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate, and paper laminated with a baryta layer or α-olefin polymer layer (eg polyethylene). These carriers can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light. The surface the support is generally subjected to a treatment to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.

The color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.

Binding agents, silver halide grains and color couplers are essential components of the photographic emulsion layers.

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-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, 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 sufficient resistant layers can be produced by reaction with suitable curing agents. Such functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.

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

The silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide. For example, the halide content of at least one layer can be 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol%. consist of bromide. In the case of color negative and color reversal films, silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions are usually used. It can be predominantly compact crystals that are, for example, regular cubic or octahedral or Transitional shapes can preferably also be platelet-shaped crystals, 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 substantially greater than 5: 1, for example 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 μm and 2.0 μm, the grain size distribution can be either homodisperse or heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate more than + 30% from the mean grain size. 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 using 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 Emulsions, The Focal Press, London (1966) from soluble silver salts and soluble halides become.

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, preferably the so-called pAg-controlled method is 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 be physically ripened (Ostwald ripened) in the presence of excess halide and / or silver halide complexing agent to grow. 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.

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

Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (for example gold, platinum, palladium, iridium). Thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic compounds can also be used Nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia of Industrial Chemistry, 4th edition, vol. 18, pp. 431 ff. and Research Disclosure No. 17643, Section III). Alternatively or additionally, a reduction sensitization with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid) by hydrogen, by low pAg (z, B, less than 5) and / or high pH (e.g. above 8 ) be performed.

In addition to the compounds according to the invention, azaindenes, preferably tetra- and penta-azaindenes, are suitable, 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. Furthermore, 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, optionally substituted benzotriazoles or benzothiazolium salts are used.

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.

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.). In addition to natural surface-active compounds, for example saponin, synthetic surface-active compounds (surfactants) are mainly used: non-ionic surfactants, for example alkylene oxide compounds, glycerol compounds or glycidol compounds, cationic surfactants, for example higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group, for example carboxylic acid, sulfonic acid, phosphonium compounds, anionic surfactants containing an acid group, for example carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, for example amino acid and aminosulfonic acid compounds and sulfur or phosphoric acid esters of an amino alcohol.

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

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

• 1. als Rotsensibilisatoren
     9-Ethylcarbocyanine mit Benzthiazol, Benzselenazol oder Naphthothiazol als basische Endgruppen, die in 5- und/oder 6-Stellung durch Halogen, Methyl, Methoxy, Carbalkoxy, Aryl substituiert sein können sowie 9-Ethyl-naphthoxathia- bzw. -selencarbocyanine und 9-Ethyl-naphthothiaoxa- bzw. -benzimidazocarbocyanine, vorausgesetzt, daß die Farbstoffe mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff tragen.
• 2. als Grünsensibilisatoren
     9-Ethylcarbocyanine mit Benzoxazol, Naphthoxazol oder einem Benzoxazol und einem Benzthiazol als basische Endgruppen sowie Benzimidazocarbocyanine, die ebenfalls weiter substituiert sein können und ebenfalls mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff enthalten müssen.
• 3. als Blausensibilisatoren
     symmetrische oder asymmetrische Benzimidazo-, Oxa-, Thia- oder Selenacyanine mit mindestens einer Sulfoalkylgruppe am heterocyclischen Stickstoff und gegebenenfalls weiteren Substituenten am aromatischen Kern, sowie Apomerocyanine mit einer Rhodaningruppe.

The following dyes, sorted by spectral range, are particularly suitable:

• 1. as red sensitizers
  9-ethylcarbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups, the can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl and 9-ethyl-naphthoxathia or -selenecarbocyanine and 9-ethyl-naphthothiaoxa- or -benzimidazocarbocyanine, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.
• 2. as green sensitizers
  9-ethyl carbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzthiazole as basic end groups, and also benzimidazocarbocyanines, which may also be further substituted and must likewise contain at least one sulfoalkyl group on the heterocyclic nitrogen.
• 3. as blue sensitizers
  symmetrical or asymmetrical benzimidazo, oxa, thia or selenacyanines with at least one sulfoalkyl group on the heterocyclic nitrogen and optionally further substituents on the aromatic nucleus, and apomerocyanines with a rhodanine group.

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

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

Color couplers for producing the blue-green partial color image are usually couplers of the phenol or α-naphthol type.

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

Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the α-acylacetamide type; suitable examples are α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers.

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 colorless ones are, as well as those that have an intense intrinsic color, which disappears during the color coupling or is replaced by the color of the image dye produced (mask coupler), and the white couplers, which essentially result in colorless products when reacted with color developer oxidation 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), a certain desired photographic activity unfolds, for example as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR and FAR couplers.

DIR couplers which release development inhibitors of the azole type, for example triazoles and benzotriazoles, are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 27 26 180, 36 26 219, 36 30 564, 36 36 824, 36 44 416 and 28 42 063. Further advantages for color reproduction, ie, color separation and color purity, and for detail reproduction, ie, sharpness and granularity, can be achieved with those DIR couplers which, for example, do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after a further follow-up reaction, which is achieved, for example, with a timing group. Examples of this are in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-157 146 and 204 175, in US-A-4 146 396 and 4 438 393 and in GB-A-2 072 363.

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

When using DIR couplers, in particular those which release a well-diffusible development inhibitor, improvements in color rendering, e.g. achieve a more differentiated color rendering, as described, for example, in EP-A-115 304, 167 173, GB-A-2 165 058, DE-A-37 00 419 and US-A-4 707 436.

The DIR couplers can be added to a wide variety of layers in a multilayer photographic material, for example also light-insensitive or intermediate layers. However, they are preferably added to the light-sensitive silver halide emulsion layers, the characteristic properties of the silver halide emulsion, for example its iodide content, the structure of the silver halide grains or their grain size distribution having an influence on the photographic properties achieved. The influence of the inhibitors released can, for example, be incorporated an inhibitor capture layer according to DE-A-24 31 223 are limited. For reasons of reactivity or stability, it may be advantageous to use a DIR coupler which forms a color in the coupling in the respective layer in which it is introduced, which color differs from the color to be produced in this layer.

To increase the sensitivity, the contrast and the maximum density, DAR or FAR couplers can be used, which release a development accelerator or an fogger. Compounds of this type are, for example, in DE-A-25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-89 834, 110 511, 118 087, 147 765 and described in US-A-4,618,572 and 4,656,123.

As an example of the use of BAR couplers (Bleach Accelerator Releasing Coupler), reference is made to EP-A-193 389.

It can be advantageous to modify the effect of a photographically active group which is split off from a coupler in that an intermolecular reaction of this group occurs after its release with another group according to DE-A-35 06 805.

Since in the DIR, DAR and FAR couplers the effectiveness of the residue released during the coupling is mainly desired and the color-forming properties of these couplers are less important, these are also DIR, DAR or FAR couplers are suitable which, when coupled, result in essentially colorless products (DE-A-15 47 640).

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).

The material may further contain compounds other than couplers, which can liberate, for example, a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR hydroquinones and other compounds as described, for example, in US Pat US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.

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. You can but can also be obtained by polyaddition or polycondensation.

The couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it 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-26 09 741 and DE-A-26 09 742.

Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-O 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. Is referred for example on DE-A-25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-A-0 014 921, EP-A-0 069 671, EP-AO 130 115, US A-4 291 113.

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

Examples of suitable oil formers are dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert.-amylphenol, dioctylacelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-doxy-5-butyl-2-butyl -octylaniline, paraffin, dodecylbenzene and diisopropylnaphthalene.

Each of the differently sensitized, light-sensitive layers can consist of a single layer or also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470). In this case, red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.

If the green or red-sensitive layers are suitably low in their own sensitivity, other layer arrangements can be selected without the yellow filter layer, 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 undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.

Suitable agents, which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), Chapter VII, 17 842/1979, pages 94-97 and 18.716 / 1979, page 650 and in EP-A- 69,070, 98,072, 124,877, 125,522 and in US-A-463,226.

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 through other layers, e.g. separated by layers of other spectral sensitization. For example, all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).

The photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides 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, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.

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

Certain layers of binder, in particular the layer furthest away from the support, but also occasionally intermediate layers, especially if they represent the layer furthest away from the support during manufacture, can contain photographically inert particles of an inorganic or organic nature, for example as matting agents or as spacers (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).

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

Additives to improve dye, coupler and whiteness stability and to reduce the color fog (Research Disclosure 17 643/1978, Chapter VII) can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromans, spiroindanes, p- Alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.

Compounds that have both a hindered amine partial structure and a hindered phenol partial structure in one molecule (US-A-4,268,593) are particularly effective in preventing the deterioration (degradation) of yellow color images as a result the development of heat, Moisture and light. In order to prevent the deterioration (deterioration or degradation) of crimson color images, in particular their impairment (deterioration or degradation) as a result of exposure to light, Spiroindane (JP-A-159 644/81) and chromanes are caused by Hydroquinone diethers or monoethers are particularly effective (JP-A-89 835/80).

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

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

There are slow-acting and fast-acting hardeners and so-called instant hardeners, which are particularly advantageous, in the classes listed. 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 caused by the crosslinking reaction and the swelling of the layer structure occurs . 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.

There are diffusible curing agents that have the same curing effect on all layers within a layer structure. But there are also layer-limited, non-diffusing, low-molecular and high-molecular hardeners. With them, individual layers, e.g. crosslink the protective layer particularly strongly. This is important if the silver halide layer is hardened little because of the increase in silver opacity and the mechanical layer has to be improved with the protective layer (EP-A 0 114 699).

Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step. All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound. Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -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 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.

After the color development, an acidic stop bath or watering can follow.

Usually the material is bleached and fixed immediately after color development. As bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used. Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulfates and peroxides, e.g. Hydrogen peroxide.

The bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.

Favorable results can be obtained using a subsequent final bath which contains little or no formaldehyde.

However, the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent. When formaldehyde is added, this stabilizing bath also acts as a final bath.

In the case of color reversal materials, development is first carried out using a black and white developer whose oxidation product is not capable of reacting with the color couplers. This is followed by a diffuse second exposure or chemical fogging and then development with a color developer, bleaching and fixing.

example

This example shows the advantages of the antifoggants according to the invention and the stabilizers when used in color reversal materials.

Color photographic recording materials for reverse processing are produced by successively applying the layers listed below to a cellulose triacetate support provided with an adhesive layer.

Recording material

• 1, (antihalation layer)
  black colloidal silver sol with
  0.2 g Ag
  1.2 g gelatin
  0.10 g UV absorber UV-1
  0.20 g UV absorber UV-2
  0.02 g tricresyl phosphate (CPM)
  0.03 g dibutyl phthalate (DBP)
• 2. (Mikrat intermediate layer)
  Mikrat-silver bromide iodide emulsion
  (0.5 mol% iodide;
  average grain diameter 0.07 µm)
  0.25 g AgNO₃, with
  1.0 g gelatin
  0.10 g CPM
• 3. A red-sensitized silver halide emulsion, average grain diameter 0.5 μm, containing 70 g of gelatin, 60 g of silver (thereof 96 mol% in the form of the bromide and 4 mol% in the form of the iodide) and 55 g of the cyan coupler BG per kg.
  The silver application per m² is 2.5 g of silver nitrate.
• 4. A 2% by weight aqueous gelatin solution with a wet application of 60 g / m 2, containing 4 g of the polymeric white coupler W per kg.
• 5. A green-sensitized silver halide emulsion, average grain diameter 0.45 μm, containing 70 g of gelatin, 60 g of silver (thereof 96 mol% in the form of the bromide and 4 mol% in the form of the iodide) and 60 g of the purple coupler PP per kg.
  The silver application per m² is 2.8 g of silver nitrate.
• 6. A yellow silver dispersion containing per kg the amount of silver corresponding to 1.8 g of silver nitrate and 12 g of gelatin. The color density of the yellow filter layer, measured behind a blue filter, is 0.6; the silver application per m² is 0.2 g silver nitrate.
• 7. An unsensitized silver halide emulsion, average grain diameter 0.6 µm, containing 70 g of gelatin, 60 g of silver (thereof 95 mol% in the form of the bromide and 5 mol% in the form of the iodide) and 140 g of the yellow coupler GB per kg.
  The silver application per m² is 1.5 g of silver nitrate.
• 8. A 1% by weight gelatin solution with a wet application of 60 g per m².
• 9. A 1% strength by weight aqueous solution of hardener H with a wet application of 60 g per m²:
  
  
  
  
  
  
  Weight ratio x: y = 7:13
  

Samples of the photographic reversal material described above were prepared, with Comparative Material No. 1 containing no antifoggants and stabilizers according to the invention. The silver halide-containing casting solutions for the magenta layer of photographic materials 2 to 17 are added with certain amounts of the compounds according to the invention.

The samples thus prepared were exposed under a step wedge and subjected to color reversal development as described in "Manual for Processing Kodak Ektachrome Film Using Process E 7", Eastman Kodak Company, 1977 (see Kodak Publication No. Z-119).

The following data for the purple layer were recorded in Table 1 below.

G1

Anstieg der Gradationskurve zwischen den Punkten 0,2 über Schleier und dem Punkt der Gradationskurve, der bei 0,65 Ig I · t geringerer Belichtung resultiert

E =

Empfindlichkeit: 1g I · t-Wert bei Dichte 1,0

The measurement parameters specified there are defined as follows:

G1

Rise in the gradation curve between points 0.2 over fog and the point on the gradation curve which results at 0.65 Ig I · t less exposure

E =

Sensitivity: 1g I · t value at density 1.0

The measured values of experiments 4, 5, 7, 8, 10, 11, 13, 14, 16, 17 clearly show that when using compounds I and II according to the invention, the sensitivity and the gradation can be controlled independently of one another.

Claims (3)

1. Photographic recording material with a film support and at least one photosensitive silver halide emulsion layer arranged thereon, characterised in that at least one silver halide emulsion layer contains an anti-fogging agent of the formula (I)

   

   together with a stabiliser of the formula (II) in a quantity of 10⁻⁵ to 10⁻² mol per mol of silver halide

   

   in which

   X   means H, a cation of a metal atom or of a non-metallic residue, a group with a covalent bond to the nitrogen atom of the triazole, which bond is broken to release the triazole only when the material is processed,

   R₁   means H, optionally substituted C₁-C₉ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, SR₃,

   R₂   means H, optionally substituted C₁-C₉ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, C₅-C₁₀ heteroaryl, Cl, Br, -COOR₃, -COR₃, -OCOR₃,

   R₃   means optionally substituted C₁-C₉ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, C₅-C₁₀ heteroaryl,

   Me   means H, NH₄, alkali metals such as Na, K, divalent metals such as Zn, Ca or cations of non-metallic residues such as trialkylammonium

   Z   means the members required to complete a 5- or 6-membered heterocyclic ring, for example to complete the following rings:
   imidazole, oxazole, thiazole, selenazole, triazole, thiadiazole, oxadiazole, tetrazole, pyridine, pyrimidine, triazine and the benzo or naphtho derivatives thereof.
2. Photographic recording material according to claim 1, characterised in that at least one silver halide emulsion layer contains an anti-fogging agent of the formula (I) in a quantity of 10⁻⁵ to 10⁻² mol per mol of silver halide.
3. Photographic recording material according to claim 1, characterised in that it is a colour photographic recording material with a film support and at least three photosensitive silver halide emulsion layers of differing spectral sensitivity arranged thereon, with which a yellow coupler, a magenta coupler and a cyan coupler are spectrally associated.