EP0652474B1 - Colour photographic recording material - Google Patents

Description

The invention relates to a negative type color photographic silver halide material with improved sensitivity.

It is known to increase the sensitivity of photographic silver halide materials with the aid of so-called DAR and FAR (development accelerator releasing or fogging agent releasing coupler) couplers, which split off either a development accelerator or a fogging agent during the coupling reaction with the developer oxidation product. However, the increase in sensitivity achieved in this way is not yet sufficient for many applications. In addition, the veil is undesirably increased.

It is also known to use compounds adhering to the silver grain which react with the developer oxidation product and which improve the sensitivity / granularity ratio (EP-A-377 181) or compounds which adhere to the silver grain and develop an active fogging agent during development which improve the sensitivity (EP-A-358 071).

The object of the present invention was to provide additives for photographic materials with which an increase in sensitivity can be achieved without a simultaneous increase in fog.

It has now surprisingly been found that such an increase in sensitivity is achieved if compounds are used which release a 4-equivalent coupler which has a silver-affinity adhesive group during development. Such connections are referred to below as ACR connections (Adsorbing Coupler Releasing). The connection residue splitting off the 4-equivalent coupler carries a ballast group that makes the connection diffusion-resistant, while the splitted off coupler has a silver-affine group with which it is adsorbed on the silver grain.

enthält, wobei

A

einen Ballastrest,

B

den Rest einer Verbindung, die bei der Entwicklung unter Abspaltung von (T₁)_m-(COUP-D)-T₂)_n reagiert,

T₁ und T₂

Zeitsteuerglieder, die bei der Entwicklung abgespalten werden können,

m, n

0 oder 1,
COUP den Rest eines 4-Äquivalent-Kupplers und

D

eine silberaffine Gruppe bedeuten.

The invention therefore relates to a color photographic silver halide material of the negative type, characterized in that at least one silver halide emulsion layer is a compound of the formula $${\text{AB- (T}}_{\text{1}}{\text{)}}_{\text{m}}{\text{- (COUP-D) - (T}}_{\text{2nd}}{\text{)}}_{\text{n}}$$

contains, where

A

a ballast remnant,

B

the rest of a compound which reacts during development with the elimination of (T ₁ ) _m - (COUP-D) -T ₂ ) _n ,

T ₁ and T ₂

Timers that can be split off during development

m, n

0 or 1,
COUP the rest of a 4-equivalent coupler and

D

mean a silver-loving group.

worin

Z₁

die restlichen Glieder zur Vervollständigung eines vorzugsweise 5- oder 6-gliedrigen Ringes, der wenigstens ein weiteres Heteroatom wie ein Stickstoff- oder Schwefelatom enthält,

Z₂

die restlichen Glieder zur Vervollständigung eines vorzugsweise 5- oder 6-gliedrigen Ringes,

X

-NH₂, -NHR,

-NH-NH₂, -NH-NHR, -SR, -OR,

Y

-S-, -NR-, -O-,

R

einen aliphatischen, aromatischen oder heterocyclischen Rest und

R₁, R₂

H, einen aliphatischen, aromatischen oder heterocyclischen Rest oder gemeinsam die restlichen Gliedereines 5- oder 6-gliedrigen Ringes

bedeuten.Suitable silver affinity groups D preferably correspond to formulas IIa to IIe:

wherein

Z ₁

the remaining members to complete a preferably 5- or 6-membered ring which contains at least one further heteroatom such as a nitrogen or sulfur atom,

Z ₂

the remaining links to complete a preferably 5- or 6-membered ring,

X

-NH ₂ , -NHR,

-NH-NH ₂ , -NH-NHR, -SR, -OR,

Y

-S-, -NR-, -O-,

R

an aliphatic, aromatic or heterocyclic radical and

R ₁ , R ₂

H, an aliphatic, aromatic or heterocyclic radical or together the rest Links of a 5- or 6-membered ring

mean.

The silver-affine group can be linked directly or via an intermediate link Z to the 4-equivalent coupler.

(COUP-D) kann mit T₁ über eine Bindung zu COUP oder zu D verbunden sein. Entsprechendes gilt für T₂.Preferred divalent intermediate members Z are alkylene groups, arylene groups, -COCH ₂ -, -COCH ₂ -S-, -COCH ₂ -O-,

(COUP-D) can be connected to T ₁ via a bond to COUP or to D. The same applies to M ₂ .

The group AB can be a coupler residue, a redox compound or a residue which can split off the group (T ₁ ) _m - (COUP-D) - (T ₂ ) _{n in a} non-imagewise manner, for example solely through the alkali of the developer. Suitable redox compounds are oxidizable compounds which, after their oxidation, can split off the group (T ₁ ) _m - (COUP-D) - (T ₂ ) _n .

The release of (COUP-D) from a compound of formula I in which B is a coupler residue takes place by reaction with the developer oxidation product EOP according to the scheme:

oder

oder ein Kupplerrest sein.Known timing elements T ₁ are described in US 4 146 396, 4 248 962, 4 409 323, 4 421 845, DE 26 26 315 and US 4 546 073. T ₁ can also be a coupler residue. T ₂ can be a hydrolyzable group such as -OCOCH ₂ Cl, -OCO-phenyl, -OSO ₂ CH ₃ ,

or

or a coupler residue.

The group AB is preferably the remainder of a 2-equivalent coupler which contains the remainder (T ₁ ) _m - (COUP-D) - (T ₂ ) _n bound to the coupling point. (COUP-D) is preferably linked to B via the silver-affine group D. (COUP-D) preferably does not contain any diffusion-resistant ballast residue.

As coupler residues, B and COUP can be the residues of yellow, purple or cyan couplers or the residues of couplers that do not produce color.

The compounds of the formula I are used in particular in an amount of 0.0005 to 0.05 mmol / m ^{2 of} photographic material, it being possible for the total amount to be used in one layer or distributed over several layers. The compounds of the formula I are preferably used in double- or triple-layer packages in the highly sensitive layers. Instead of a compound of the formula I, mixtures of several compounds of the formula I can also be used, the amount given above also being the total amount in this case.

Examples of negative type color photographic materials are color negative films, color photographic paper, color reversal films and color reversal paper. The invention is particularly valuable for color negative films.

Suitable supports for the production of such 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 barite 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 of the support is generally subjected to a treatment in order 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-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. 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 consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide. The color photographic material according to the invention preferably contains silver bromide iodide emulsions with 5 to 15 mol% of silver iodide.

It can be predominantly compact crystals, which are, for example, regularly cubic or octahedral or can have transitional forms. Preferably can but there are also 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 e.g. Doping of the individual grain areas are different. The average grain size of the emulsions is preferably between 0.2 μm and 2.0 μm, the grain size distribution can be either homodisperse or heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ± 30%. In addition to the silver halide, the emulsions can also contain organic silver salts, e.g. 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 Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides become.

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.

After crystal formation has been completed or at an earlier point in time, the soluble salts are removed from the emulsion, for example by pasta and washing, by flaking 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 e.g. described 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) 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, formamidinesulfinic acid) by hydrogen, by low pAg (eg less than 5) and / or high pH (eg above 8).

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 pentaazaindenes, 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 can be used as antifoggants. Heterocycles containing mercapto groups, for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to 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 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, for preventing electrical charging, for improving the sliding properties, for emulsifying the dispersion, for preventing adhesion and for improving 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, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, for example amino acid and Aminosulfonic acid compounds as well as sulfuric 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-ethyl carbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl and 9-ethyl-naphthoxathia or -selencarbocyanines and 9- Ethyl naphthothiaoxa or benzimidazocarbocyanines, 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 benzothiazole 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.

Suitable compounds of formula I are

Preparation of compound I-1

30.6 g of compound I-1-a and 14.1 g of compound I-1-b are stirred in 200 ml of dimethylacetamide; then 7.8 ml of tetramethylguanidine are added and the mixture is stirred at room temperature for 1.5 h. The reaction mixture becomes a mixture of ice water / wss. HCl added and the precipitate filtered off, washed with water and methanol and dried. The residue is stirred hot with 200 ml of 1-chlorobutane, filtered off after cooling to room temperature, washed with 1-chlorobutene and stirred with 150 ml of a mixture of methanol / ethyl acetate / 4: 1, filtered and washed.

25.4 g of compound I-1 are obtained, which melts at 158 to 161 ° C.

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 producing the purple partial color image are usually 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 those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products. The 2-equivalent couplers also include those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and either directly or after one or after the residue from the primary cleavage group several other groups have been split off (e.g. DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolds, e.g. as a development inhibitor (DIR coupler).

DIR couplers, the development inhibitors of the azole type, e.g. Triazoles and benzotriazoles are released in DE-A-2 414 006, 2 610 546, 2 659 417, 2 754 281, 2 726 180, 3 626 219, 3 630 564, 3 636 824, 3 644 416 and 2 842 063 described. Further advantages for color rendering, i.e. color separation and color purity, and for detail rendering i.e. sharpness and granularity can be achieved with such DIR couplers which e.g. do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after a further subsequent reaction, which is achieved, for example, with a timing group. Examples of these are in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-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 makes trouble-free Development and processing consistency achieved.

When using DIR couplers, in particular those that 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-3 700 419 and US-A-4 707 436.

The DIR couplers can be added to a wide variety of layers in a multilayer photographic material, e.g. also light-insensitive or intermediate layers. However, they are preferably added to the photosensitive silver halide emulsion layers, the characteristics of the silver halide emulsion, e.g. whose iodide content, the structure of the silver halide bodies or their grain size distribution influence the photographic properties achieved. The influence of the inhibitors released can be limited, for example, by incorporating an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it can 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.

It can be advantageous to modify the effect of a photographically active group which is split off from a coupler by causing an intermolecular reaction of this group after its release with another group according to DE-A-3 506 805.

Since with the compounds of the formula I and the DIR couplers the effectiveness of the radical released during the coupling is mainly desired and the color-forming properties of these couplers are less important, substances which result in essentially colorless products during the coupling are also suitable ( DE-A-1 547 640).

The material may further contain compounds other than couplers, which can, for example, release 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-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-3 145 640, 2 515 213, 2 447 079 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. However, they 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-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.

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, dioctyl acylate, 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 two or more silver halide emulsion partial layers include (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.

With a suitably low intrinsic sensitivity of the green or Red-sensitive layers can be selected 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.

Suitable agents, which are also called scavengers or EDP scavengers, are described in Research Disclosure 17.643 / 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 1 958 709, DE-A 2 530 645, DE-A 2 622 922).

The photographic material can also contain UV light absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _Min dyes, additives for improving the stabilization of dyes, couplers and whites and for reducing the color fog and others.

The layers of the photographic material can be hardened with the usual hardening agents. Suitable curing agents are, for example, formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and others Compounds containing reactive halogen (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 (U.S. 3,017,280 and U.S. 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 2 225 230 and DE-A 2 439 551); Carbamoyloxypyridinium compounds (DE-A-2 408 814); 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 after 8 hours at the latest, 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.

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 in the form of their oxidation product can be used as the color developer compound to react product with color couplers to azomethine or indophenol 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-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. For example, Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used as bleaching agents. Iron (III) complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, and alkyliminodicarboxylic acids and corresponding phosphonic acids are particularly preferred. Persulphates are also suitable as bleaching agents.

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.

example 1

• 1. Schicht (Antihalo-Schicht)

  0,3 g

  schwarzes kolloidales Silber

  1,2 g

  Gelatine

  0,4 g

  UV-Absorber UV 1

  0,02 g

  Trikresylphosphat (TKP)

• 2. Schicht (Mikrat-Zwischenschicht)

  0,25 g

  AgNO₃ einer Mikrat-Ag(BrJ)-Emulsion, mittlerer Korndurchmesser 0,07 µm, 0,5 Mol-% Iodid

  1,0 g

  Gelatine

• 3. Schicht (niedrig-rotempfindliche Schicht)

  2,7 g

  AgNO₃ einer spektral rotsensibilisierten Ag(Br,J)-Emulsion mit 4 Mol-% Iodid, mittlerer Korndurchmesser 0,5 µm

  2,0 g

  Gelatine

  0,88 g

  farbloser Kuppler C1

  0,02 g

  DIR-Kuppler D 1

  0,05 g

  farbiger Kuppler RC-1

  0,07 g

  farbiger Kuppler YC-1

  0,75 g

  TKP

• 4. Schicht (hoch-rotempfindliche Schicht)

  2,2 g

  AgNO₃ der spektral rotsensibilisierten Ag(Br,J)-Emulsion, 12 Mol-% Iodid, mittlerer Korndurchmesser 1,0 µm,

  1,8 g

  Gelatine

  0,19 g

  farbloser Kuppler C 2

  0,17 g

  TKP

• 5. Schicht (Zwischenschicht)

  0,4 g

  Gelatine

  0,15 g

  Weißkuppler W-1

  0,06 g

  Aluminiumsalz der Aurintricarbonsäure

• 6. Schicht (niedrig-grünempfindliche Schicht)

  1,9 g

  AgNO₃ einer spektral grünsensibilisierten Ag(Br,J)-Emulsion, 4 Mol-% Iodid, mittlerer Korndurchmesser 0,35 µm

  1,8 g

  Gelatine

  0,54 g

  farbloser Kuppler M-1

  0,24 g

  DIR-Kuppler D-1

  0,065 g

  farbiger Kuppler YM-1

  0,6 g

  TKP

• 7. Schicht (hoch-grünempfindliche Schicht)

  1,25 g

  AgNO₃ einer spektral grünsensibilisierten Ag(Br,J)-Emulsion, 9 Mol-% Iodid, mittlerer Korndurchmesser 0,8 µm,

  1,1 g

  Gelatine

  0,195 g

  farbloser Kuppler M-2

  0,05 g

  farbiger Kuppler YM-2

  0,245 g

  TKP

• 8. Schicht (Gelbfilterschicht)

  0,09 g

  gelbes kolloidales Silber

  0,25 g

  Gelatine

  0,08 g

  Scavenger SC1

  0,40 g

  Formaldehydfänger FF-1

  0,08 g

  TKP

• 9. Schicht (niedrig-blauempfindliche Schicht)

  0,9 g

  einer spektral blausensibilisierten Ag(Br,J)-Emulsion, 6 Mol-% Iodid, mittlerer Korndurchmesser 0,6 µm

  2,2 g

  Gelatine

  1,1 g

  farbloser Kuppler Y-1

  0,037 g

  DIR-Kuppler D-1

  1,14 g

  TKP

• 10. Schicht (hoch-blauempfindliche Schicht)

  0,6 g

  AgNO₃ einer spektral blausensibilisierten Ag(Br,J)-Emulsion, 10 Mol-% Iodid, mittlerer Korndurchmesser 1,2 µm,

  0,6 g

  Gelatine

  0,2 g

  farbloser Kuppler Y-1

  0,003 g

  DIR-Kuppler D-1

  0,22 g

  TKP

• 11. Schicht (Mikrat-Schicht)

  0,06 g

  AgNO₃ einer Mikrat-Ag(Br,J)-Emulsion, mittlerer Korndurchmesser 0,06 µm, 0,5 Mol-% Iodid,

  1 g

  Gelatine

  0,3 g

  UV-Absorber UV-2

  0,3 g

  TKP

• 12. Schicht (Schutz- und Härtungsschicht)

  0,25 g

  Gelatine

  0,75 g

  Härtungsmittel der Formel

  

     Sodaß der Gesamtschichtaufbau nach der Härtung einen Quellfaktor ≤ 3,5 hatte.

A color photographic recording material for color negative color development was produced (layer structure 1A) by applying the following layers in the order given to a transparent layer support made from cellulose triacetate. The quantities given relate to 1 m ² . For the silver halide application, the corresponding amounts of AgNO _{3 are} stabilized with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

• 1st layer (antihalo layer)

  0.3 g

  black colloidal silver

  1.2 g

  gelatin

  0.4 g

  UV absorber UV 1

  0.02 g

  Tricresyl phosphate (CPM)

• 2nd layer (intermediate layer )

  0.25 g

  AgNO _{3 of} a Mikrat-Ag (BrJ) emulsion, average grain diameter 0.07 µm, 0.5 mol% iodide

  1.0 g

  gelatin

• 3rd layer (low red sensitive layer)

  2.7 g

  AgNO _{3 of} a spectrally red-sensitized Ag (Br, J) emulsion with 4 mol% iodide, average grain diameter 0.5 µm

  2.0 g

  gelatin

  0.88 g

  colorless coupler C1

  0.02 g

  DIR coupler D 1

  0.05 g

  colored coupler RC-1

  0.07 g

  colored coupler YC-1

  0.75 g

  CPM

• 4th layer (highly red-sensitive layer)

  2.2 g

  AgNO _{3 of} the spectrally red-sensitized Ag (Br, J) emulsion, 12 mol% iodide, average grain diameter 1.0 µm,

  1.8 g

  gelatin

  0.19 g

  colorless coupler C 2

  0.17 g

  CPM

• 5th layer (intermediate layer )

  0.4 g

  gelatin

  0.15 g

  White coupler W-1

  0.06 g

  Aluminum salt of aurintricarboxylic acid

• 6th layer (low green sensitive layer)

  1.9 g

  AgNO _{3 of} a spectrally green-sensitized Ag (Br, J) emulsion, 4 mol% iodide, average grain diameter 0.35 µm

  1.8 g

  gelatin

  0.54 g

  colorless coupler M-1

  0.24 g

  DIR coupler D-1

  0.065 g

  colored coupler YM-1

  0.6 g

  CPM

• 7th layer (highly green-sensitive layer)

  1.25 g

  AgNO _{3 of} a spectrally green-sensitized Ag (Br, J) emulsion, 9 mol% iodide, average grain diameter 0.8 µm,

  1.1 g

  gelatin

  0.195 g

  colorless coupler M-2

  0.05 g

  colored coupler YM-2

  0.245 g

  CPM

• 8th layer (yellow filter layer )

  0.09 g

  yellow colloidal silver

  0.25 g

  gelatin

  0.08 g

  Scavenger SC1

  0.40 g

  Formaldehyde scavenger FF-1

  0.08 g

  CPM

• 9th layer (low blue-sensitive layer)

  0.9 g

  a spectrally blue-sensitized Ag (Br, J) emulsion, 6 mol% iodide, average grain diameter 0.6 µm

  2.2 g

  gelatin

  1.1 g

  colorless coupler Y-1

  0.037 g

  DIR coupler D-1

  1.14 g

  CPM

• 10th layer (highly blue-sensitive layer)

  0.6 g

  AgNO _{3 of} a spectrally blue-sensitized Ag (Br, J) emulsion, 10 mol% iodide, average grain diameter 1.2 µm,

  0.6 g

  gelatin

  0.2 g

  colorless coupler Y-1

  0.003 g

  DIR coupler D-1

  0.22 g

  CPM

• 11th layer (Mikrat layer)

  0.06 g

  AgNO _{3 of} a Mikrat-Ag (Br, J) emulsion, average grain diameter 0.06 µm, 0.5 mol% iodide,

  1 g

  gelatin

  0.3 g

  UV absorber UV-2

  0.3 g

  CPM

• 12th layer (protective and hardening layer )

  0.25 g

  gelatin

  0.75 g

  Hardening agent of the formula

  

  So that the total layer structure had a swelling factor ≤ 3.5 after curing.

Substances used in example 1:

In the case of the layer structures 1B-1K, a compound according to the invention or a comparison compound was additionally added to the 10th layer in an amount of 4.25 μmol / m ² . The compounds and the results are shown in Table 1.

After exposing a gray wedge, the development is carried out according to "The British Journal of Photography", 1974, pages 597 and 598. Table 1 material connection relative sensitivity yellow comment 1A - 100 comparison 1B V1 99 comparison 1C V2 100 comparison 1D V3 99 comparison 1E V4 101 comparison 1F I-1 115 invention 1G I-5 113 invention 1H I-12 109 invention 1I I-19 110 invention 1K I-20 107 invention

As can be seen, the compounds according to the invention have an increase in sensitivity.

Example 2

In the case of materials 2B to 2G, a compound according to the invention or a comparative compound is added in an amount of 4.25 μmol / m ² per layer to the 4th, 7th and 10th layers of the layer structure 2. The compounds and the results are shown in Table 2. Part of the material is kept for 2 weeks at 60 ° C and 35% relative humidity, another part of the material is stored in a room climate (23 ° C 60% RH). All materials are exposed and processed as described in Example 1. The increase in fog of the warmer material compared to the material stored in the indoor climate is taken as a measure of the instability. Table 2 material Coupler Fog increase after storage at 23 ° C, 60% RH comment gb pp bg 2A = 1A - 8th 1 3rd comparison 2 B V-5 15 10th 7 comparison 2C V-6 10th 4th 6 comparison 2D V-7 31 14 10th comparison 2E I-1 9 1 3rd invention 2F I-8 8th 2nd 4th invention 2G I-17 7 2nd 3rd invention gb = yellow, pp = purple, bg = teal.

As can be seen, the comparison compounds show a strong increase in fog, while the compounds according to the invention show the storage behavior of the reference material 2A.

Example 3

Schicht 9

(1. blauempfindliche Schicht, gering empfindlich)
blausensibilisierte Silberbromidiodidemulsion (6 mol-% Iodid; mittlerer Korndurchmesser 0,60 µm) aus
0,75 g AgNO₃, mit
2,2 g Gelatine
1,1 g Gelbkuppler Y-2
0,034 g DIR-Kuppler D-1
1,1 g TKP

Schicht 10

(2. blauempfindliche Schicht, hochempfindlich),
blausensibilisierte Silberbromidiodidemulsion (10 mol-% Iodid; mittlerer Korndurchmesser 1,20 µm) aus
0,48 g AgNO₃, mit
0,6 g Gelatine
0,2 g Gelbkuppler Y-2
0,003 g DIR-Kuppler D-1
0,22 g TKP
0,003 g Verbindung 1-6

A material was produced whose 1st to 8th and 11th layers corresponded to the material according to Example 1A.

Layer 9

(1st blue-sensitive layer, slightly sensitive)
blue-sensitized silver bromide iodide emulsion (6 mol% iodide; average grain diameter 0.60 µm)
0.75 g AgNO ₃ , with
2.2 g gelatin
1.1 g yellow coupler Y-2
0.034 g DIR coupler D-1
1.1 g CPM

Layer 10

(2nd blue sensitive layer, highly sensitive),
blue-sensitized silver bromide iodide emulsion (10 mol% iodide; average grain diameter 1.20 µm)
0.48 g AgNO ₃ , with
0.6 g gelatin
0.2 g yellow coupler Y-2
0.003 g DIR coupler D-1
0.22 g CPM
0.003 g of compound 1-6

Material with a layer structure 1A and material according to Example 3 were exposed and processed as described in Example 1. The sensitometric results are in Table 3 given. In addition, the edge transfer function (KÜF) of a bar grid with 40 line pairs per mm in relation to the input modulation (= 100) is specified as the sharpness parameter. Table 3 material comment rel. sensitivity KÜF at 40 Lp / mm gb pp bg pp bg 1A comparison 100 100 100 70 25th 3rd invention 101 99 101 75 28

As can be seen, the material according to the invention shows improved sharpness with the same sensitivity with a lower amount of silver.

Claims (5)

1. Colour photographic silver halide material of the negative type, characterised in that at least one silver halide emulsion layer contains a compound of the formula $${\text{A-B-(T}}_{\text{1}}{\text{)}}_{\text{m}}{\text{-(COUP-D)-(T}}_{\text{2}}{\text{)}}_{\text{n}}$$

   

   wherein

   A   represents a ballast group,

   B   represents the radical of a compound which reacts to release (T₁)_m-(COUP-D)-(T₂)_n during development,

   T₁ and T₂   represent time-regulating units which can be released during development,

   m, n   are 0 or 1,

   COUP   represents the radical from a 4-equivalent coupler and

   D   represents a group with an affinity for silver.
2. Colour photographic silver halide material according to claim 1 in which D corresponds to the formulas IIa to IIe

   

   in which

   Z₁   represents the remaining members for completion of a preferably 5 or 6-membered ring which contains at least one other hetero-atom such as a nitrogen or sulphur atom,

   Z₂   represents the remaining members for completion of a preferably 5 or 6-membered ring,

   X   represents -NH₂, -NHR, -N(R)₂, -NH-NH₂, NH-NHR, -SR, -OR

   Y   represents -S-, -NR- -O-

   R   represents an aliphatic, aromatic or heterocyclic group and

   R₁, R₂   represent H, an aliphatic, aromatic or heterocyclic group or together represent the remaining members of a 5 or 6-membered ring.
3. Colour photographic silver halide material according to Claim 1, wherein A-B is the radical from a 2-equivalent coupler which contains the group (T₁)_m-(COUP-D)-(T₂)_n bonded at the coupling site, which is linked to B via the group D which has an affinity for silver, wherein COUP-D contains no ballast radicals which make it diffusion-resistant.
4. Colour photographic silver halide material according to Claim 1, wherein the compound of the formula I is used in an amount of 0.0005 to 0.05 mmol/m² of photographic material.
5. Colour photographic silver halide material according to Claim 1, which contains at least two red-sensitive cyan-coupling silver halide emulsion layers of different sensitivity, at least two green-sensitive, magenta-coupling silver halide emulsion layers of different sensitivity and at least two blue-sensitive yellow-coupling silver halide emulsion layers, wherein at least one high-sensitivity silver halide emulsion layer contains a compound of the formula I.