EP0585672A2 - Photographic recording material - Google Patents

Abstract

A photographic recording material which contains a support and thereon at least one light-sensitive silver halide emulsion layer and a gelatin-containing protective layer over the light-sensitive layer and optionally a gelatin-containing backing layer, and the gelatin-containing protective layer and / or the gelatin-containing backing layer contains a silicone oil of the formula I <IMAGE>, in which R1 : Hydroxy, alkoxy, cycloalkoxy, aryloxy, R2: a radical of the formula <IMAGE> or R1; R3, R4: alkyl, aryl, cycloalkyl, R5, R6: H, alkyl, aminoalkyl, polyaminoalkyl, A: a straight-chain or branched alkylene radical having 3 to 20 C atoms, with a carbon chain between the Si atom and the N atom of at least 3 carbon atoms, m: 10 to 1000 and; p: 1 to 350, and is hardened, is distinguished by equally good static and sliding friction coefficients before and after processing, and by consistently good dry scratch resistance.

Description

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

Photographic recording materials usually consist of a support on which at least one photosensitive silver halide emulsion layer and at least one protective layer are applied. Gelatin, which is hardened with a suitable hardening agent, is usually used as the binder for the silver halide grains, so that the photographic materials can also be processed at temperatures above 30 _° C. after exposure.

The photographic materials are usually available as rolls or as a single sheet stack. In both cases, it is required that the static friction and the sliding friction coefficient have an optimal value, which should be the same before and after processing, if possible. If these coefficients are too low, that is, the lubricity is too high, exact stacks cannot be formed; the individual leaves slide away from each other. Correspondingly, rolls do not form flush edges, which leads to problems in the foundry after drying, in assembly, when used in development machines, cameras, etc. If these coefficients are too high, the sheets adhere to one another too strongly, or, in the case of rolls, excessive forces have to be applied to unroll, which leads to static discharges and flashing, tears in the material and defects in the transport mechanisms of developing machines or cameras.

If an initially optimally adjusted coefficient deteriorates due to the processing, the same problems arise on the processing product.

For these reasons, lubricants are usually added to the outermost layers of a photographic material, e.g. Dialkyl silicones or paraffins. With these products, improved static and sliding friction coefficients are achieved, but they do not remain sufficiently constant in processing.

The object of the invention was therefore to provide a photographic material which has optimally set static friction and sliding friction coefficients which, at most, change only slightly as a result of the processing.

Stiction is the friction that has to be overcome to bring the material from the rest position to sliding, sliding friction is the friction during sliding.

worin

• R₁ Hydroxy, Alkoxy, Cycloalkoxy, Aryloxy,
• R₂ einen Rest der Formel
  
  oder R₁
• R₃, R₄ Alkyl, Aryl, Cycloalkyl,
• Rs, R₆ H, Alkyl, Aminoalkyl, Polyaminoalkyl,
• A einen geradkettigen oder verzweigten Alkylenrest mit 3 bis 20 C-Atomen, wobei zwischen dem Si-Atom und dem N-Atom eine Kohlenstoffkette von wenigstens 3 C-Atomen ist,
• m 10 bis 1000, vorzugsweise 50 bis 200,
• p 1 bis 350, vorzugsweise 10 bis 100 bedeuten,

einbringt und die Schicht härtet.Surprisingly, this object can be achieved by adding a silicone oil of the formula I to at least one of the two outer layers of a photographic material containing gelatin

wherein

• R ₁ hydroxyl, alkoxy, cycloalkoxy, aryloxy,
• R _{2 is} a radical of the formula
  
  or R ₁
• R ₃ , R ₄ alkyl, aryl, cycloalkyl,
• Rs, R ₆ H, alkyl, aminoalkyl, polyaminoalkyl,
• A is a straight-chain or branched alkylene radical having 3 to 20 C atoms, a carbon chain of at least 3 C atoms being between the Si atom and the N atom,
• m 10 to 1000, preferably 50 to 200,
• p is 1 to 350, preferably 10 to 100,

and the layer hardens.

The invention therefore relates to a photographic recording material which contains a support and thereon at least one light-sensitive silver halide emulsion layer and a protective layer over the light-sensitive layer and optionally a back layer, the protective layer and / or back layer containing gelatin, characterized in that the gelatin-containing protective layer and / or the gelatin-containing back layer contains a silicone oil of the formula I and is hardened.

The silicone oil is preferably used in the protective layer over the at least one light-sensitive layer. This protective layer contains in particular 0.2 to 2 g of gelatin per m ^2. The silicone oil is used in particular in an amount of 1 to 100 mg / m ² , preferably 2 to 20 mg / m ² .

All common hardening agents can be used, e.g. Triazine hardeners, vinyl sulfone hardeners, but especially so-called instant hardeners.

• Die Messung erfolgt in Anlehnung an DIN 53 375. Unter einem Schlitten (Masse = 450 g; Auflagefläche 64 cm) wird der Prüfling mit der Schicht- (oder Rück-)seite angebracht und auf die Schichtseite einer Probe des gleichen Materials gestellt. Über eine Feder wird Kraft auf den Schlitten ausgeübt. Die Gleitreibungskraft ist die Kraft, die unmittelbar nach Überwindung der Haftreibung bei der vorgegebenen Gleitgeschwindigkeit von 10 mm/s auf einem Weg von 135 mm bei einer Auflagezeit bis zum Beginn der Messung von 10 s noch wirksam bleibt. Aus der Gleitreibungskraft und der Normalkraft berechnet sich der Gleitreibungskoeffizient.

The coefficient of sliding friction is determined as follows:

• The measurement is based on DIN 53 375. Under a slide (mass = 450 g; support surface 64 cm) the test specimen is attached with the layer (or back) side and placed on the layer side of a sample of the same material. Force is exerted on the sled by a spring. The sliding friction force is the force that remains effective immediately after overcoming the static friction at the specified sliding speed of 10 mm / s over a distance of 135 mm with a contact time up to the start of the measurement of 10 s. The sliding friction coefficient is calculated from the sliding friction force and the normal force.

The sliding friction coefficient should be between 0.3 and 0.4 before and after processing the material.

The static friction coefficient is determined analogously to the measurement of the sliding friction coefficient and is the initial value of the measurement.

The measurements are dust-free in a clean room at 23 ° C and 55% rel. Humidity.

The coefficient of static friction should also be between 0.3 and 0.4 before and after processing.

• R₁ C₁ bis C₄-Alkoxy,
• R₂ C₁ bis C₄-Alkoxy oder einen Rest der Formel
  
• R₃, R₄ C₁ bis C₄-Alkyl, insbesondere CH₃ oder C₂H_s
• R₅, R₆ Wasserstoff, C₁ bis C₄-Alkyl, Cyclohexyl, Phenyl, einen Rest -CH₂-CH₂-NH₂ oder einen Rest -(CH₂-CH₂-NH)_q-CH₂-CH₂-NH₂
• m 50 bis 200,
• n 3 bis 8,
• p 30 bis 150 und
• q 1 bis 8.

In formula I preferably mean

• R ₁ C ₁ to C ₄ alkoxy,
• R ₂ C ₁ to C ₄ alkoxy or a radical of the formula
  
• R ₃ , R ₄ C ₁ to C ₄ alkyl, in particular CH ₃ or C ₂ H _s
• R ₅ , R _{6 are} hydrogen, C ₁ to C ₄ alkyl, cyclohexyl, phenyl, a radical -CH ₂ -CH ₂ -NH ₂ or a radical - (CH ₂ -CH ₂ -NH) _q -CH ₂ -CH ₂ -NH _2nd
• m 50 to 200,
• n 3 to 8,
• p 30 to 150 and
• q 1 to 8.

Die Aufbringung des Silikonöls kann zusammen mit der Gelatine der Schutzschicht erfolgen.Suitable compounds of formula 1 are, for example

The silicone oil can be applied together with the gelatin of the protective layer.

However, a gelatin layer can also first be cast and the silicone oil, optionally together with the hardener solution, can be applied to it.

The silicone oils are particularly applied in the form of an aqueous emulsion, such an emulsion e.g. consists of 35 wt .-% silicone oil, 3 wt .-% emulsifier and 62 wt .-% water. Suitable emulsifiers are anionic (e.g. sodium lauryl sulfate), non-ionic (e.g. octyl polyglycol ether) or cationic (e.g. cetylammonium bromide) emulsifiers.

The dry scratch resistance is determined by passing a diamond with an angle of the diamond tip of 90 and a radius of the diamond tip of 76 μm over the surface of the material with increasing contact force. The contact force is given at the first visible layer injury.

The photographic material can be a black and white or color material.

Examples of color photographic materials are 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.

Suitable supports for the production of color photographic materials are e.g. Films and sheets 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 a-olefin polymer layer (e.g. 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, polyN-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, 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. In the case of color negative and color reversal films, silver bromide iodide emulsions, in In the case of color negative and color reversal paper, silver chloride bromide emulsions with a high chloride content are usually used up to pure silver chloride emulsions. It can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms. However, platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain. However, the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, e.g. 12: 1 to 30: 1.

The silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. Doping of the individual grain areas are different. The average grain size of the emulsions is preferably between 0.2 .mu.m and 2.0 .mu.m, 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.

During the precipitation of the silver halides and / or the physical ripening of the silver halide grains, salts or complexes of metals such as Cd, Zn, Pb, TI, Bi, Ir, Rh, Fe can also be present.

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 exchanger.

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).

The 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 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 17643 (Dec. 1978), Chapter 111). Alternatively or additionally, a reduction sensitization can be carried out with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidinesulfinic acid) using hydrogen, by means of low pAg (for example less than 5) and / or high pH (for example over 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 penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such compounds are described, for example, by 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. 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 17643 (Dec. 1978), Chapter 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, 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, e.g. Saponin, mainly synthetic surface-active compounds (surfactants) are used: non-ionic surfactants, e.g. Alkylene oxide compounds, glycerin compounds or glycidol compounds, cationic surfactants, e.g. higher alkyl amines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, e.g. 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 (Dec. 1978), Chapter IV, provides an overview of the polymethine dyes suitable as spectral sensitizers, their suitable combinations and combinations having 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 which 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 benzimidazocarbocyanines, which may also be further substituted and must also 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 generally couplers of the phenol or a-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 a-acylacetamide type; suitable examples are a-benzoylacetanilide couplers and a-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 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 ( 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 or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.

DIR couplers, the development inhibitors of the azole type, e.g. Release triazoles and benzotriazoles are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281.28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416. Other advantages for color rendering, i.e. Color separation and color purity, and for detail reproduction, i.e. Sharpness and graininess can be achieved with such DIR couplers, 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-0 157 146 and 0 204 175, in US-A-4 146 396 and 4 438 393 as well 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-0 167 168 and 0 219 713. This measure ensures trouble-free development and processing consistency.

When using DIR couplers, in particular those which release an easily diffusible development inhibitor, suitable measures can be taken to improve the color rendering, e.g. achieve a more differentiated color rendering, as described, for example, in EP-A-0 115 304, 0 167 173, 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, 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 grains 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.

To increase the sensitivity, the contrast and the maximum density, DAR or. FAR couplers are used that split off a development accelerator or an fogging agent. 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-0 089 834, 0 110 511, 0 118 087 , 0 147 765 and in U.S.-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 with DIR, DAR or FAR couplers mainly the effectiveness of the residue released during coupling is desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-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, 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-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. 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-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-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-25 41 230, DE-A-25 41 274, DE-A-28 35 856, 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 dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, 2-ethylphosphate, tridecoxyphosphate, tri-ethylphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, , Dodecylbenzoate, 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-t-amylphenol, dioctylacelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N-2-t-2-n-N-2-n-N-2-t-butyl -octylaniline, paraffin, dodecylbenzene and diisopropylnaphthalene.

Each of the differently sensitized, light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470). 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 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), chapters VII, 17 842 (Feb. 1979) and 18 716 (Nov. 1979), page 650 and in EP A-0 069 070, 0 098 072, 0 124 877, 0 125 522.

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. Sub-layers of the same spectral sensitization can adjacent to one another or separated by other layers, for example 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 a-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 carrier, but also occasionally intermediate layers, especially if they represent the layer furthest away from the carrier during production, can contain photographically inert particles of an inorganic or organic nature, e.g. 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 protective layer according to the invention preferably contains such spacers, in particular in an amount of 2 to 10 mg / m ^2.

The average particle diameter of the spacers is in particular in the range from 0.2 to 10 μm, preferably in the range from 0.7 to 2.5 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 (Dec. 1978), Chapter VII) can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, 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 which 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 of yellow color images as a result of the development of heat, moisture and light. In order to prevent the deterioration of magenta color images, in particular their impairment as a result of exposure to light, spiroindanes (JP-A-159 644/81) and chromanes which are substituted by hydroquinone diethers or monoethers (JP-A-89 835 / 80) particularly effective.

The layers of the photographic material are hardened according to the invention. 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 compound formations (US-A-4 013 468), 2-sulfonyloxypyridinium salts (JP-A-110 762/81), formamidinium salts (EP-A-0 162 308), compounds with 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 and the swelling of the layer structure occurs as a result of the crosslinking reaction . Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).

These hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.

The instant hardeners are preferably used in an amount of 0.1 to 3.0 g / m ² .

worin

• R¹ Alkyl, Aryl oder Aralkyl bedeutet,
• R² die gleiche Bedeutung wie R¹ hat oder Alkylen, Arylen, Aralkylen oder Alkaralkylen bedeutet, wobei die zweite Bindung mit einer Gruppe der Formel
  
  verknüpft ist, oder
• R¹ und R² zusammen die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes erforderlichen Atome bedeuten, wobei der Ring z.B. durch C1-C3-Alkyl oder Halogen substituiert sein kann,
• R³ für Wasserstoff, Alkyl, Aryl, Alkoxy, -NR^4-COR^s, -(CH₂)-_m-NR⁸R⁹, -(CH₂)_"-CONR¹³R¹⁴ oder
  
  oder ein Brückenglied oder eine direkte Bindung an eine Polymerkette steht, wobei
• R⁴, R⁶, R⁷, R⁹, R¹⁴, R¹⁵, R¹⁷, R¹⁸, und R19 Wasserstoff oder C₁-C₄-Alkyl,
• _R ⁵ Wasserstoff, C₁-C₄-Alkyl oder NR6 R7,
• R⁸ -COR¹⁰
• ^R10 NR¹1_R12
• R¹¹ C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,
• _R ¹² Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,
• _R ¹3 Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,
• R¹⁶ Wasserstoff, C₁-C₄-Alkyl, -COR¹⁸ oder - CONHR¹⁹, m eine Zahl 1 bis 3
• n eine Zahl 0 bis 3
• p eine Zahl 2 bis 3 und
• Y O oder NR¹⁷ bedeuten oder
• R¹³ und R¹⁴ gemeinsam die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes erforderlichen Atome darstellen, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,
• Z die zur Vervollständigung eines 5- oder 6-gliedrigen aromatischen heterocyclischen Ringes, gegebenenfalls mit anelliertem Benzolring, erforderlichen C-Atome und
• _X ^e ein Anion bedeuten, das entfällt, wenn bereits eine anionische Gruppe mit dem übrigen Molekül verknüpft ist; (b)
  
  worin
• R¹, R², R³ und X^e die für Formel (a) angegebene Bedeutung besitzen.

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

wherein

• R ¹ denotes alkyl, aryl or aralkyl,
• R ^{2 has} the same meaning as R ¹ or means alkylene, arylene, aralkylene or alkaralkylene, the second bond being with a group of the formula
  
  is linked, or
• R ¹ and R ² together denote the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, it being possible for the ring to be substituted, for example, by C1-C3-alkyl or halogen,
• R ³ for hydrogen, alkyl, aryl, alkoxy, -NR ^4- COR ^s , - (CH ₂ ) - _m -NR ⁸ R ⁹ , - (CH ₂ ) _" -CONR ¹³ R ¹⁴ or
  
  or a bridge link or a direct bond to a polymer chain, wherein
• R ⁴ , R ⁶ , R ⁷ , R ⁹ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , and R19 are hydrogen or C ₁ -C ₄ alkyl,
• _R ^{5 is} hydrogen, C ₁ -C ₄ alkyl or NR6 R7,
• R ⁸ -COR ¹⁰
• ^R10 NR ¹ 1 _R12
• R ^{11 is} C ₁ -C ₄ alkyl or aryl, in particular phenyl,
• _R ^{12 is} hydrogen, C ₁ -C ₄ alkyl or aryl, in particular phenyl,
• _R ¹ 3 is hydrogen, C ₁ -C ₄ alkyl or aryl, in particular phenyl,
• R ^{16 is} hydrogen, C ₁ -C ₄ alkyl, -COR ¹⁸ or - CONHR ¹⁹ , m is a number 1 to 3
• n is a number 0 to 3
• p is a number 2 to 3 and
• YO or NR ¹⁷ mean or
• R ¹³ and R ¹⁴ together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, the ring being able to be substituted, for example, by C ₁ -C ₃ alkyl or halogen,
• Z is the carbon atoms and necessary for the completion of a 5- or 6-membered aromatic heterocyclic ring, optionally with a fused benzene ring
• _X ^{e is} an anion which is omitted if an anionic group is already linked to the rest of the molecule; (b)
  
  wherein
• R ¹ , R ² , R ³ and X ^{e have} the meaning given for formula (a).

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 protective layer has to improve the mechanical properties (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. 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 aminopolycarbon are particularly preferred acids, in particular, for example, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulphates and peroxides, for example hydrogen peroxide, 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.

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 and then development with a color developer, bleaching and fixing.

Examples

A color photographic recording material was produced by applying the following layers in the order given on a paper coated on both sides with polyethylene. The amounts given relate in each case to 1 m ^2. The corresponding amounts of AgNO ₃ are given for the silver halide application.

example 1

Layer structure 1

• 1st layer (substrate layer)
• 0.2 g gelatin
• 2nd layer (blue-sensitive layer)
• blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.78 μm) from 0.50 g AgN0 ₃ with
• 1.38 g gelatin
• 0.60 g yellow coupler Y-1
• 0.48 g tricresyl phosphate (CPM)
• 3rd layer (intermediate layer)
• 1.18 g gelatin
• 0.08 g 2,5-dioctyl hydroquinone
• 0.08 g dibutyl phthalate (DBP)
• 4th layer (green-sensitive layer)
• green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.45 μm) from 0.40 g AgN0 ₃ with
• 1.02 g gelatin
• 0.37 g purple coupler M-1
• 0.40 g DBP
• 5th layer (intermediate layer)
• 1.20 g gelatin
• 0.66 g UV absorber of the formula
  
• 0.052 g 2,5-dioctyl hydroquinone
• 0.36 g CPM
• 6th layer (red-sensitive layer)
• red-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.42 μm) from 0.28 g AgN0 ₃ with
• 0.84 g gelatin
• 0.39 g of cyan coupler C-1
• 0.39 g CPM
• 7th layer (UV protective layer)
• 0.65 g gelatin
• 0.21 g UV absorber as in 5th layer
• 0.11 g CPM
• 8th layer (protective layer)
• 0.65 g gelatin
• 0.39 g of curing agent of the formula
  
• 0.005 g of polymethyl methacrylate particles with a particle diameter of 1 µm
  
  
  
  

processing

• a) Color developer - 45 s - 35 _° C
  
• b) bleach-fix bath - 45 s - 35 ° C
  
• c) Soak - 2 min - 33 ° C

Examples 2 to 11

These examples differ from example 1 in that the 8th layer additionally contains the compounds specified in the table below.

The materials of Examples 1 to 11 determine the sliding friction coefficient (GK) before and after processing, the static friction coefficient (HK) before and after processing and the dry scratch resistance (TKF) before and after processing. The results are shown in Table 1.

• V 1 is a polydimethylsiloxane of the formula
  
• V 2 is a cross-linked methoxy group-containing dimethylpolysiloxane, produced from the hydrolysis of
  • Mixture:
  • 52 g trichloromonomethylsilane,
  • 130 g dimethyldichlorosilane,
  • 22 g trimethylmonochlorosilane in xylene / methanol / water.
• V 3 is a highly cross-linked butoxy group-containing methylsiloxane in xylene / butanol, produced from the
  • Hydrolysis of the mixture:
  • 840 g trichloromonomethylsilane,
  • 90 g dimethyldichlorosilane,
  • 14 g trimethylmonochlorosilane in xylene / butanol / water.

It can be seen that Examples 5 to 8 according to the invention provide constant values for GK, HK and TKF before and after processing, while the comparative tests are either too poor or, if the value is good, deteriorate considerably through processing.

Claims (7)

1. Photographic recording material which contains a support and at least one photosensitive silver halide emulsion layer and a protective layer over the photosensitive layer and optionally a back layer, the protective layer and / or back layer containing gelatin, characterized in that the gelatin-containing protective layer and / or the gelatin-containing back layer Formula I silicone oil

contains what R ₁ hydroxyl, alkoxy, cycloalkoxy, aryloxy, R _{2 is} a radical of the formula

or R ₁ R ₃ , R ₄ alkyl, aryl, cycloalkyl, Rs, R ₆ H, alkyl, aminoalkyl, polyaminoalkyl, A is a straight-chain or branched alkylene radical having 3 to 20 C atoms, a carbon chain of at least 3 C atoms being between the Si atom and the N atom, m 10 to 1000 and p is 1 to 350,
and is hardened. 2. Photographic material according to claim 1, characterized in that the silicone oil of formula I is used in the protective layer over the at least one light-sensitive layer. 3. Photographic material according to claim 2, characterized in that the protective layer contains 0.2 to 2 g of gelatin per m ² and the silicone oil in an amount of 1 to 100 mg / m ² . 4. Photographic material according to claim 1, characterized in that R ₁ C1-C4 alkoxy R _{2 is} C, -C ₄ alkoxy or a radical of the formula

R ₃ , R ₄ C ₁ to C ₄ alkyl R ₅ , R _{6 are} hydrogen, C ₁ to C ₄ alkyl, cyclohexyl or phenyl, a radical -CH ₂ -CH ₂ -NH ₂ or a radical - (CH ₂ -CH ₂ -NH) q-CH ₂ -CH ₂ -NH _2nd A - (- CH ₂ -CH ₂ -) _n - m 50 to 200, n 3 to 8, p 30 to 150 and q mean 1 to 8. 5. Photographic material according to claim 1, characterized in that the protective layer and / or back layer contain inert particles of organic or inorganic nature. 6. Photographic material according to claim 5, characterized in that the inert particles have a particle diameter of 0.7 to 2.5 µm and are used in an amount of 1 to 10 mg / m ² . 7. Photographic material according to claim 1, characterized in that the curing is carried out with an instant hardener.