DE4414987A1 - Colour photographic print material esp. paper giving positive inter-image effect without DIR coupler - Google Patents

Abstract

Colour photographic Ag halide (AgX) print material has blue-sensitive (BS) and green-sensitive (GS) AgX emulsion layer(s) contg. yellow and magenta coupler(s) respectively and an intermediate layer between BS and GS layer(s). The novel features are that (a) the intermediate layer contains a white coupler, (b) the yellow coupler is an acylacetanilide of formula (I); and (c) the magenta coupler is a pyrazolotriazole of formula (II): R<1> = alkyl, aryl or heterocyclyl; R<2> = H or a gp. released by coupling; R<3> = alkyl or aryl; R<4>, R<5>, R<6>, R<7> = (ar)alkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, amino, anilino, acylamino, CN, alkoxycarbonyl, carbamoyl or sulphamoyl; o R<4>, R<7> = H; all the above gps. may have other substits.; x = 1-4; R<8> = H, -SiMe3 or -COCH3; X = H or a gp. released by chromogenic development; L = alkylene, opt. with -SO2-, -NR<9>-CO-, -O-, -CO-NR<9>- or -N(R<1->)- in the chain and opt. substd. by COOH; R<9> = H or alkyl; R<10> = phenyl.

Description

The invention relates to a color photographic record material with improved color rendering.

For color pictures, a higher color brilliance and color To achieve purity, it is not desirable that at Development of an emulsion layer the developer oxide dationsprodukt in an adjacent, coupler-containing Layer diffuses and there occurs a color reaction. This co-coupling leads to color distortions and Reduction of the color purity of the picture.

On the other hand, it is desirable that when developing two emulsions the one by stronger exposure also more developed, the one in its development inhibits less pronounced by lower exposure ent wraps. This phenomenon is called the positive inter- Image effect. Unlike the film, the IIE occurs (Inter-image effect) in paper so far not on, since the in film to achieve a positive Interimageeffek TES required DIR coupler in paper so far none Use found.  

The object of the invention is in a color photographic Print material, especially a color paper to generate positive interimage effect, without DIR coupler to use.

Print material becomes a photographic material understood, to which a negative image exposed and that is subjected to a negative development, whereupon positive image emerges. The carrier of the print material may be transparent, but is preferably reflective tierend (color paper).

It has now been found that through the use of certain Yellow coupler, certain magenta coupler and certain White coupler, the latter being in the intermediate layer between the yellow coupler and the purple coupler containing silver halide emulsion layer used even in a color photographic print material, especially a color photographic paper IIE effects can be achieved.

The strength of the IIE effect can be determined using a matrix represent values <1 in the diagonal a positive (desired) IIE effect in the ent speaking color layer. In the non-diagonal positions Values <0 mean a positive IIE effect. by virtue of the mathematical algorithms in the calculation of Matrix is the IEE matrix normalized and symmetric.

Yellow couplers according to the invention correspond to the formula I.

wherein
R¹ is alkyl, aryl or the solid of a heterocycle
R² is hydrogen or a group cleavable in the case of chromogenic development
R 3 is alkyl or aryl
R⁴ is hydrogen, alkyl, aralkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, carbamoyl or sulfamoyl and
x is an integer from 1 to 4,
where all radicals may be further substituted.

Inventive magenta couplers correspond to the formula II

wherein
R⁵ and R⁶ are alkyl, aralkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, carbamoyl and sulfamoyl, where these radicals may be further substituted,
R⁷ is hydrogen or R⁵,
R⁸ is hydrogen, -Si (CH₃) ₃ or

X is hydrogen or a group cleavable in the case of chromogenic development,
L is a straight-chain or branched, optionally substituted by -SO₂-, -NR⁹-CO-, -O-, -CO-NR⁹-, -N (R¹⁰) -, -SO₂NR⁹- or -NR⁹SO₂- interrupted, if appropriate substituted by carboxyl groups alkylene group,
R⁹ is hydrogen or alkyl and
R¹⁰ phenyl.

As white couplers compounds are used with the developer oxidation product to a colorless Ver Coupling bond. Preferred white couplers correspond to Formula III

wherein
R¹¹ is substituted or unsubstituted alkyl with ballast function,
R¹² alkyl, especially methyl and
R¹³ represents optionally substituted phenyl, in particular 4-C₁-C₃-alkylsulfonylphenyl.

White couplers can in a preferred embodiment also be used as polymeric white couplers. before Preferred polymeric white couplers have recurring ones units II and III:

wherein
R⁸, R⁹ are identical or different: hydrogen, alkyl having 1-4 C atoms, halogen, in particular Cl,
Y¹, Y² are identical or different: divalent functional group, in particular -CONH-, -NHCONH-, -NHCOO- or a chemical bond,
A¹, A² are identical or different: a divalent organic link, in particular an optionally substituted alkylene, aylene or aralkylene radical or a chemical bond,
Z¹, Z² are identical or different: a bivalent functional group, in particular -O-, -S-, -SO-, -SO₂-, -CONH-, COO- or a chemical bond,
B¹, B² are identical or different: a divalent organic link, in particular a given substituted alkylene radical or a chemical bond,
X: a divalent organic group, in particular -CONH-, -NHCONH-, -NHCOO-, -OCONH,
Ku: mean a 5-pyrazolone white coupler residue.

In a particularly preferred embodiment corresponds to the 5-pyrazolone white coupler residue -Ku following formula

wherein
R¹⁰ a usual for a pyrazolone white coupler substituent, in particular an alkyl radical having 1 to 4 carbon atoms and
Ar is an optionally substituted aryl, in particular phenyl.

In a particularly preferred embodiment is in the polymer additionally a polymerized ethylenic unsaturated compound M included.

In particularly preferred polymers, in each case in % By weight, contain:

Recurring Units II: 10-30 Recurring Units III: 3-20 Polymerized ethylenically unsaturated compound M: 87-50.

Suitable white couplers are:

The yellow coupler is preferably in an amount of 0.4 to 2.3 mmol / m², the magenta coupler preferably in one Amount of 0.4 to 2.5 mmol / m² and the white coupler before zugt in an amount of 0.01 to 0.5 mmol / m² puts.

For polymeric compounds, the statement refers "mmol" on the coupling part in the polymer.  

Measurement of the IIE effect and creation of the IEE matrix

Descriptions can be found in:
SPSE Handbook of Photographic Science and Engineering (p. 461 ff)
Ullmann's Encyclopedia of Industrial Chemistry (459 ff.)
To determine the IIE effect, the gradation curves of the individual layers are calculated from mixed exposures with blue and green light. The ana lysed densities are used.

The strength of an IIE effect is recognizable by the Numerical values of the transformation matrix, which are the Density values that occur without IIE effect (from the Single exposures - only green light or only red Light - determined) in the measured density values Mixed exposure transferred.

If no IIE effect occurs, then the diagonal elements are the matrix = 1, the non-diagonal elements = 0.  

For positive IIE effects, the diagonal elements are the Matrix <1, with negative IIE effects (co-coupling) are the diagonal elements <1. The non-diagonalele Elements of the matrix result from the standardization rule Condition of the matrix.

It is particularly preferred in the invention appropriate material to a material that specified in the Order on a carrier at least one blue temp sensitive, at least one yellow coupler containing Silver halide emulsion layer, an intermediate layer, at least one green sensitive, at least one Magenta coupler containing silver halide emulsions layer, an intermediate layer, at least one red sensitive, at least one cyan coupler enthal silver halide emulsion layer and at least contains a protective layer.

As silver halides the color coupler-containing and the color coupler-free silver halide emulsion layers com AgBr, AgBrCl, AgBrClI and AgCl.

Preferably, the silver halides all contain light sensitive layers at least 80 mol% chloride,  in particular 95 to 100 mol% chloride, 0 to 5 mol% Bromide and 0 to 1 mole% iodide. The silver halide emuls sions can be directly positive or preferential se be negative working emulsions.

The silver halide may be predominantly com pact crystals act, the z. B. regular cubic or octaetric or may have transitional forms. But it can also be twinned, z. B. platelet-shaped Crystals are present, whose average ratio from diameter to thickness preferably at least 5: 1, wherein the diameter of a grain is defined as the Diameter of a circle with a circle content ent speaking the projected area of the grain. The However, layers can also be tabular silver halide have crystals in which the ratio of Diameter to thickness greater than 5: 1, z. B. 12: 1 to 30: 1.

The silver halide grains may also be multiply have layered grain structure, in the simplest case with an inner and an outer grain area (corel shell), wherein the halide composition and / or son stige modifications, such. B. doping of the single grain areas are different. The middle Grain size of the emulsions is preferably between 0.2 μm and 2.0 μm, the particle size distribution can be both homo- as well as heterodisperse. The emulsions can in addition to the silver halide, organic silver salts included, for. B. silver benzotriazolate or silver behenate.  

There can be two or more types of silver halide emulsions that are prepared separately as Mixture be used.

The photographic emulsions can be different Methods (eg P. Glafkides, Chimie et Physique Photo graphique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman et al., Making and Coating Photo graphic emulsion, The Focal Press, London (1966) soluble silver salts and soluble halides be presented.

The precipitation of the silver halide is preferably carried out in Presence of the binder, e.g. As the gelatin and can in the acidic, neutral or alkaline pH range are conducted, preferably Silberhalogenidkom Plexbildner additionally be used. To the latter belong z. As ammonia, thioether, imidazole, ammonium thiocyanate or excess halide. The together guidance of the water-soluble silver salts and the halogens one after the other after the single-jet or simultaneously using the double-jet method or according to any combination of both methods. Prefers is the dosage with increasing inflow rates, the "critical" feed rate, just barely no new germs arise, can not be exceeded should. The pAg region may be precipitated during precipitation wide limits vary, preferably the soge called pAg-controlled method, in which a certain pAg value kept constant or defi  Named pAg profile is passed through during the precipitation. In addition to the preferred precipitation at halide excess but also the so-called inverse precipitation in silver ion excess possible. Except by precipitation, the Silver halide crystals also by physical Rei (Ostwald ripening), in the presence of excess Halide and / or silver halide complexing agent to grow. The growth of the emulsion grains can even predominantly by Ostwaldreifung done, where before preferably a fine-grained, so-called Lippmann Emul mixed with a sparingly soluble emulsion and is redirected to the latter.

The precipitation of the silver halide grains may be in the presence of "growth modifiers", these are substances that affect the growth so that special Kornfor grains and grain surfaces (eg 111 surfaces in AgCl) arise.

During precipitation and / or physical ripening The silver halide grains may also be salts or complexes xe from group 8, 1b, 2b, 3a, 4a and 5a of the period Systems of elements for doping the silver halides be used.

Furthermore, the precipitation can also in the presence of Sensibili Sierungsfarbstoffen done. complexing and / or dyes can be added to any Make ineffective, eg. B. by changing the pH Value or by an oxidative treatment.  

The binder used is preferably gelatin. However, this can be done in whole or in part by others synthetic, semi-synthetic or natural occurring polymers are replaced. synthetic Gelatine substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrolidone, polyacrylamides, poly acrylic acid and its derivatives, in particular their Copolymers. Naturally occurring gelatin Substances are, for example, other proteins such as Albumin or casein, cellulose, sugar, starch or Alginates. Semisynthetic gelatin substitutes are in usually modified natural products. cellulose derivatives such as hydroxyalkylcellulose, carboxymethylcellulose and Phthalylcellulose and gelatin derivatives by Reaction with alkylating or acylating agents or by grafting on of polymerizable monomers have been obtained are examples of this.

The binders should be over a sufficient amount functional groups, so that by implementation sufficient resistance with suitable curing agents capable layers can be generated. Such radio tional groups are especially amino groups, but also carboxyl groups, hydroxyl groups and active methyl lengruppen.

The gelatin preferably used can be acidic or alkaline digestion. The manufacturer Such gelatins, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, p  295 ff. The gelatine used in each case should have the lowest possible content of photographic contain active impurities (inert gelatin). Gelatins with high viscosity and low swelling are particularly advantageous. The gelatin can partially or completely oxidized.

After completed crystal formation or already too at an earlier point in time, the soluble salts become the emulsion removed, z. By noodles and washing, by flocculation and washing, by ultrafiltration or by ion exchanger.

The photographic emulsions may be compounds for Prevention of fogging or stabilization the photographic function during production, the Storage or photographic processing enthal th.

Particularly suitable are azaindene, preferably tetrainden and pentaazaindenes, especially those with Hydroxyl or amino groups are substituted. such Connections are z. B. von Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Furthermore, as Antifoggant salts of metals, aromatic Sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, Nitroindazole, (subst.) Benzotriazoles or benzthiazolium salts are used. Particularly suitable are mercap tocene-containing heterocycles, eg. B. mercaptobenzene thiazoles, mercaptobenzimidazoles, mercaptotetrazoles, Mercaptothiadiazoles, mercaptopyrimidines, these being  Mercaptoazole also a water-solubilizing group, z. As a carboxyl group or sulfo group included can. Other suitable compounds are in Research Disclosure No. 17643 (1978), Section VI, published light.

The stabilizers can be added to the silver halide emulsions be added before, during or after their maturation. Of course, you can also thee connections ren photographic layers containing a silver halide layer are assigned, enforce.

It can also be mixtures of two or more of mentioned compounds are used.

The silver halide emulsions usually become chemically matured, for example, by the action of Gold compounds or compounds of the bivalent Sulfur.

The photographic emulsion layers or other hydro phile colloid layers of the invention produced Photosensitive material can be surface-active Means for various purposes included, such as coating help to prevent electrical charging, to Improvement of gliding properties, to emulsify the Dispersion, to prevent adhesion and Ver improvement of the photographic characteristics (eg Ent acceleration, high contrast, sensibilisation tion, etc.).  

Suitable sensitizing dyes are cyanine color substances, in particular the following classes:

• 1. Rotsensitizers
  Dicarbocyanines with naphthothiazole or benzothiazole as basic end groups, which may be substitu- tuiert in the 5- and / or 6-position by halogen, methyl, methoxy and 9.11-alkylene-bridged, especially 9.11-Neopentylenthiadicarbocyanine with alkyl or sulfoalkyl substituents on the nitrogen.
• 2. Green sensitizers
  9-Ethyloxacarbocyanine which are substituted in the 5-position by chlorine or phenyl and nitrogen on the nitrogen of the benzoxazole alkyl or sulfoalkyl radicals, preferably carry sulfoalkyl substituents.
• 3. Blue sensitizers
  Methine cyanines with benzoxazole, benzothiazole, benzselenazole, naphthoxazole, naphthothiazole as basic end groups, which may be substituted in the 5- and / or 6-position by halogen, methyl, methoxy and carrying at least one, preferably two, sulfoalkyl substituents on the nitrogen. Further, apomerocyanines having a rhodanine group.

Sensitisers can be omitted if for a specific spectral range the Eigenempfindlich  keits of the silver halide is sufficient, for example show the blue sensitivity of silver bromide iodides.

Color coupler for producing the cyan partial colors picture are usually phenolic or coupler Naphthol.

The color couplers can be 4-equivalent couplers but also about 2-equivalent couplers. Latter derive from the 4-equivalent couplers in that they contain a substituent in the coupling site th, which is split off during the clutch.

The couplers usually contain a ballast residue, to diffusion within the material, d. H. either within a layer or from layer to layer, impossible to do. Instead of couplers with one Ballast residue can also be high molecular weight couplers be set.

Suitable color couplers or literature references in which such are described in Research Disclo sure 17 643 (1978), Chapter VII.

High molecular color couplers are described, for example, in DE-C-12 97 417, 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 described. The high molecular color couplers are in usually by polymerization of ethylenically unge  saturated monomeric color couplers produced. You can but also by polyaddition or polycondensation he to hold.

The incorporation of the couplers or other compounds in silver halide emulsion layers can in the way be done first by the relevant connection a solution, a dispersion or an emulsion and then the casting solution for the concerned Layer is added. The selection of the appropriate Solvent or dispersant depends on the jewei solubility of the compound.

Methods for introducing into water substantially insoluble compounds by grinding processes are For example, in DE-A 26 09 741 and DE-A 26 09 742 described.

Hydrophobic compounds can also be made using high-boiling solvents, so-called oil formers, be introduced into the casting solution. Appropriate 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 beschrie ben.

Instead of the high-boiling solvents, oligo mers or polymers, so-called polymeric oil-formers Ver find a turn.

The compounds may also be in the form of loaded latices be introduced into the casting solution. Is referred  For example, 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, US Pat. No. 4,291,113.

The diffusion-resistant storage of anionic water sol Licher compounds (eg of dyes) can also with Help of cationic polymers, so-called pickling made of polymers.

Suitable oil formers are z. Phthalic acid alkyl ester, Phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, tri mesinic 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-ethyl hexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2- ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethyl hexyl p-hydroxybenzoate, diethyl dodecanamide, N-tetra decylpyrrolidone, isostearyl alcohol, 2,4-di-tert-amyl phenol, trioctyl citrate, N, N-dibutyl-2-butoxy-5-tert. octylaniline, paraffin, dodecylbenzene and diisopropyl naphthalene.

The photographic material may further UV-absorbing compounds, whiteners, spacers, filter dyes, formalin scavenger, white couplers, light stabilizers, antioxidants, D _min dyes, additives to improve the dye, coupler and willow stabilization and to reduce color fog, plasticizer (Latices), biocides, and others.

UV-absorbing compounds on the one hand the image dyes from fading by UV-rich Protecting daylight and on the other hand as a filter color The UV light in the daylight during exposure absorb and thus the color rendering of a film ver improve. Usually, for the two tasks Compounds of different structure used.

Examples are aryl-substituted benzotriazole compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. No. 3,314,794 and 3,352,681), benzophenone compounds (JP-A 2784171), Cinnamic acid ester compounds (US Pat. No. 3,705,805 and US Pat No. 3,707,375), butadiene compounds US Pat. No. 4,045,229) or US Pat Benzoxazole compounds (US Pat. No. 3,700,455).

It is also possible to use ultraviolet absorbing couplers (such as Cyan coupler of the α-naphthol type) and ultraviolet absorbent polymers are used. This ultra Violet absorbents can be removed by pickling in a spe be fixed in a particular layer.

For visible light suitable filter dyes include Oxonol dyes, hemioxonol dyes, styryl color substances, merocyanine dyes, cyanine dyes and Azo dyes. Of these dyes Oxonolfarb substances, hemioxonol dyes and merocyanine dyes used particularly advantageous.  

Suitable whiteners are z. 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 ben.

Certain binder layers, in particular those of Wearer furthest away, but also gels often intermediate layers, especially if they during production the furthest from the wearer represent distant layer, can photographically inert Contain particles of inorganic or organic nature, z. B. as a matting agent or as a spacer (DE-A 33 31 542, DE-A 34 24 893, Research Disclosure 17 643, (Dec., 1978), Chapter XVI).

The mean particle diameter of the spacers is in particular in the range of 0.2 to 10 microns. The Spacers are water insoluble and can be alkaline insoluble or alkali-soluble, the alkali soluble generally in the alkaline development bath be removed from the photographic material. at Games for suitable polymers are Polymethylmethacry lat, copolymers of acrylic acid and methyl methacrylate and hydroxypropylmethylcellulose hexahydrophthalate.

Additives to improve the dye, coupler and White stability as well as to reduce the color veil (Research Disclosure 17 643/1978, Chapter VII) may belong to the following chemical classes: Hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, Spirochromans, spiroindans, p-alkoxyphenols, steric  hindered phenols, gallic acid derivatives, methylenedioxy benzenes, aminophenols, hindered amines, Deri vate with esterified or etherified phenolic Hydroxyl groups, metal complexes.

Compounds containing both a sterically hindered amine Partial structure as well as a sterically hindered Phe nol partial structure in one molecule (US Pat. No. 4,268,593), are particularly effective for preventing the Impairment (deterioration or degradation) of gel ben color images as a result of the development of heat, Moisture and light. To the impairment (Ver deterioration or degradation) of purple Farbbil particular, their impairment (deterioration degradation) as a result of the action of light, are spiroindanes (JP-A 159 644/81) and Chromans produced by hydroquinone diethers or monoethers Substituted are particularly effective (JP-A 89 835/80).

The layers of photographic material can with hardened the usual curing agents. suitable Hardeners are z. As formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethylharn substance), 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- diacrylhexahydro-1,3,5-triazine and other compounds, which contain a reactive olefin bond (US Pat. No. 3,635,718, US-A 3,232,763 and GB-A 994,869); N-hydroxy  methylphthalimide and other N-methylol compounds (US Pat. No. 2,732,316 and US Pat. No. 2,586,168); Isocyanates (US Pat. No. 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 Pat. No. 3,100,704); Carbamoylpyridiniumsalze (DE-A 22 25 230 and DE-A 24 39 551); Carbamoyloxypyridiniumverbindungen (DE-A 24 08 814); Compounds with a phosphorus-halogenated Binding (JP-A 113 929/83); N-Carbonyloximid compounds (JP-A 43353/81); M-sulphonyloximido compounds (US Pat. No. 4,111,926), Dihydroquinoline compounds (US Pat. No. 4,013,468), 2-sulfonyloxypyridinium salts (JP-A 110 762181), Formamidinium salts (EP-A 0 162 308), Ver compounds with two or more N-acyloximino groups (US-A 4 052 373), epoxy compounds (US-A-3 091 537), Verbin isoxazole-type (US Pat. No. 3,321,313 and US Pat. No. 3,543,292); Halogencarboxyaldehyde, such as mucochloric acid; Dioxane derivatives such as dihydroxydioxane and di-chlorodioxane; and inorganic hardeners such as chrome alum and zircon sulfate.

The curing can be effected in a known manner be that the curing agent of the casting solution for the is added to be hardened layer, or in that the layer to be cured is overcoated with a layer which contains a diffusible curing agent.

Among the listed classes, there are slow-acting ones and fast-acting hardeners and so-called Instant hardeners that are particularly beneficial. Under First-aiders are understood to mean connections that are ge  suitable binders so that immediately after Infusion, at the latest after 2: 4 hours, preferably late at the end of 8 hours the hardening is completed is that no further through the crosslinking reaction conditional change of sensitometry and swelling of the Layered dressing occurs. Under swelling, the Difference between wet layer thickness and dry layer thickness understood in the aqueous processing of the film (Photograph Sci., Eng. 8 (1964), 275; Photograph Sci. Eng. (1972), 449).

These are very fast reacting with gelatin means are, for. B. carbamoylpyridy nium salts containing the free carboxyl groups of gelatin to react, so that the latter with free Amino groups of gelatin to form peptide bonds and crosslinking of gelatin react.

There are diffusible curing agents that work on everyone Layers within a layer structure in the same Way hardening act. But there are also stratum-limited acting, non-diffusing, low molecular weight and high molecular weight hardener. With them you can individual Layers, z. B. the protective layer is particularly strong network. This is important when considering the silver halo genide layer little because of the silver cover force increase hardens and with the protective layer the mechanical Properties must improve (EP-A 0 114 699).

The color photographic materials of the invention are usually developed by developing, bleaching, Fi  xieren and watering or stabilizing without subsequent Watering processed, with bleaching and fixing too a processing step can be summarized. As the color developer compound, all Ent Use winder connections that have the capability zen, in the form of their oxidation product with color couplers react to azomethine or indophenol dyes. Suitable color developing agents are aromatic, at least one primary amino-containing verbin p-phenylenediamine-type compounds, for example N, N-di alkyl-p-phenylenediamines such as N, N-diethyl-p-phenylene diamine, 1- (N-ethyl-N-methanesulfonamido-ethyl) -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 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 can be an acid stop bath or follow a watering.

Usually, the material after the color development bleached and fixed. As a bleaching agent z. B. Fe (III) salts and Fe (III) complex salts such as ferricyanides, Dichromates, water-soluble cobalt complexes used become. Particularly preferred are iron (III) complexes of aminopolycarboxylic acids. in particular z. B. from Ethylenediaminetetraacetic acid, propylenediaminetetra acetic acid, diethylenetriaminepentaacetic acid, nitrilotri acetic acid, alaninediacetic acid, iminodiacetic acid, N-Hy  droxyethyl-ethylenediaminetriacetic acid, alkyliminodicar acids and corresponding phosphonic acids. Geeig Neten as bleaching agents are persulfates and Per oxides, e.g. B. hydrogen peroxide.

The bleach-fix or fixer is usually followed by one Irrigation, which is designed as countercurrent irrigation and from several tanks with their own water supply be stands.

Cheap results can be obtained by using one following final bath, the little or no form aldehyde.

The watering can be full but by a stabilizer constantly replaced, usually in countercurrent to be led. This stabilizer takes on form aldehyde addition also the function of a final bath.

Examples

A color photographic recording material which was suitable for a fast processing process has been made by putting on one side with polyethylene coated paper the following layers in the in the order indicated. The quantities Details refer to 1 m² each. for the silver halide order, the corresponding amounts of AgNO₃ specified.

Example 1 (comparison) Layer structure 1

• 1st layer (substrate layer)
  0.2 g of gelatin
• 2nd layer (blue-sensitive layer)
  blue-sensitive silver halide emulsion (99.5 mol%, chloride, 0.5 mol% bromide, mean grain diameter 0.78 microns), from 0.50 g AgNO₃,
  1.38 g of gelatin
  0.60 g yellow coupler GB 10
  0.48 g tricresyl phosphate (TKP)
• 3rd layer (intermediate layer)
  1.18 g of gelatin
  0.08 g of 2,5-dioctylhydroquinone
  0.08 g of dibutyl phthalate (DBP)
• 4th layer (green-sensitive layer)
  green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.37 microns) from 0.40 g of AgNO₃,
  1.02 g of gelatin
  0.37 g magenta coupler PP 10
  0.40 g DBP
• 5th layer (intermediate layer)
  1.20 g of gelatin
  0.66 g UV absorber of the formula 0.052 g of 2,5-dioctylhydroquinone
  0.36 g TKP
• 6th layer (red-sensitive layer)
  red-sensitized silver halide emulsion (99.5 mole% chloride, 0.5 mole-μ bromide, mean grain diameter 0.35 μm) of 0.28 g AgNO₃,
  0.84 g of gelatin
  0.39 g cyan coupler C-1
  0.39 g TKP
• 7th layer (UV protection layer)
  0.65 g of gelatin
  0.21 g UV absorber as in 5th layer
  0.11 g TKP
• 8th layer (protective layer)
  0.65 g of gelatin
  0.39 g of curing agent of the formula

Samples of the layer structures were subsequently behind Illuminated a graduated gray wedge. After that, the Materials with the following processing processing baths in the usual way.

a) Color developer - 45 s - 35 ° C

Triethanolamine | 9.0 g / l NN-diethyl 4.0 g / l diethylene glycol 0.05 g / l 3-methyl-4-amino-N-ethyl-N-methanesulfonamidoethyl-aniline sulfate 5.0 g / l potassium 0.2 g / l   triethylene 0.05 g / l potassium carbonate 22 g / l potassium hydroxide 0.4 g / l Ethylendiamintetraessigsäuredi Na salt 2.2 g / l potassium chloride 2.5 g / l 1,2-dihydroxybenzene-3,4,6-trisulfonic acid trisodium salt 0.3 g / l make up to 1000 ml with water; pH 10.0

b) Bleach-fix bath - 45 s - 35 ° C

Ammonium thiosulphate | 75 g / l sodium bisulfite 13.5 g / l ammonium acetate 2.0 g / l Ethylenediaminetetraacetic acid (ferric ammonium salt) 57 g / l Ammonia 25% by weight 9.5 g / l acetic acid 9.0 g / l make up to 1000 ml with water; pH 5.5

c) watering - 2 min - 35 ° C

d) drying

Examples 2 to 10

The following table indicates by which Purple coupler in the same amount of couplers PP10, by which yellow couplers in the same amount of the coupler GB10 were replaced and whether in the 3rd layer a white coupler was used. The amount of white couplers was always 10 mg / m².  

The compounds indicated by VK are comparative coupler, the structure of which is given below.

Hereinafter, for the examples 1 to 9 ge measure color densities in purple (Dpp) and yellow (Dgb) so as the calculated inter-image effects give. The results prove that without white couplers in the interlayer does not achieve an inter-image effect is. This applies equally to non-inventive appropriate coupler.  

Claims (2)

A color photographic silver halide printed material comprising at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, and an intermediate layer disposed between the at least one blue-sensitive and at least one green-sensitive silver halide emulsion layer characterized by the combination of:

• (a) the intermediate layer contains a white coupler,
• (b) the yellow coupler corresponds to the formula I. wherein
  R¹ is alkyl, aryl or the radical of a heterocycle
  R² is hydrogen or a group which can be split off in the coupling
  R 3 is alkyl or aryl
  R⁴ is hydrogen, alkyl, aralkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, carbamoyl or sulfamoyl and
  x is an integer from 1 to 4,
  where all radicals can be further substituted,
• (c) the magenta coupler corresponds to the formula II wherein
  R⁵ and R⁶ are alkyl, aralkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, carbamoyl and sulfamoyl, where these radicals may be further substituted,
  R⁷ is hydrogen or R⁵,
  R⁸ is hydrogen, -Si (CH₃) ₃ or X is hydrogen or a group cleavable in chromogenic development,
  L is a straight-chain or branched, if appropriate by -SO₂-, -NR⁹-CO-, -O-, -CO-NR⁹-, -N (R¹⁰) - interrupted, optionally substituted by carboxyl groups alkylene group,
  R⁹ is hydrogen or alkyl and
  R¹⁰ phenyl.

2. Color photographic print material according to patent claim 1, characterized in that the Weißkupp ler of the formula III corresponds wherein
R¹¹ is substituted or unsubstituted alkyl with ballast function,
R¹² alkyl, especially methyl and
R¹³ optionally substituted phenyl meaning th.