EP0563638B1 - Photographic recording material - Google Patents

Photographic recording material Download PDF

Info

Publication number
EP0563638B1
EP0563638B1 EP93103858A EP93103858A EP0563638B1 EP 0563638 B1 EP0563638 B1 EP 0563638B1 EP 93103858 A EP93103858 A EP 93103858A EP 93103858 A EP93103858 A EP 93103858A EP 0563638 B1 EP0563638 B1 EP 0563638B1
Authority
EP
European Patent Office
Prior art keywords
layer
alkyl
aryl
color
coupler
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP93103858A
Other languages
German (de)
French (fr)
Other versions
EP0563638A1 (en
Inventor
Jörg Dr. Hagemann
Günter Dr. Helling
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert AG
Original Assignee
Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0563638A1 publication Critical patent/EP0563638A1/en
Application granted granted Critical
Publication of EP0563638B1 publication Critical patent/EP0563638B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39232—Organic compounds with an oxygen-containing function
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
    • G03C7/3005—Combinations of couplers and photographic additives
    • G03C7/3008—Combinations of couplers having the coupling site in rings of cyclic compounds and photographic additives
    • G03C7/301—Combinations of couplers having the coupling site in pyrazoloazole rings and photographic additives

Definitions

  • the invention relates to a photographic recording material with at least one silver halide emulsion layer, the new type of light stabilizer for those at Chromogenic development produced purple azomethine dyes of pyrazoloazole type contains.
  • Color developer - developed which is in accordance oxidation product resulting from the silver image of the developer substances with the color coupler with formation of a dye image reacts.
  • a color developer are usually aromatic, containing primary amino groups Compounds, especially those of the p-phenylenediamine type, used.
  • Light stabilizing agents are essentially suitable phenolic compounds, especially derivatives of Hydroquinones, either added to the couplers or linked in the form of substituents with the coupler molecules (DE-B-1 547 803, DE-A-26 17 826, DE-A-29 52 511, JP-N 53 070 822, JP-N 54 070 830, JP-N 54 073 032).
  • the known light stabilizers are sufficient but not in all respects the one made to them Conditions.
  • the invention has for its object for photographic Novel light stabilizers specify, especially those for improvement the light stability of those from magenta couplers, of the pyrazoloazole type produced purple image dyes are suitable.
  • a radical which can be split off under alkaline conditions and is represented by R 1 is, for example, an acyl radical which is derived from aliphatic or aromatic carboxylic acids;
  • Examples of radicals which can be split off under alkaline conditions are acetyl, dichloroacetyl, alkoxycarbonyl and pyruvoyl.
  • An alkyl radical represented by R 2 to R 6 preferably contains 1 to 4 carbon atoms, examples are methyl, ethyl, propyl, isopropyl, butyl, t-butyl.
  • An aryl radical represented by R 2 to R 6 contains 6 to 10 C atoms; Examples are phenyl and naphthyl.
  • the alkyl or aryl radicals can be further substituted, for example with halogen or alkyl.
  • An alkoxy radical represented by R 2 to R 6 can contain 1 to 18 carbon atoms.
  • the acyl radical in an acylamino radical represented by R 2 to R 6 is derived from aliphatic or aromatic carboxylic or sulfonic acids.
  • the compounds of the invention can be prepared in a simple manner by reacting amines of the formula II with monomeric mono-, di- or polyisocyanates.
  • isocyanates for the preparation of compounds of the formula I are all aromatic and aliphatic Isocyanates with 1 to 4 isocyanate groups such as e.g. 3-chlorophenyl isocyanate, Phenyl isocyanate, 1,3-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, the isomers of tolylene diisocyanate, optionally a mixture, 2,4-bis (4-isocyanatobenzyl) -1-isocyanato-benzene, Tris (4-isocyanatophenyl) methane, 2-ethyl-1,2,3-tris (3-isocyanato-4-methyl-anilinocarbonyloxy) propane, Tetrakis (5-isocyanatopentylcarbonyloxymethyl) methane, preferably the aliphatic Mono- and diisocyanates such as dodecyl iso
  • the compounds S-2 to S-14 are made in an analogous manner from the corresponding compounds of formula II and Isocyanates produced.
  • the color photographic recording material according to the invention contains at least one photosensitive silver halide emulsion layer and preferably a sequence several such photosensitive silver halide emulsion layers and optionally further auxiliary layers such as in particular protective layers and between the photosensitive Layers of non-photosensitive Binder layers, according to the present invention at least one of the existing photosensitive Silver halide emulsion layers according to the invention Connection in combination with a magenta coupler of the pyrazoloazole coupler type is.
  • the compounds of the invention act in primarily as a light stabilizer, i.e. the formed from the color coupler in the chromogenic development Azomethine dyes exhibit in the presence of Compounds according to the invention increased considerably Stability against exposure to light.
  • a light stabilizer i.e. the formed from the color coupler in the chromogenic development Azomethine dyes exhibit in the presence of Compounds according to the invention increased considerably Stability against exposure to light.
  • Oil formers can be used as coupler solvents.
  • the compounds according to the invention preferably do this 10 to 60 wt .-% of the total amount of oil in the respective layer. The fact that more Oil formers may only be required in smaller quantities are beneficial for shift load and / or the total layer thickness of the invention Recording materials.
  • the compounds of the invention fall in the manufacture (Implementation of active hydrogen atoms Compounds with isocyanates) mostly as low-melting Solids on and are as a solution in aprotic (hydrophobic) solvents, e.g. Ethyl acetate, during incorporation into the casting solution for the concerned Layer, if necessary together with the respective Color coupler used.
  • aprotic (hydrophobic) solvents e.g. Ethyl acetate
  • the familiarization takes place in the usual way, if necessary further Auxiliary solvents and / or high-boiling coupler solvents, so-called oil formers can be used.
  • Silver halide can be used as halide chloride, Contain bromide or iodide or mixtures thereof.
  • the halide content can be at least one 0 to 15 mol% layer of iodide, 0 to 100 mol% consist of chloride and 0 to 100 mol% of bromide.
  • silver bromide iodide emulsions with high chloride content up to pure silver chloride emulsions are used.
  • It can are mainly compact crystals, e.g. are regular cubic or octahedral or transitional forms can have. But preferably also platelet-shaped crystals are present, their average Ratio of diameter to thickness is preferably at least 5: 1, the diameter a grain is defined as the diameter of a Circle with a circle content corresponding to the projected Area of the grain.
  • the layers can also have tabular silver halide crystals, where the ratio of diameter to thickness is significantly larger than 5: 1, e.g. 12: 1 to 30: 1.
  • the silver halide grains can also be multi-layered Have grain structure, in the simplest case with an inner and an outer grain area (core / shell), wherein the halide composition and / or other modifications, such as Endowments of the individual Grain areas are different.
  • the middle The grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be both be homo- and heterodisperse. Homodisperse grain size distribution means 95% of the grains are not deviate more than ⁇ 30% from the average grain size.
  • the emulsions can also other silver salts, e.g. contain organic silver salts, such as silver benzotriazolate or silver behenate.
  • Two or more types of silver halide emulsions which are made separately, as a mixture be used.
  • the emulsions can be chemically and in the usual way or be spectrally sensitized; you can also by suitable additives must be stabilized.
  • Suitable chemical Sensitizers, spectral sensitizing dyes and stabilizers are, for example, in Research Disclosure 17643 (December 1978); referred special attention is paid to chapters III, IV and VI.
  • the color photographic recording material according to the invention contains preferably the one according to the invention Combination of pyrazoloazole coupler and connection of the Formula I containing, normally green-sensitized Silver halide emulsion layer further silver halide emulsion layers for recording light of the other spectral ranges red and blue.
  • the purpose of the photosensitive layers is known Spectrally by suitable sensitizing dyes sensitized.
  • Suitable green sensitizers are, for example 9-ethyl carbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzthiazole as basic end groups as well as benzimidazocarbocyanines, which also may be further substituted and also at least a sulfoalkyl group on heterocyclic nitrogen must contain.
  • Each of the light-sensitive layers mentioned can consist of consist of a single layer or in a known manner, e.g. with the so-called double layer arrangement, too two or more silver halide emulsion partial layers include (DE-C-1 121 470).
  • negative films usually red sensitive silver halide emulsion layers arranged closer to the substrate than those sensitive to green Silver halide emulsion layers and these again closer than blue-sensitive, which is generally between green sensitive layers and blue sensitive Layers a non-photosensitive yellow filter layer.
  • blue-sensitive which is generally between green sensitive layers and blue sensitive Layers a non-photosensitive yellow filter layer.
  • the means for preventing the Incorrect diffusion of developer oxidation products included can.
  • Color photographic recording materials according to the invention usually contain in spatial and spectral Assignment to the silver halide emulsion layers different spectral sensitivity color coupler to generate the different part color images Cyan, magenta and yellow, with the invention Connections together with the respective color coupler preferably a green-sensitive silver halide emulsion layer assigned.
  • Spatial assignment is understood to mean that the color coupler is in such a spatial Relationship to the silver halide emulsion layer finds that an interaction between them is possible which is a visual match between the silver picture formed during development and the allows the color coupler generated color image. This is in usually achieved in that the color coupler in the Silver halide emulsion layer itself is included or in a neighboring one if necessary non-photosensitive binder layer.
  • Spectral assignment means that the Spectral sensitivity of each of the photosensitive Silver halide emulsion layers and the color of the the spatially assigned color coupler Partial color image in a certain relationship to each other stand, each of the spectral sensitivities (Red, green, blue) another color of the concerned Partial color image (generally e.g. the colors cyan, Purple or yellow in this order).
  • Each of the different spectrally sensitized silver halide emulsion layers can one or can also several color couplers can be assigned. When multiple silver halide emulsion layers same spectral sensitivity are present, each of them can be one Color couplers included, but these color couplers are not necessarily need to be identical. You should only at least approximately in the color development result in the same color, usually a color that is complementary to the color of the light for which the silver halide emulsion layers concerned predominantly are sensitive.
  • couplers can be 4 equivalent couplers, but also act as 2-equivalent couplers.
  • the latter are derived from the 4 equivalent couplers that they have a substituent in the coupling site included, which split off at the clutch becomes.
  • the 2-equivalent couplers include those which are colorless, as well as those which are intense Have their own color in the color coupling disappears or due to the color of the image dye produced is replaced (mask coupler), but also the White couplers that react with color developer oxidation products essentially colorless products surrender.
  • Coupler to be expected in the coupling point releasable residue contained in the reaction with color developer oxidation products is set free and either directly or after from the primary split off remainder one or more 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 specific one desired photographic effectiveness unfolds, e.g. as a development inhibitor or accelerator.
  • Examples the known ones for such 2-equivalent couplers DIR couplers as well as DAR or. FAR coupler.
  • the couplers used especially those according to the invention used pyrazoloazole type magenta couplers, for example of the formulas IV and V, can also in polymeric form, e.g. as a polymer latex for use reach.
  • 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 color couplers are usually by polymerizing ethylenically unsaturated monomers Color couplers manufactured.
  • the color couplers used can also be those that Dyes with poor or limited mobility deliver.
  • a mobility that is measured in this way is that the contours of chromogenic development formed discrete dye stains run and are smeared into each other.
  • This degree of mobility is to be distinguished on the one hand from the usual Case of complete immobility in photographic Layers used in conventional photographic materials for the color couplers or from them Dyes produced is aimed at a possible to achieve high sharpness, and on the other hand by the case of complete mobility of the dyes, the for example in color diffusion processes becomes.
  • the latter dyes usually have about at least one group they are in alkaline Make medium soluble.
  • the extent of the invention aimed weak mobility can be controlled are made by varying substituents, for example the solubility in the organic medium of the oil former or the affinity for the binder matrix in a more targeted manner Way to influence.
  • the color photographic Recording material of the present Invention contain other additives, such as Antioxidants, dye stabilizers and Means for influencing the mechanical and electrostatic Properties as well as UV absorbers.
  • additional connections are combined with the compounds of the invention, i.e. in the same Binding agent layer or in adjacent to each other Binder layers used.
  • Additives to improve the dye, coupler and White stability and to reduce the color fog can belong to the following chemical substance classes: Hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, Spirochromanes, spiroindanes, p-alkoxyphenols, steric hindered phenols, gallic acid derivatives, Methylenedioxybenzenes, aminophenols, sterically hindered Amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
  • R -C 8 H 17 -t
  • R 1 -C 3 H 7 -i R
  • R 1 -C 4 H 9 -t
  • R 1 -C 5 H 11 -t
  • 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 Cyan couplers of the ⁇ -naphthol type
  • ultraviolet absorbing Polymers are used. These ultraviolet absorbents can be done by pickling in a special Layer fixed.
  • the invention is used to produce color photographic images color photographic recording material, assigned to at least one silver halide emulsion layer a color coupler and a connection of the Formula I contains, with a color developer compound developed.
  • Can be used as a color developer compound use all developer connections that the Have ability in the form of their oxidation product Color couplers react to azomethine dyes.
  • Suitable Color developer compounds are aromatic at least compounds containing a primary amino group of the p-phenylenediamine type, for example N, N-dialkyl-p-phenylenediamine, such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3-methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl-3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
  • N, N-dialkyl-p-phenylenediamine such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3-methyl-p-phenylenediamine, 1- (N-ethyl-
  • the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together.
  • the usual compounds can be used as bleaching agents, for example Fe 3+ salts and Fe 3+ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes, etc.
  • Particularly preferred are iron III complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediamine triacetic acid, alkyliminodicarboxylic acids and alkyliminodicarboxylic acids of corresponding phosphonic acids.
  • Persulphates are also suitable as bleaching agents.
  • Samples 2 to 12 were prepared in the same way as sample 1, with the difference that the tricresyl phosphate used in sample 1 was replaced in sample 2 (also compare samples 6-9) and that a light stabilizer was additionally used in samples 3-12 , namely in samples 3-11 a compound of formula I (according to the invention) and in sample 12 the comparison compound of formula: Samples 1-12 contained either tricresyl phosphate or dibutyl phthalate as oil formers (see Table 1).
  • the samples obtained were then exposed behind a graduated gray wedge.
  • the materials were then processed in the following manner using the processing baths listed below: development 210 s, 33 ° C bleaching 50 s, 20 ° C Fix 60 s, 20 ° C Water 120 s, 20 ° Dry.
  • the example shows that the compounds of the invention high maximum color densities can be achieved and at the same time improves the light stability of the image dye becomes.
  • the connection used as a comparison VP-1 according to GB 2 135 788 causes less improvement the light stability.
  • Example 1 As described in Example 1, it becomes a layer structure produced with the difference that in the green sensitive Layer instead of the magenta coupler M-5 Magenta coupler M-14 is used. You get that Sample 13 (comparison).
  • Samples 14-18 are prepared in the same manner as sample 13, except that layer 3 in sample 13 has one of the compounds according to the invention added. In the same way, sample 19 is prepared using the comparative compound VP-1. Processing and testing are carried out as described in Example 1.
  • the example shows that by using the invention Compounds the light stability of the image dyes is improved.
  • the used as a comparison Connection VP-1 according to GB 2 135 788 causes a lower one Improve light stability.
  • a color photographic recording material suitable for a rapid processing process was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene.
  • the quantities given relate to 1 m 2 .
  • the corresponding amounts of AgNO 3 are given for the silver halide application.
  • Samples 21 to 27 were produced in the same way as sample 20, with the difference that the 4th layer (sensitive to green) is a light stabilizer according to the invention of the formula I (samples 21 to 25) or the comparative compounds VP-1 and VP-2 (samples 26 or 27) were added.
  • the example shows a significant improvement in Light stability of the image dyes by the invention Connections as opposed to those for comparison used connections VP-1 and VP-2.
  • a color photographic recording material suitable for reversal processing was produced by applying the following layers in the order given to a transparent layer support made of cellulose triacetate provided with an adhesive layer.
  • the quantities given relate to 1 m 2 .
  • the corresponding amounts of AgNO 3 are given for the silver halide application.
  • Samples 29-33 are made in the same manner like sample 28 with the difference that the 6th and the 7th layer (green-sensitive layers) according to the invention Compound of formula I (samples 29-32) or the Compound VP-2 (sample 33) is added.
  • the maximum color density was then measured (Tab. 4) and the samples were exposed to the light of a xenon lamp standardized for daylight and exposed to 7.2 x 10 6 lx ⁇ h; the percentage decrease in density was then measured.
  • the example shows that the compounds according to the invention improve the light stability of the image dyes.
  • the connection VP-2 set as a comparison causes less improvement.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Description

Die Erfindung betrifft ein fotografisches Aufzeichnungsmaterial mit mindestens einer Silberhalogenidemulsionsschicht, das neuartige Lichtschutzmittel für die bei der chromogenen Entwicklung erzeugten purpurfarbenen Azomethinfarbstoffe von Pyrazoloazol-Typ enthält.The invention relates to a photographic recording material with at least one silver halide emulsion layer, the new type of light stabilizer for those at Chromogenic development produced purple azomethine dyes of pyrazoloazole type contains.

Es ist bekannt, farbige fotografische Bilder durch chromogene Entwicklung herzustellen, d.h. dadurch, daß man bildmäßig belichtete Silberhalogenidemulsionsschichten in Gegenwart geeigneter Farbkuppler mittels geeigneter farbbildender Entwicklersubstanzen - sogenannter Farbentwickler - entwickelt, wobei das in Übereinstimmung mit dem Silberbild entstehende Oxidationsprodukt der Entwicklersubstanzen mit dem Farbkuppler unter Bildung eines Farbstoffbildes reagiert. Als Farbentwickler werden gewöhnlich aromatische, primäre Aminogruppen enthaltende Verbindungen, insbesondere solche vom p-Phenylendiamintyp, verwendet. It is known to go through colored photographic images to produce chromogenic development, i.e. as a result of that exposed silver halide emulsion layers in the presence of suitable color couplers by means of suitable color-forming developer substances - so-called Color developer - developed, which is in accordance oxidation product resulting from the silver image of the developer substances with the color coupler with formation of a dye image reacts. As a color developer are usually aromatic, containing primary amino groups Compounds, especially those of the p-phenylenediamine type, used.

Es ist auch bekannt, daß die durch chromogene Entwicklung erzeugten Bildfarbstoffe in unterschiedlichem Ausmaß unter dem Einfluß der Umweltbedingungen gewisse Veränderungen erleiden. Besonders auffällig ist dies, was die Einwirkung von Licht betrifft. Bekanntlich bleichen hierbei die aus Pyrazoloazolkupplern erzeugten Magentafarbstoffe besonders stark aus, während sich die aus phenolischen Kupplern erzeugte Blaugrünfarbstoffe in dieser Hinsicht als besonders wenig anfällig erwiesen.It is also known that through chromogenic development generated image dyes to varying degrees certain changes under the influence of environmental conditions suffer. What is particularly striking is what affects the effect of light. As is well known, bleaching the magenta dyes produced from pyrazoloazole couplers particularly strong while the out phenolic couplers produced cyan dyes in proven to be particularly unaffected in this regard.

Es hat nicht an Versuchen gefehlt, diesem Mangel durch besondere Maßnahmen abzuhelfen. Namentlich im Fall der Magentakuppler ist es gelungen, durch lichtstabilisierende Zusätze oder besondere Ausgestaltung der Kuppler zu verbesserter Lichtbeständigkeit zu gelangen. Als lichtstabilisierende Mittel eignen sich im wesentlichen phenolische Verbindungen, insbesondere Derivate des Hydrochinons, die entweder den Kupplern beigemischt oder in Form von Substituenten mit den Kupplermolekülen verknüpft werden (DE-B-1 547 803, DE-A-26 17 826, DE-A-29 52 511, JP-N 53 070 822, JP-N 54 070 830, JP-N 54 073 032). Die bekannten Lichtschutzmittel genügen jedoch noch nicht in jeder Hinsicht den an sie gestellten Anforderungen.There has been no shortage of attempts to overcome this lack to remedy special measures. Especially in the case of Magenta couplers have succeeded through light stabilizing Additions or special design of the couplers to achieve improved light resistance. As Light stabilizing agents are essentially suitable phenolic compounds, especially derivatives of Hydroquinones, either added to the couplers or linked in the form of substituents with the coupler molecules (DE-B-1 547 803, DE-A-26 17 826, DE-A-29 52 511, JP-N 53 070 822, JP-N 54 070 830, JP-N 54 073 032). The known light stabilizers are sufficient but not in all respects the one made to them Conditions.

Der Erfindung liegt die Aufgabe zugrunde, für fotografische Aufzeichnungsmaterialien neuartige Lichtschutzmittel anzugeben, insbesondere solche, die für die Verbesserung der Lichtstabilität der aus Magentakupplern, vom Typ der Pyrazoloazole erzeugten purpurfarbigen Bildfarbstoffe geeignet sind. The invention has for its object for photographic Novel light stabilizers specify, especially those for improvement the light stability of those from magenta couplers, of the pyrazoloazole type produced purple image dyes are suitable.

Gegenstand der Erfindung ist ein farbfotografisches Aufzeichnungsmaterial mit mindestens einer Silberhalogenidemulsionsschicht und einem dieser zugeordneten Farbkuppler, dadurch gekennzeichnet, daß es in einer Silberhalogenidemulsionsschicht oder in einer hierzu benachbarten nicht lichtempfindlichen Bindemittelschicht eine Kombination aus einem Pyrazoloazolkuppler und einer Verbindung der allgemeinen Formel I bzw. der Formen VI -X enthält:

Figure 00030001
Figure 00030002
Figure 00030003
Figure 00030004
Figure 00030005
Figure 00030006
worin bedeuten

R1
H, einen unter alkalischen Bedingungen abspaltbaren Rest, Alkyl oder Aryl;
R2
-OH, Alkyl, Aryl, Alkoxy oder
Figure 00030007
R3, R4, R5 und R6
H, -OH, -COOH, -SO3H, -SO2H, Alkyl, Aryl, Alkoxy, Alkylsulfonyl, Arylsulfonyl, gegebebenenfalls z.B. durch Alkyl und/oder Aryl substituiertes Sulfamoyl, Acylamino oder
Figure 00050001
worin mindestens einer der Reste R2, R3, R4, R5 und R6 ein Rest der Formel ist,
A
Alkylen mit 1-6 C-Atomen;
n
0 oder 1;
R7
H oder gegebenenfalls beispielsweise mit -COOH oder -SO3H substituiertes Alkyl, z.B. Carboxymethyl;
R8
durch eine Gruppe der Formel
Figure 00050003
worin R1 bis R7, A und n die bereits angegebenen Bedeutungen haben, ein- oder mehrfach substituiertes Alkyl, Cycloalkyl, oder Aryl mit 4 bis 20 C-Atomen, insbesondere 10 bis 18 C-Atomen; oder unsubstituiertes Alkyl, Cycloalkyl oder Aryl mit 4-20 C-Atomen
R1 und R3
können einen 5- oder 6-gliedrigen Ring bilden, wobei R2 = -OH oder Alkoxy;
R2 und R4
können einen 5- oder 6-gliedrigen carboxyclischen Ring bilden.
The invention relates to a color photographic recording material having at least one silver halide emulsion layer and a color coupler assigned to it, characterized in that it contains a combination of a pyrazoloazole coupler and a compound of the general formula I or forms VI in a silver halide emulsion layer or in a non-light-sensitive binder layer adjacent thereto -X contains:
Figure 00030001
Figure 00030002
Figure 00030003
Figure 00030004
Figure 00030005
Figure 00030006
in what mean
R 1
H, a radical which can be split off under alkaline conditions, alkyl or aryl;
R 2
-OH, alkyl, aryl, alkoxy or
Figure 00030007
R 3 , R 4 , R 5 and R 6
H, -OH, -COOH, -SO 3 H, -SO 2 H, alkyl, aryl, alkoxy, alkylsulfonyl, arylsulfonyl, optionally, for example, substituted by alkyl and / or aryl sulfamoyl, acylamino or
Figure 00050001
wherein at least one of the radicals R 2 , R 3 , R 4 , R 5 and R 6 is a radical of the formula is
A
Alkylene with 1-6 C atoms;
n
0 or 1;
R 7
H or optionally alkyl, for example substituted with -COOH or -SO 3 H, for example carboxymethyl;
R 8
through a group of formula
Figure 00050003
wherein R 1 to R 7 , A and n have the meanings already given, mono- or polysubstituted alkyl, cycloalkyl, or aryl having 4 to 20 C atoms, in particular 10 to 18 C atoms; or unsubstituted alkyl, cycloalkyl or aryl with 4-20 C atoms
R 1 and R 3
can form a 5- or 6-membered ring, wherein R 2 = -OH or alkoxy;
R 2 and R 4
can form a 5- or 6-membered carboxyclic ring.

Verbindungen der Formel (I), in denen R8 den Rest eines durch Polykondensation erzeugten Polymers bedeutet, sind aus EP-A-542 053 (Art 54(3) EPÜ) bekannt.Compounds of formula (I) in which R 8 represents the remainder of a polymer produced by polycondensation are known from EP-A-542 053 (Art 54 (3) EPC).

Ein durch R1 dargestellter unter alkalischen Bedingungen abspaltbarer Rest ist beispielsweise ein Acylrest, der sich ableitet von aliphatischen oder aromatischen Carbonsäuren; Beispiele für unter alkalischen Bedingungen abspaltbare Reste sind Acetyl, Dichloracetyl, Alkoxycarbonyl, Pyruvoyl.A radical which can be split off under alkaline conditions and is represented by R 1 is, for example, an acyl radical which is derived from aliphatic or aromatic carboxylic acids; Examples of radicals which can be split off under alkaline conditions are acetyl, dichloroacetyl, alkoxycarbonyl and pyruvoyl.

Ein durch R2 bis R6 dargestellter Alkylrest enthält, vorzugsweise 1 bis 4 C-Atome, Beispiele sind Methyl, Ethyl, Propyl, Isopropyl, Butyl, t-Butyl. Ein durch R2 bis R6 dargestellter Arylrest enthält 6 bis 10 C-Atome; Beispiele sind Phenyl und Napthyl. Die Alkyl- bzw. Arylreste können weiter substituiert sein, z.B. mit Halogen oder Alkyl. Ein durch R2 bis R6 dargestellter Alkoxyrest kann 1 bis 18 C-Atome enthalten Der Acylrest in einem durch R2 bis R6 dargestellten Acylaminorest leitet sich ab von aliphatischen oder aromatischen Carbon- oder Sulfonsäuren. An alkyl radical represented by R 2 to R 6 preferably contains 1 to 4 carbon atoms, examples are methyl, ethyl, propyl, isopropyl, butyl, t-butyl. An aryl radical represented by R 2 to R 6 contains 6 to 10 C atoms; Examples are phenyl and naphthyl. The alkyl or aryl radicals can be further substituted, for example with halogen or alkyl. An alkoxy radical represented by R 2 to R 6 can contain 1 to 18 carbon atoms. The acyl radical in an acylamino radical represented by R 2 to R 6 is derived from aliphatic or aromatic carboxylic or sulfonic acids.

Beispiele für erfindungsgemäße Stabilisierungsmittel sind im folgenden angegeben.

Figure 00070001
Figure 00070002
Figure 00070003
Figure 00070004
Figure 00080001
Figure 00080002
Figure 00080003
Figure 00080004
Figure 00090001
Figure 00090002
Figure 00090003
Figure 00090004
Figure 00100001
Figure 00100002
Figure 00100003
Figure 00100004
Figure 00100005
Figure 00110001
Figure 00110002
Examples of stabilizing agents according to the invention are given below.
Figure 00070001
Figure 00070002
Figure 00070003
Figure 00070004
Figure 00080001
Figure 00080002
Figure 00080003
Figure 00080004
Figure 00090001
Figure 00090002
Figure 00090003
Figure 00090004
Figure 00100001
Figure 00100002
Figure 00100003
Figure 00100004
Figure 00100005
Figure 00110001
Figure 00110002

Die Herstellung der erfindungsgemäßen Verbindungen kann auf einfache Weise durch Umsetzung von Aminen der Formel II mit monomeren Mono-, Di- oder Polyisocyanaten erfolgen.

Figure 00110003
The compounds of the invention can be prepared in a simple manner by reacting amines of the formula II with monomeric mono-, di- or polyisocyanates.
Figure 00110003

In Formel II haben R1, A und n die bei Formel I angegebene Bedeutung;

R2'
steht für -OH, Alkyl, Aryl, Alkoxy oder -(A)n-NH2;
R3', R4', R5' und R6'
stehen für H, -OH, -COOH, -SO3H, -SO2H, Alkyl, Aryl, Alkoxy, Alkylsulfonyl, Arylsulfonyl, gegebenenfalls durch Alkyl und/oder Aryl substituiertes Sulfamoyl, Acylamino oder -(A)n-NH2,
mit der Maßgabe, daß mindestens einer der Reste R2', R3', R4', R5' und R6' für -(A)n-NH2 steht.In formula II, R 1 , A and n have the meaning given for formula I;
R 2 '
represents -OH, alkyl, aryl, alkoxy or - (A) n -NH 2 ;
R 3 ' , R 4' , R 5 ' and R 6'
stand for H, -OH, -COOH, -SO 3 H, -SO 2 H, alkyl, aryl, alkoxy, alkylsulfonyl, arylsulfonyl, sulfamoyl optionally substituted by alkyl and / or aryl, acylamino or - (A) n -NH 2 ,
with the proviso that at least one of the radicals R 2 ' , R 3' , R 4 ' , R 5' and R 6 'is - (A) n -NH 2 .

Als Isocyanate zur Herstellung von Verbindungen der Formel I eignen sich alle aromatischen und aliphatischen Isocyanate mit 1 bis 4 Isocyanatgruppen wie z.B. 3-Chlorphenylisocyanat, Phenylisocyanat, 1,3-Phenylendiisocyanat, 1,5-Naphthylendiisocyanat, 4,4'-Diphenylmethandiisocyanat, die Isomere des Toluylendiisocyanat, gegebenenfalls eine Mischung, 2,4-Bis-(4-isocyanatobenzyl)-1-isocyanato-benzol, Tris-(4-isocyanatophenyl)-methan, 2-Ethyl-1,2,3-tris-(3-isocyanato-4-methyl-anilinocarbonyloxy)-propan, Tetrakis-(5-isocyanatopentylcarbonyloxy-methyl)-methan, vorzugsweise die aliphatischen Mono- und Diisocyanate wie Dodecylisocyanat, Cyclohexylisocyanat, Stearylisocyanat, Octylisocyanat, Hexadecylisocyanat, Hexan-1,6-diisocyanat, Dicyclohexylmethandiisocyanat, Cyclohexan-1,4-diisocyanat, Isophorondiisocyanat. As isocyanates for the preparation of compounds of the formula I are all aromatic and aliphatic Isocyanates with 1 to 4 isocyanate groups such as e.g. 3-chlorophenyl isocyanate, Phenyl isocyanate, 1,3-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, the isomers of tolylene diisocyanate, optionally a mixture, 2,4-bis (4-isocyanatobenzyl) -1-isocyanato-benzene, Tris (4-isocyanatophenyl) methane, 2-ethyl-1,2,3-tris (3-isocyanato-4-methyl-anilinocarbonyloxy) propane, Tetrakis (5-isocyanatopentylcarbonyloxymethyl) methane, preferably the aliphatic Mono- and diisocyanates such as dodecyl isocyanate, Cyclohexyl isocyanate, stearyl isocyanate, octyl isocyanate, Hexadecyl isocyanate, hexane-1,6-diisocyanate, dicyclohexylmethane diisocyanate, Cyclohexane-1,4-diisocyanate, Isophorone diisocyanate.

Herstellung von Verbindung S-1Preparation of compound S-1

Eine Lösung von 67,7 g 2-Hydroxy-5-methylanilin in 1000 ml Aceton wird bei 20°C langsam mit einer Lösung von 147,5 g Stearylisocyanat in 500 ml Aceton versetzt. Nach 6-stündigem Rühren destilliert man das Aceton am Rotationsverdampfer ab und löst den Rückstand in Essigester. Die organische Phase wird gründlich mit 10%iger Salzsäure gewaschen und über Na2SO4 getrocknet. Abdestillieren des Essigesters liefert 199 g S-1. Die Ausbeute beträgt 98 %.A solution of 67.7 g of 2-hydroxy-5-methylaniline in 1000 ml of acetone is slowly mixed with a solution of 147.5 g of stearyl isocyanate in 500 ml of acetone at 20 ° C. After stirring for 6 hours, the acetone is distilled off on a rotary evaporator and the residue is dissolved in ethyl acetate. The organic phase is washed thoroughly with 10% hydrochloric acid and dried over Na 2 SO 4 . Distilling off the ethyl acetate gives 199 g of S-1. The yield is 98%.

Die Verbindungen S-2 bis S-14 werden in analoger Weise aus den entsprechenden Verbindungen der Formel II und Isocyanaten hergestellt.The compounds S-2 to S-14 are made in an analogous manner from the corresponding compounds of formula II and Isocyanates produced.

Das erfindungsgemäße farbfotografische Aufzeichnungsmaterial enthält mindestens eine lichtempfindliche Silberhalogenidemulsionsschicht und vorzugsweise eine Abfolge mehrerer solcher lichtempfindlichen Silberhalogenidemulsionsschichten und gegebenenfalls weitere Hilfsschichten wie insbesondere Schutzschichten und zwischen den lichtempfindlichen Schichten angeordnete nicht lichtempfindliche Bindemittelschichten, wobei nach vorliegender Erfindung mindestens einer der vorhandenen lichtempfindlichen Silberhalogenidemulsionsschichten eine erfindungsgemäße Verbindung in Kombination mit einem Magentakuppler vom Typ der Pyrazoloazolkuppler, zugeordnet ist. The color photographic recording material according to the invention contains at least one photosensitive silver halide emulsion layer and preferably a sequence several such photosensitive silver halide emulsion layers and optionally further auxiliary layers such as in particular protective layers and between the photosensitive Layers of non-photosensitive Binder layers, according to the present invention at least one of the existing photosensitive Silver halide emulsion layers according to the invention Connection in combination with a magenta coupler of the pyrazoloazole coupler type is.

Die erfindungsgemäßen Verbindungen wirken dabei in erster Linie als Lichtstabilisierungsmittel, d.h. die aus dem Farbkuppler bei der chromogenen Entwicklung gebildeten Azomethinfarbstoffe weisen in Gegenwart der erfindungsgemäßen Verbindungen eine beträchtlich erhöhte Stabilität gegenüber der Einwirkung von Licht auf. Daneben übernehmen die erfindungsgemäßen Verbindungen teilweise auch die Funktion eines Ölbildners für den Farbkuppler, d.h. sie können zusammen mit anderen bekannten Ölbildnern als Kupplerlösungsmittel verwendet werden. Dabei machen die erfindungsgemäßen Verbindungen vorzugsweise 10 bis 60 Gew.-% der gesamten Ölbildnermenge in der jeweiligen Schicht aus. Der Umstand, daß weitere Ölbildner gegebenenfalls nur in geringerer Menge erforderlich sind, wirkt sich günstig auf die Schichtbelastung und/oder die Gesamtschichtdicke der erfindungsgemäßen Aufzeichnungsmaterialien aus.The compounds of the invention act in primarily as a light stabilizer, i.e. the formed from the color coupler in the chromogenic development Azomethine dyes exhibit in the presence of Compounds according to the invention increased considerably Stability against exposure to light. Besides partially take over the compounds according to the invention also the function of an oil generator for the color coupler, i.e. they can be known along with others Oil formers can be used as coupler solvents. The compounds according to the invention preferably do this 10 to 60 wt .-% of the total amount of oil in the respective layer. The fact that more Oil formers may only be required in smaller quantities are beneficial for shift load and / or the total layer thickness of the invention Recording materials.

Die erfindungsgemäßen Verbindungen fallen bei der Herstellung (Umsetzung der aktive Wasserstoffatome enthaltenden Verbindungen mit Isocyanaten) meist als niedrigschmelzende Feststoffe an und werden als Lösung in aprotischen (hydrophoben) Lösungsmitteln, z.B. Ethylacetat, bei der Einarbeitung in die Gießlösung für die betreffende Schicht, gegebenenfalls zusammen mit dem jeweiligen Farbkuppler, eingesetzt. Die Einarbeitung erfolgt in der üblichen Weise, wobei gegebenenfalls weitere Hilfslösungsmittel und/oder hochsiedende Kupplerlösungsmittel, sogenannte Ölbildner, verwendet werden können. The compounds of the invention fall in the manufacture (Implementation of active hydrogen atoms Compounds with isocyanates) mostly as low-melting Solids on and are as a solution in aprotic (hydrophobic) solvents, e.g. Ethyl acetate, during incorporation into the casting solution for the concerned Layer, if necessary together with the respective Color coupler used. The familiarization takes place in the usual way, if necessary further Auxiliary solvents and / or high-boiling coupler solvents, so-called oil formers can be used.

Das als lichtempfindlicher Bestandteil in dem erfindungsgemäßen fotografischen Aufzeichnungsmaterial befindliche Silberhalogenid kann als Halogenid Chlorid, Bromid oder Iodid bzw. Mischungen davon enthalten. Beispielsweise kann der Halogenidanteil wenigstens einer Schicht zu 0 bis 15 mol-% aus Iodid, zu 0 bis 100 mol-% aus Chlorid und zu 0 bis 100 mol-% aus Bromid bestehen.That as a photosensitive component in the invention photographic recording material Silver halide can be used as halide chloride, Contain bromide or iodide or mixtures thereof. For example the halide content can be at least one 0 to 15 mol% layer of iodide, 0 to 100 mol% consist of chloride and 0 to 100 mol% of bromide.

Im Falle von Farbnegativ- und Farbumkehrfilmen werden üblicherweise Silberbromidiodidemulsionen, im Falle von Farbnegativ-und Farbumkehrpapier üblicherweise Silberchloridbromidemulsionen mit hohem Chloridanteil bis zu reinen Silberchloridemulsionen verwendet. Es kann sich um überwiegend kompakte Kristalle handeln, die z.B. regular kubisch oder oktaedrisch sind oder Übergangsformen aufweisen können. Vorzugsweise können aber auch plättchenförmige Kristalle vorliegen, deren durchschnittliches Verhältnis von Durchmesser zu Dicke bevorzugt wenigstens 5:1 ist, wobei der Durchmesser eines Kornes definiert ist als der Durchmesser eines Kreises mit einem Kreisinhalt entsprechend der projizierten Fläche des Kornes. Die Schichten können aber auch tafelförmige Silberhalogenidkristalle aufweisen, bei denen das Verhältnis von Durchmesser zu Dicke wesentlich größer als 5:1 ist, z.B. 12:1 bis 30:1.In the case of color negative and color reversal films usually silver bromide iodide emulsions, in the case of Color negative and color reversal paper usually silver chloride bromide emulsions with high chloride content up to pure silver chloride emulsions are used. It can are mainly compact crystals, e.g. are regular cubic or octahedral or transitional forms can have. But preferably also platelet-shaped crystals are present, their average Ratio of diameter to thickness is preferably at least 5: 1, the diameter a grain is defined as the diameter of a Circle with a circle content corresponding to the projected Area of the grain. The layers can also have tabular silver halide crystals, where the ratio of diameter to thickness is significantly larger than 5: 1, e.g. 12: 1 to 30: 1.

Die Silberhalogenidkörner können auch einen mehrfach geschichteten Kornaufbau aufweisen, im einfachsten Fall mit einem inneren und einem äußeren Kornbereich (core/shell), wobei die Halogenidzusammensetzung und/oder sonstige Modifizierungen, wie z.B. Dotierungen der einzelnen Kornbereiche unterschiedlich sind. Die mittlere Korngröße der Emulsionen liegt vorzugsweise zwischen 0,2 µm und 2,0 µm, die Korngrößenverteilung kann sowohl homo- als auch heterodispers sein. Homodisperse Korngröβenverteilung bedeutet, daß 95 % der Körner nicht mehr als ± 30% von der mittleren Korngröße abweichen. Die Emulsionen können neben dem Silberhalogenid auch andere Silbersalze, z.B. organische Silbersalze enthalten, wie etwa Silberbenztriazolat oder Silberbehenat.The silver halide grains can also be multi-layered Have grain structure, in the simplest case with an inner and an outer grain area (core / shell), wherein the halide composition and / or other modifications, such as Endowments of the individual Grain areas are different. The middle The grain size of the emulsions is preferably between 0.2 µm and 2.0 µm, the grain size distribution can be both be homo- and heterodisperse. Homodisperse grain size distribution means 95% of the grains are not deviate more than ± 30% from the average grain size. In addition to the silver halide, the emulsions can also other silver salts, e.g. contain organic silver salts, such as silver benzotriazolate or silver behenate.

Es können zwei oder mehrere Arten von Silberhalogenidemulsionen, die getrennt hergestellt werden, als Mischung verwendet werden.Two or more types of silver halide emulsions, which are made separately, as a mixture be used.

Die Emulsionen können in der üblichen Weise chemisch und oder spektral sensibilisiert sein; sie können auch durch geeignete Zusätze stabilisiert sein. Geeignete chemische Sensibilisatoren, spektrale Sensibilisierungsfarbstoffe und Stabilisatoren sind beispielsweise in Research Disclosure 17643 (Dezember 1978) beschrieben; verwiesen wird insbesondere auf die Kapitel III, IV und VI.The emulsions can be chemically and in the usual way or be spectrally sensitized; you can also by suitable additives must be stabilized. Suitable chemical Sensitizers, spectral sensitizing dyes and stabilizers are, for example, in Research Disclosure 17643 (December 1978); referred special attention is paid to chapters III, IV and VI.

Das erfindungsgemäße farbfotografische Aufzeichnungsmaterial enthält bevorzugt außer der die erfindungsgemäße Kombination aus Pyrazoloazolkuppler und Verbindung der Formel I enthaltenden, im Normalfall grünsensibilisierten Silberhalogenidemulsionsschicht weitere Silberhalogenidemulsionsschichten für die Aufzeichnung von Licht der anderen Spektralbereiche Rot und Blau. Zu diesem Zweck sind die lichtempfindlichen Schichten in bekannter Weise durch geeignete Sensibilisierungsfarbstoffe spektral sensibilisiert.The color photographic recording material according to the invention contains preferably the one according to the invention Combination of pyrazoloazole coupler and connection of the Formula I containing, normally green-sensitized Silver halide emulsion layer further silver halide emulsion layers for recording light of the other spectral ranges red and blue. To this The purpose of the photosensitive layers is known Spectrally by suitable sensitizing dyes sensitized.

Eine Übersicht über die als Spektralsensibilisatoren geeigneten Polymethinfarbstoffe, deren geeignete Kombinationen und supersensibilisierend wirkenden Kombinationen enthält Research Disclosure 17643 (Dez. 1978),Kapitel IV.An overview of those suitable as spectral sensitizers Polymethine dyes, their suitable combinations and super-sensitizing combinations contains Research Disclosure 17643 (Dec. 1978), chapter IV.

Als Grünsensibilisatoren sind beispielsweise geeignet 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.Suitable green sensitizers are, for example 9-ethyl carbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzthiazole as basic end groups as well as benzimidazocarbocyanines, which also may be further substituted and also at least a sulfoalkyl group on heterocyclic nitrogen must contain.

Als Beispiele seien, insbesondere für Negativ- und Umkehrfilm, die nachfolgend aufgeführen Grünsensibilisatoren GS genannt, die jeweils einzeln oder in Kombination miteinander eingesetzt werden können, z.B. GS-1 und GS-2.

Figure 00170001

GS-1:
R1, R3, R7, R9 = H; R2 = Phenyl;
Figure 00170002
R5 = -C2H5; R6 = -SO3 ⊖;
R8 = Cl; m = 2; n = 3; X, Y = O;
GS-2:
R1, R2, R7, R8 = Cl; R3, R5, R6, R9 = H;
Figure 00180001
m, n = 2; X, Y = N-C2H5;
GS-3:
R1, R7 = H; R2, R3 sowie R8, R9 zusammen
-CH=CH-CH=CH-; R4 = SO3 ⊖ Na⊕; R5 = C2H5;
R6 = SO3 ⊖; m, n = 3; X, Y = O;
GS-4:
R1, R3, R4, R7, R8, R9 = H; R2 = -OCH3; R5 = -C2H5;
R6 = SO3 ⊖; m = 2; n = 4; X = O; Y = S;
Examples include, in particular for negative and reverse film, the green sensitizers GS listed below, which can be used individually or in combination with one another, for example GS-1 and GS-2.
Figure 00170001
GS-1:
R 1 , R 3 , R 7 , R 9 = H; R 2 = phenyl;
Figure 00170002
R 5 = -C 2 H 5 ; R 6 = -SO 3 ⊖ ;
R 8 = Cl; m = 2; n = 3; X, Y = O;
GS-2:
R 1 , R 2 , R 7 , R 8 = Cl; R 3 , R 5 , R 6 , R 9 = H;
Figure 00180001
m, n = 2; X, Y = NC 2 H 5 ;
GS-3:
R 1 , R 7 = H; R 2 , R 3 and R 8 , R 9 together
-CH = CH-CH = CH-; R 4 = SO 3 ⊖ Na ⊕ ; R 5 = C 2 H 5 ;
R 6 = SO 3 ⊖ ; m, n = 3; X, Y = O;
GS-4:
R 1 , R 3 , R 4 , R 7 , R 8 , R 9 = H; R 2 = -OCH 3 ; R 5 = -C 2 H 5 ;
R 6 = SO 3 ⊖ ; m = 2; n = 4; X = O; Y = S;

Jede der genannten lichtempfindlichen Schichten kann aus einer einzigen Schicht bestehen oder in bekannter Weise, z.B. bei der sogenannten Doppelschichtanordnung, auch zwei oder auch mehr Silberhalogenidemulsionsteilschichten umfassen (DE-C-1 121 470). Bei Negativfilmen sind üblicherweise rotempfindliche Silberhalogenidemulsionsschichten dem Schichtträger näher angeordnet als grünempfindliche Silberhalogenidemulsionsschichten und diese wiederum näher als blauempfindliche, wobei sich im allgemeinen zwischen grünempfindlichen Schichten und blauempfindlichen Schichten eine nicht lichtempfindliche gelbe Filterschicht befindet. Es sind aber auch andere Anordnungen denkbar, z.B. bei Colorpapier. Zwischen Schichten unterschiedlicher Spektralempfindlichkeit ist in der Regel eine nicht lichtempfindliche Zwischenschicht angeordnet, die Mittel zur Unterbindung der Fehldiffusion von Entwickleroxidationsprodukten enthalten kann. Falls mehrere Silberhalogenidemulsionsschichten gleicher Spektralempfindlichkeit vorhanden sind, können diese einander unmittelbar benachbart sein oder so angeordnet sein, daß sich zwischen ihnen eine lichtempfindliche Schicht mit anderer Spektralempfindlichkeit befindet (DE-A-1 958 709, DE-A-2 530 645, DE-A-2 622 922).Each of the light-sensitive layers mentioned can consist of consist of a single layer or in a known manner, e.g. with the so-called double layer arrangement, too two or more silver halide emulsion partial layers include (DE-C-1 121 470). With negative films usually red sensitive silver halide emulsion layers arranged closer to the substrate than those sensitive to green Silver halide emulsion layers and these again closer than blue-sensitive, which is generally between green sensitive layers and blue sensitive Layers a non-photosensitive yellow filter layer. But there are also others Arrangements conceivable, e.g. for color paper. Between Layers of different spectral sensitivity usually a non-photosensitive intermediate layer arranged, the means for preventing the Incorrect diffusion of developer oxidation products included can. If multiple layers of silver halide emulsion have the same spectral sensitivity, can these be directly adjacent to each other or be arranged so that there is a light-sensitive between them Layer with a different spectral sensitivity (DE-A-1 958 709, DE-A-2 530 645, DE-A-2 622 922).

Erfindungsgemäße farbfotografische Aufzeichnungsmaterialien enthalten üblicherweise in räumlicher und spektraler Zuordnung zu den Silberhalogenidemulsionsschichten unterschiedlicher Spektralempfindlichkeit Farbkuppler zur Erzeugung der unterschiedlichen Teilfarbenbilder Cyan, Magenta und Gelb, wobei die erfindungsgemäßen Verbindungen zusammen mit dem jeweiligen Farbkuppler bevorzugt einer grünempfindlichen Silberhalogenidemulsionsschicht zugeordnet sind.Color photographic recording materials according to the invention usually contain in spatial and spectral Assignment to the silver halide emulsion layers different spectral sensitivity color coupler to generate the different part color images Cyan, magenta and yellow, with the invention Connections together with the respective color coupler preferably a green-sensitive silver halide emulsion layer assigned.

Unter räumlicher Zuordnung ist dabei zu verstehen, daß der Farbkuppler sich in einer solchen räumlichen Beziehung zu der Silberhalogenidemulsionsschicht befindet, daß eine Wechselwirkung zwischen ihnen möglich ist, die eine bildgemäße Übereinstimmung zwischen dem bei der Entwicklung gebildeten Silberbild und dem aus dem Farbkuppler erzeugten Farbbild zuläßt. Dies wird in der Regel dadurch erreicht, daß der Farbkuppler in der Silberhalogenidemulsionsschicht selbst enthalten ist oder in einer hierzu benachbarten gegebenenfalls nichtlichtempfindlichen Bindemittelschicht.Spatial assignment is understood to mean that the color coupler is in such a spatial Relationship to the silver halide emulsion layer finds that an interaction between them is possible which is a visual match between the silver picture formed during development and the allows the color coupler generated color image. This is in usually achieved in that the color coupler in the Silver halide emulsion layer itself is included or in a neighboring one if necessary non-photosensitive binder layer.

Unter spektraler Zuordnung ist zu verstehen, daß die Spektralempfindlichkeit jeder der lichtempfindlichen Silberhalogenidemulsionsschichten und die Farbe des aus dem jeweils räumlich zugeordneten Farbkuppler erzeugten Teilfarbenbildes in einer bestimmten Beziehung zueinander stehen, wobei jeder der Spektralempfindlichkeiten (Rot, Grün, Blau) eine andere Farbe des betreffenden Teilfarbenbildes (im allgemeinen z.B. die Farben Cyan, Purpur bzw. Gelb in dieser Reihenfolge) zugeordnet ist.Spectral assignment means that the Spectral sensitivity of each of the photosensitive Silver halide emulsion layers and the color of the the spatially assigned color coupler Partial color image in a certain relationship to each other stand, each of the spectral sensitivities (Red, green, blue) another color of the concerned Partial color image (generally e.g. the colors cyan, Purple or yellow in this order).

Jeder der unterschiedlich spektral sensibilisierten Silberhalogenidemulsionsschichten kann ein oder können auch mehrere Farbkupper zugeordnet sein. Wenn mehrere Silberhalogenidemulsionsschichten gleicher Spektralempfindlichkeit vorhanden sind, kann jeder von ihnen einen Farbkuppler enthalten, wobei diese Farbkuppler nicht notwendigerweise identisch zu sein brauchen. Sie sollen lediglich bei der Farbentwicklung wenigstens anähernd die gleiche Farbe ergeben, normalerweise eine Farbe, die komplementär ist zu der Farbe des Lichtes, für das die betreffenden Silberhalogenidemulsionsschichten überwiegend empfindlich sind. Each of the different spectrally sensitized silver halide emulsion layers can one or can also several color couplers can be assigned. When multiple silver halide emulsion layers same spectral sensitivity are present, each of them can be one Color couplers included, but these color couplers are not necessarily need to be identical. You should only at least approximately in the color development result in the same color, usually a color that is complementary to the color of the light for which the silver halide emulsion layers concerned predominantly are sensitive.

Die erfindungsgemäß verwendeten Farbkuppler zur Erzeugung des Teilfarbenbildes Magenta sind Kuppler vom Typ der Pyrazoloazole; geeignete Beispiele hierfür sind:

Figure 00210001

M-1:
Figure 00210002
R2 = -CH3
M-2:
Figure 00210003
R2 = -CH3
M-3:
Figure 00210004
R2 = -C4H9-t
M-4:
Figure 00210005
R2 = -CH3
M-5:
Figure 00210006
R2 = -CH3
M-6:
Figure 00220001
R2 = -CH3
M-7:
Figure 00220002
R2 = -CH3
Figure 00220003
M-8:
Figure 00220004
R2 = -CH3
M-9:
Figure 00220005
R2 = -CH3
M-10:
Figure 00230001
R2 = -C3H7-i
M-11:
Figure 00230002
R2 = -CH3
M-12:
R1 = -C3H7-i
Figure 00230003
M-13:
Figure 00230004
The color couplers used according to the invention for producing the partial color image magenta are couplers of the pyrazoloazole type; suitable examples are:
Figure 00210001
M-1:
Figure 00210002
R 2 = -CH 3
M-2:
Figure 00210003
R 2 = -CH 3
M-3:
Figure 00210004
R 2 = -C 4 H 9 -t
M-4:
Figure 00210005
R 2 = -CH 3
M-5:
Figure 00210006
R 2 = -CH 3
M-6:
Figure 00220001
R 2 = -CH 3
M-7:
Figure 00220002
R 2 = -CH 3
Figure 00220003
M-8:
Figure 00220004
R 2 = -CH 3
M-9:
Figure 00220005
R 2 = -CH 3
M-10:
Figure 00230001
R 2 = -C 3 H 7 -i
M-11:
Figure 00230002
R 2 = -CH 3
M-12:
R 1 = -C 3 H 7 -i
Figure 00230003
M-13:
Figure 00230004

Pyrazoloazolkuppler der allgemeinen Formeln IV und V

Figure 00230005
sind beispielsweise in US-A-3 725 067 und US-A-4 540 654 beschrieben. In den Formeln IV und V bedeuten:

X
H oder eine unter den Bedingungen der Farbentwicklung freisetzbare Gruppe;
R1, R2, H,
Alkyl, Aralkyl, Aryl, Alkoxy, Aroxy, Alkylthio, Arylthio, Amino, Anilino, Acylamino, Cyano, Alkoxycarbonyl, Carbamoyl, Sulfamoyl, wobei diese Reste weiter substituiert sein können.
Pyrazoloazole couplers of the general formulas IV and V
Figure 00230005
are described, for example, in US-A-3,725,067 and US-A-4,540,654. In formulas IV and V:
X
H or a group releasable under the conditions of color development;
R 1 , R 2 , H,
Alkyl, aralkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, carbamoyl, sulfamoyl, where these radicals can be further substituted.

Außer der erfindungsgemäß verwendeten Kombination aus Pyrazoloazolkuppler und Verbindung der Formel I kann das erfindungsgemäße Aufzeichnungsmaterial in der betreffenden Schicht weitere Kuppler enthalten, insbesondere Magentakuppler, die nicht der Klasse der Pyrazoloazole angehören müssen.In addition to the combination of Pyrazoloazole couplers and compounds of the formula I can do this recording material according to the invention in the relevant Layer contain further couplers, especially magenta couplers, that do not belong to the pyrazoloazole class have to.

Bei diesen weiteren Kupplern kann es sich um 4-Äquivalentkuppler, aber auch um 2-Äquivalentkuppler handeln. Letztere leiten sich von den 4-Äquivalentkupplern dadurch ab, daß sie in der Kupplungsstelle einen Substituenten enthalten, der bei der Kupplung abgespalten wird. Zu den 2-Äquivalentkupplern sind solche zu rechnen, die farblos sind, wie auch solche, die eine intensive Eigenfarbe aufweisen, die bei der Farbkupplung verschwindet bzw. durch die Farbe des erzeugten Bildfarbstoffes ersetzt wird (Maskenkuppler), aber auch die Weißkuppler, die bei Reaktion mit Farbentwickleroxidationsprodukten im wesentlichen farblose Produkte ergeben. Zu den 2-Äquivalentkupplern sind ferner solche Kuppler zu rechnen, die in der Kupplungsstelle einen abspaltbaren Rest enthalten, der bei Reaktion mit Farbentwickleroxidationsprodukten in Freiheit gesetzt wird und dabei entweder direkt oder nachdem aus dem primär abgespaltenen Rest eine oder mehrere weitere Gruppen abgespalten worden sind (z.B. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), eine bestimmte erwünschte fotografische Wirksamkeit entfaltet, z.B. als Entwicklungsinhibitor oder -accelerator. Beispiele für solche 2-Äquivalentkuppler sind die bekannten DIR-Kuppler wie auch DAR-bzw. FAR-Kuppler.These other couplers can be 4 equivalent couplers, but also act as 2-equivalent couplers. The latter are derived from the 4 equivalent couplers that they have a substituent in the coupling site included, which split off at the clutch becomes. The 2-equivalent couplers include those which are colorless, as well as those which are intense Have their own color in the color coupling disappears or due to the color of the image dye produced is replaced (mask coupler), but also the White couplers that react with color developer oxidation products essentially colorless products surrender. In addition to the 2-equivalent couplers, there are also such Coupler to be expected in the coupling point releasable residue contained in the reaction with color developer oxidation products is set free and either directly or after from the primary split off remainder one or more 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 specific one desired photographic effectiveness unfolds, e.g. as a development inhibitor or accelerator. Examples the known ones for such 2-equivalent couplers DIR couplers as well as DAR or. FAR coupler.

Die verwendeten Kuppler, insbesondere die erfindungsgemäß verwendeten Magentakuppler vom Typ der Pyrazoloazole, beispielsweise der Formeln IV und V, können auch in polymerer Form, z.B. als Polymerisatlatex zur Anwendung gelangen.The couplers used, especially those according to the invention used pyrazoloazole type magenta couplers, for example of the formulas IV and V, can also in polymeric form, e.g. as a polymer latex for use reach.

Hochmolekulare Farbkuppler sind beispielsweise beschrieben 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. 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.

Die hochmolekularen Farbkuppler werden in der Regel durch Polymerisation von ethylenisch ungesättigten monomeren Farbkupplern hergestellt.The high molecular color couplers are usually by polymerizing ethylenically unsaturated monomers Color couplers manufactured.

Die verwendeten Farbkuppler können auch solche sein, die Farbstoffe mit einer schwachen bzw. eingeschränkten Beweglichkeit liefern.The color couplers used can also be those that Dyes with poor or limited mobility deliver.

Unter einer schwachen bzw. eingeschränkten Beweglichkeit ist eine Beweglichkeit zu verstehen, die so bemessen ist, daß die Konturen der bei der chromogenen Entwicklung gebildeten diskreten Farbstoffflecken verlaufen und ineinander verschmiert werden. Dieses Ausmaß der Beweglichkeit ist einerseits zu unterscheiden von dem üblichen Fall der völligen Unbeweglichkeit in fotografischen Schichten, der in herkömmlichen fotografischen Aufzeichnungsmaterialien für die Farbkuppler bzw. die daraus hergestellten Farbstoffe angestrebt wird, um eine möglichst hohe Schärfe zu erzielen, und andererseits von dem Fall der völligen Beweglichkeit der Farbstoffe, der beispielsweise bei Farbdiffusionsverfahren angestrebt wird. Die letztgegenannten Farbstoffe verfügen meist über mindestens eine Gruppe, die sie im alkalischen Medium löslich machen. Das Ausmaß der erfindungsgemäß angestrebten schwachen Beweglichkeit kann gesteuert werden durch Variation von Substituenten, um beispielsweise die Löslichkeit im organischen Medium des Ölbildners oder die Affinität zur Bindemittelmatrix in gezielter Weise zu beeinflussen.Under poor or restricted mobility is to be understood a mobility that is measured in this way is that the contours of chromogenic development formed discrete dye stains run and are smeared into each other. This degree of mobility is to be distinguished on the one hand from the usual Case of complete immobility in photographic Layers used in conventional photographic materials for the color couplers or from them Dyes produced is aimed at a possible to achieve high sharpness, and on the other hand by the case of complete mobility of the dyes, the for example in color diffusion processes becomes. The latter dyes usually have about at least one group they are in alkaline Make medium soluble. The extent of the invention aimed weak mobility can be controlled are made by varying substituents, for example the solubility in the organic medium of the oil former or the affinity for the binder matrix in a more targeted manner Way to influence.

Über die genannten Bestandteile hinaus kann das farbfotografische Aufzeichnungsmaterial der vorliegenden Erfindung weitere Zusätze enthalten, wie zum Beispiel Antioxidantien, farbstoffstabilisierende Mittel und Mittel zur Beeinflussung der mechanischen und elektrostatischen Eigenschaften sowie UV-Absorber. Vorteilhaft werden solche zusätzlichen Verbindungen kombiniert mit den erfindungsgemäßen Verbindungen, d.h. in derselben Bindungsmittelschicht oder in zueinander benachbarten Bindemittelschichten verwendet.In addition to the components mentioned, the color photographic Recording material of the present Invention contain other additives, such as Antioxidants, dye stabilizers and Means for influencing the mechanical and electrostatic Properties as well as UV absorbers. Advantageous such additional connections are combined with the compounds of the invention, i.e. in the same Binding agent layer or in adjacent to each other Binder layers used.

Zusätze zur Verbesserung der Farbstoff-, Kuppler- und Weißenstabilität sowie zur Verringerung des Farbschleiers (Research Disclosure 17 643 (Dez. 1978), Kapitel VII) können den folgenden chemischen Stoffklassen angehören: Hydrochinone, 6-Hydroxychromane, 5-Hydroxycumarane, Spirochromane, Spiroindane, p-Alkoxyphenole, sterische gehinderte Phenole, Gallussäurederivate, Methylendioxybenzole, Aminophenole, sterisch gehinderte Amine, Derivate mit veresterten oder verätherten phenolischen Hydroxylgruppen, Metallkomplexe.Additives to improve the dye, coupler and White 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, steric hindered phenols, gallic acid derivatives, Methylenedioxybenzenes, aminophenols, sterically hindered Amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.

Verbindungen, die sowohl eine sterisch gehinderte Amin-Partialstruktur als auch eine sterisch gehinderte Phenol-Partialstruktur in einem Molekül aufweisen (US-A-4 268 593), sind besonders wirksam zur Verhinderung der Beeinträchtigung von gelben Farbbildern als Folge der Entwicklung von Wärme, Feuchtigkeit und Licht. Um die Beeinträchtigung von purpurroten Farbbildern, insbesondere ihre Beeinträchtigung als Folge der Einwirkung von Licht, zu verhindern, sind Spiroindane (JP-A-159 644/81) und Chromane, die durch Hydrochinondiether oder -monoether substituiert sind (JP-A-89 835/80) besonders wirksam.Compounds that have both a sterically hindered amine partial structure as well as a sterically hindered Have phenol partial structure in one molecule (US-A-4 268 593), are particularly effective in preventing the Impairment of yellow color images as a result of Development of heat, moisture and light. To the Impairment of purple color images, in particular their impairment as a result of exposure to prevent light are spiroindanes (JP-A-159 644/81) and chromane by hydroquinone diether or monoethers are substituted (JP-A-89 835/80) particularly effective.

Beispiele besonders geeigneter Verbindungen sind:

Figure 00290001
Figure 00290002
R = -C8H17-t ; R1 = -CH3
R = -C8H17 ; R1 = -C3H7-i
Figure 00290003
Figure 00290004
R, R1 = -C4H9-t
R, R1 = -C5H11-t
Figure 00290005
Figure 00290006
Figure 00300001
Figure 00300002
Figure 00300003
UV-Licht absorbierende Verbindungen sollen einerseits die Bildfarbstoffe vor dem Ausbleichen durch UV-reiches Tageslicht schützen und andererseits als Filterfarbstoffe das UV-Licht im Tageslicht bei der Belichtung absorbieren und so die Farbwiedergabe eines Films verbessern. Üblicherweise werden für die beiden Aufgaben Verbindungen unterschiedlicher Struktur eingesetzt. Beispiele sind arylsubstituierte Benzotriazolverbindungen (US-A-3 533 794), 4-Thiazolidonverbindungen (US-A-3 314 794 und 3 352 681), Benzophenonverbindungen (JP-A-2784/71), Zimtsäureesterverbindungen (US-A-3 705 805 und 3 707 375), Butadienverbindungen (US-A-4 045 229) oder Benzoxazolverbindungen (US-A-3 700 455). Examples of particularly suitable compounds are:
Figure 00290001
Figure 00290002
R = -C 8 H 17 -t; R 1 = -CH 3
R = -C 8 H 17 ; R 1 = -C 3 H 7 -i
Figure 00290003
Figure 00290004
R, R 1 = -C 4 H 9 -t
R, R 1 = -C 5 H 11 -t
Figure 00290005
Figure 00290006
Figure 00300001
Figure 00300002
Figure 00300003
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).

Beispiele besonders geeigneter Verbindungen sind

Figure 00310001
R, R1 = H; R2 = -C4H9-t
R = H;    R1, R2 = -C4H9-t
R = H;    R1, R2 = -C5H11-t
R = H;    R1 = -C4H9-s;    R2 = -C4H9-t
R = Cl;    R1 = -C4H9-t;    R2 = -C4H9-s
R = Cl;    R1,R2 = -C4H9-t
R = Cl;    R1 = -C4H9-t;    R2 = -CH2-CH2-COOC8H17
R = H;    R = -C12H25-i;    R2 = -CH3
R, R1, R2 = -C4H9-t
Figure 00310002
R1, R2 = -C6H13 ;    R3, R4 = -CN R1, R2 = -C2H5;
Figure 00320001
R4 = -CO-OC8H17
R1, R2 = -C2H5;
Figure 00320002
R4 = -COO-C12H25
R1, R2 = -CH2=CH-CH2; R3, R4 = -CN
Figure 00320003
R1, R2 = H; R3 = -CN; R4 = -CO-NHC12H25
R1, R2 = -CH3; R3 = -CN; R4 = -CO-NHC12H25
Figure 00320004
Examples of particularly suitable compounds are
Figure 00310001
R, R 1 = H; R 2 = -C 4 H 9 -t
R = H; R 1 , R 2 = -C 4 H 9 -t
R = H; R 1 , R 2 = -C 5 H 11 -t
R = H; R 1 = -C 4 H 9 -s; R 2 = -C 4 H 9 -t
R = Cl; R 1 = -C 4 H 9 -t; R 2 = -C 4 H 9 -s
R = Cl; R 1 , R 2 = -C 4 H 9 -t
R = Cl; R 1 = -C 4 H 9 -t; R 2 = -CH 2 -CH 2 -COOC 8 H 17
R = H; R = -C 12 H 25 -i; R 2 = -CH 3
R, R 1 , R 2 = -C 4 H 9 -t
Figure 00310002
R 1 , R 2 = -C 6 H 13 ; R 3 , R 4 = -CN R 1 , R 2 = -C 2 H 5 ;
Figure 00320001
R 4 = -CO-OC 8 H 17
R 1 , R 2 = -C 2 H 5 ;
Figure 00320002
R 4 = -COO-C 12 H 25
R 1 , R 2 = -CH 2 = CH-CH 2 ; R 3 , R 4 = -CN
Figure 00320003
R 1 , R 2 = H; R 3 = -CN; R 4 = -CO-NHC 12 H 25
R 1 , R 2 = -CH 3 ; R 3 = -CN; R 4 = -CO-NHC 12 H 25
Figure 00320004

Es können auch ultraviolettabsorbierende Kuppler (wie Blaugrünkuppler des α-Naphtholtyps) und ultraviolettabsorbierende Polymere verwendet werden. Diese Ultraviolettabsorbentien können durch Beizen in einer speziellen Schicht fixiert sein. Ultraviolet absorbing couplers (such as Cyan couplers of the α-naphthol type) and ultraviolet absorbing Polymers are used. These ultraviolet absorbents can be done by pickling in a special Layer fixed.

Zur Herstellung farbfotografischer Bilder wird das erfindungsgemäße farbfotografische Aufzeichnungsmaterial, das zugeordnet zu mindestens einer Silberhalogenidemulsionsschicht einen Farbkuppler und eine Verbindung der Formel I enthält, mit einer Farbentwicklerverbindung entwickelt. Als Farbentwicklerverbindung lassen sich sämtliche Entwicklerverbindungen verwenden, die die Fähigkeit haben in Form ihres Oxidationsproduktes mit Farbkupplern zu Azomethinfarbstoffen zu reagieren. Geeignete Farbentwicklerverbindungen sind aromatische mindestens eine primäre Aminogruppe enthaltende Verbindungen vom p-Phenylendiamintyp, beispielsweise N,N-Dialkyl-p-phenylendiamine, wie N,N-Diethyl-p-phenylendiamin, 1-(N-ethyl-N-methylsulfonamidoethyl)-3-meLhyl-p-phenylendiamin, 1-(N-ethyl-N-hydroxyethyl-3-methyl-p-phenylendiamin und 1-(N-ethyl-N-methoxyethyl)-3-methyl-p-phenylendiamin.The invention is used to produce color photographic images color photographic recording material, assigned to at least one silver halide emulsion layer a color coupler and a connection of the Formula I contains, with a color developer compound developed. Can be used as a color developer compound use all developer connections that the Have ability in the form of their oxidation product Color couplers react to azomethine dyes. Suitable Color developer compounds are aromatic at least compounds containing a primary amino group of the p-phenylenediamine type, for example N, N-dialkyl-p-phenylenediamine, such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3-methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl-3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.

Weitere brauchbare Farbentwickler sind beispielsweise beschrieben in J. Amer. Chem. Soc. 73, 3100 (1951) und in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, Seiten 545 ff.Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3100 (1951) and in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, pages 545 ff.

Nach der Farbentwicklung wird das Material üblicherweise gebleicht und fixiert. Bleichung und Fixierung können getrennt voneinander oder auch zusammen durchgeführt werden. Als Bleichmittel können die üblichen Verbindungen verwendet werden, z.B. Fe3+-Salze und Fe3+-Komplexsalze wie Ferricyanide, Dichromate, wasserlösliche Kobaltkomplexe usw. Besonders bevorzugt sind Eisen-III-Komplexe von Aminopolycarbonsäuren insbesondere z.B. Ethylendiamintetraessigsäure, N-Hydroxyethylethylendiamintriessigsäure, Alkyliminodicarbonsäuren und von entsprechenden Phosphonsäuren. Geeignet als Bleichmittel sind weiterhin Persulfate. After color development, the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together. The usual compounds can be used as bleaching agents, for example Fe 3+ salts and Fe 3+ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes, etc. Particularly preferred are iron III complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediamine triacetic acid, alkyliminodicarboxylic acids and alkyliminodicarboxylic acids of corresponding phosphonic acids. Persulphates are also suitable as bleaching agents.

BeispieleExamples Beispiel 1example 1 Probe 1 (Vergleich)Sample 1 (comparison)

Ein Schichtträger aus beidseitig mit Polyethylen beschichtetem Papier wurde mit folgenden Schichten versehen. Die Mengenangaben beziehen sich auf 1 m2.

Schicht 1
Eine Substratschicht aus 200 mg Gelatine mit KNO3- und Chromalaunzusatz.
Schicht 2
Eine Haftschicht aus 320 mg Gelatine.
Schicht 3
Eine grünempfindliche Silberbromidchloridemulsionsschicht (20 mol-% Chlorid) aus
  • 530 mg AgNO3 mit 750 mg Gelatine,
  • 0,61 g Magentakuppler M-5, emulgiert mit
  • 0,61 g Trikresylphosphat (TKP)
    •
    Schicht 4
    Eine Schutzschicht aus 1 g Gelatine und 16 mg eines Netzmittels der Formel C8F17 SO3 ⊖ N(C2H5)4 ⊕    (NM-1) Auf diese Schicht trägt man eine Härtungsschicht auf, die pro m2 120 mg Härtungsmittel der Formel
    Figure 00360001
    enthält.A layer support made of paper coated on both sides with polyethylene was provided with the following layers. The quantities given relate to 1 m 2 .
    Layer 1
    A substrate layer made of 200 mg gelatin with addition of KNO 3 and chrome alum.
    Layer 2
    An adhesive layer made of 320 mg gelatin.
    Layer 3
    A green sensitive silver bromide chloride emulsion layer (20 mol% chloride)
  • 530 mg AgNO 3 with 750 mg gelatin,
  • 0.61 g magenta coupler M-5, emulsified with
  • 0.61 g tricresyl phosphate (CPM)
    • Layer 4
    A protective layer of 1 g of gelatin and 16 mg of a wetting agent of the formula C 8 F 17 SO 3 ⊖ N (C 2 H 5 ) 4 ⊕ (NM-1) A hardening layer is applied to this layer, 120 mg of hardening agent of the formula per m 2
    Figure 00360001
    contains.

    Proben 2 bis 12Samples 2 through 12

    Proben 2 bis 12 wurden in der gleichen Weise wie Probe 1 hergestellt mit dem Unterschied, daß das in Probe 1 verwendete Trikresylphosphat bei Probe 2 (vergleiche auch Proben 6-9) ersetzt wurde und daß bei den Proben 3-12 zusätzlich ein Lichtschutzmittel verwendet wurde, und zwar bei den Proben 3-11 eine Verbindung der Formel I (gemäß der Erfindung) und bei Probe 12 die Vergleichsverbindung der Formel:

    Figure 00360002
    Als Ölbildner enthielten die Proben 1-12 entweder Trikresylphosphat oder Dibutylphthalat (s. Tabelle 1).Samples 2 to 12 were prepared in the same way as sample 1, with the difference that the tricresyl phosphate used in sample 1 was replaced in sample 2 (also compare samples 6-9) and that a light stabilizer was additionally used in samples 3-12 , namely in samples 3-11 a compound of formula I (according to the invention) and in sample 12 the comparison compound of formula:
    Figure 00360002
    Samples 1-12 contained either tricresyl phosphate or dibutyl phthalate as oil formers (see Table 1).

    Die erhaltenen Proben wurden anschließend hinter einem graduierten Graukeil belichtet. Anschließend wurden die Materialien mit den nachfolgend aufgeführten Verarbeitungsbädern in folgender Weise verarbeitet: Entwicklung 210 s, 33°C Bleichen 50 s, 20°C Fixieren 60 s, 20°C Wässern 120 s, 20° Trocknen. The samples obtained were then exposed behind a graduated gray wedge. The materials were then processed in the following manner using the processing baths listed below: development 210 s, 33 ° C bleaching 50 s, 20 ° C Fix 60 s, 20 ° C Water 120 s, 20 ° Dry.

    Zusammensetzung der BäderComposition of the bathrooms Entwickler:Developer: BenzylalkoholBenzyl alcohol 13 ml13 ml HydroxylammoniumsulfatHydroxylammonium sulfate 3 g3 g NatriumsulfitSodium sulfite 2 g2 g 4-Amino-N-ethyl-N(β-methan-sulfonamidoethyl)-m-toluidin-sesquisulfat (Monohydrat)4-amino-N-ethyl-N (β-methanesulfonamidoethyl) -m-toluidine-sesquisulfate (monohydrate) 4,5 g4.5 g KaliumcarbonatPotassium carbonate 36 g36 g KaliumbromidPotassium bromide 1,4 g1.4 g Diethylen-triamino-pentaessigsaure, PentanatriumsalzDiethylene triamino pentaacetic acid, pentasodium salt 2 g2 g DiethylenglykolDiethylene glycol 12 ml12 ml Auffüllen mit Wasser auf 1 Liter
    pH = 10,4    Make up to 1 liter with water
    pH = 10.4         Bleichbad:Bleaching bath: Wasserwater 700 ml700 ml NH4-Fe-EDTANH 4 -Fe-EDTA 65 g65 g EDTAEDTA 10 g10 g MH4BrMH 4 Br 100 g100 g mit Essigsäure auf pH 6,0 einstellen, Auffüllen mit Wasser aus 1 Literadjust to pH 6.0 with acetic acid, fill up with water from 1 liter Fixierbad:Fixing bath: AmmoniumthiosulfatAmmonium thiosulfate 100 g100 g Na-sulfit, sicc.Na sulfite, sicc. 10 g10 g Na-disulfitNa disulfite 3 g3 g mit Wasser auffüllen auf 1 Liter.fill up to 1 liter with water.

    Danach wurde die maximale Farbdichte gemessen (Tabelle 1).The maximum color density was then measured (Table 1).

    Außerdem wurden die Proben dem Licht einer für Tageslicht normierten Xenonlampe ausgesetzt und mit 4,2 x 106 lx.h belichtet; danach wurde die prozentuale Dichteabnahme gemessen (Tabelle 1).

    Figure 00390001
    In addition, the samples were exposed to the light of a xenon lamp standardized for daylight and exposed to 4.2 x 10 6 lx.h; the percentage decrease in density was then measured (Table 1).
    Figure 00390001

    Das Beispiel zeigt, daß durch die erfindungsgemäßen Verbindungen hohe maximale Farbdichten erzielt werden und gleichzeitig die Lichtstabilität des Bildfarbstoffs verbessert wird. Die als Vergleich eingesetzte Verbindung VP-1 gemäß GB 2 135 788 bewirkt eine geringere Verbesserung der Lichtstabilität.The example shows that the compounds of the invention high maximum color densities can be achieved and at the same time improves the light stability of the image dye becomes. The connection used as a comparison VP-1 according to GB 2 135 788 causes less improvement the light stability.

    Beispiel 2Example 2

    Es wird wie in Beispiel 1 beschrieben ein Schichtaufbau hergestellt mit dem Unterschied, daß in der grünempfindlichen Schicht anstelle des Magentakupplers M-5 der Magentakuppler M-14 verwendet wird. Man erhält so die Probe 13 (Vergleich).As described in Example 1, it becomes a layer structure produced with the difference that in the green sensitive Layer instead of the magenta coupler M-5 Magenta coupler M-14 is used. You get that Sample 13 (comparison).

    Die Proben 14-18 werden in der gleichen Weise wie Probe 13 hergestellt mit dem Unterschied, daß die Schicht 3 in Probe 13 eine der erfindungsgemäßen Verbindungen zugesetzt wurde. In gleicher Weise wird Probe 19 unter Verwendung der Vergleichsverbindung VP-1 hergestellt. Die Verarbeitung und Prüfung erfolgt wie in Beispiel 1 beschrieben.

    Figure 00400001
    Figure 00410001
    Samples 14-18 are prepared in the same manner as sample 13, except that layer 3 in sample 13 has one of the compounds according to the invention added. In the same way, sample 19 is prepared using the comparative compound VP-1. Processing and testing are carried out as described in Example 1.
    Figure 00400001
    Figure 00410001

    Das Beispiel zeigt, daß durch den Einsatz der erfindungsgemäßen Verbindungen die Lichtstabilität der Bildfarbstoffe verbessert wird. Die als Vergleich eingesezte Verbindung VP-1 gemäß GB 2 135 788 bewirkt eine geringere Verbesserung der Lichtstabilität.The example shows that by using the invention Compounds the light stability of the image dyes is improved. The used as a comparison Connection VP-1 according to GB 2 135 788 causes a lower one Improve light stability.

    Beispiel 3Example 3

    Ein für einen Schnellverarbeitungsprozeß geeignetes farbfotografisches Aufzeichnungsmaterial wurde hergestellt, indem auf einen Schichtträger aus beidseitig mit Polyethylen beschichtetem Papier die folgenden Schichten in der angegebenen Reihenfolge aufgetragen wurden. Die Mengenangaben beziehen sich jeweils auf 1 m2. Für den Silberhalogenidauftrag werden die entsprechenden Mengen AgNO3 angegeben.A color photographic recording material suitable for a rapid processing process was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene. The quantities given relate to 1 m 2 . The corresponding amounts of AgNO 3 are given for the silver halide application.

    Probe 20:Sample 20:

    Schicht 1:
    (Substratschicht)
    0,2 g Gelatine
    Schicht 2:
    (blauempfindliche Schicht)
    blauempfindliche Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Korndurchmesser 0,8 µm) aus 0,63 g AgNO3 mit
  • 1,38 g Gelatine
  • 0,95 g Gelbkuppler Y-1
  • 0,2 g Weißkuppler W-1
  • 0,29 g Trikresylphosphat (TKP)
    •
    Schicht 3:
    (Schutzschicht)
  • 1,1 g Gelatine
  • 0,06 g 2,5-Dioctylhydrochinon
  • 0,06 g Dibutylphthalat (DBP)
    •
    Schicht 4:
    (grünempfindliche Schicht)
    grünsensibilisierte Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Korndurchmesser 0,6 µm) aus 0,45 g AgNO3 mit
  • 1,08 g Gelatine
  • 0,40 g Magentakuppler M-15
  • 0,16 g α-(3-t-Butyl-4-hydroxyphenoxy)-myristinsäure-ethylester
  • 0,08 g 2,5-Dioctylhydrochinon
  • 0,34 g DBP
  • 0,04 g TKP
    •
    Schicht 5:
    (UV-Schutzschicht)
  • 1,15 g Gelatine
  • 0,6 g UV-Absorber der Formel
    Figure 00430001
  • 0,045g 2,5-Dioctylhydrochinon
  • 0,04 g TKP
    •
    Schicht 6:
    (rotempfindliche Schicht)
    rotsensibilisierte Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Korndurchmesser 0,5 µm) aus
  • 0,3 g AgNO3 mit
  • 0,75 g Gelatine
  • 0,36 g Cyankuppler C-1
  • 0,36 g TKP
    •
    Schicht 7:
    (UV-Schutzschicht)
  • 0,35 g Gelatine
  • 0,15 g UV-Absorber wie in Schicht 5
  • 0,2 g TKP
    •
    Schicht 8:
    (Schutzschicht)
  • 0,9 g Gelatine
  • 0,3 g Härtungsmittel Carbamoylpyridiniumsalz (CAS Reg.No. 65411-60-1)
    •
    Figure 00440001
    Figure 00450001
    Figure 00450002
    Figure 00450003
    Layer 1:
    (Substrate layer)
    0.2 g gelatin
    Layer 2:
    (blue sensitive layer)
    Blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 µm) from 0.63 g AgNO 3 with
  • 1.38 g gelatin
  • 0.95 g yellow coupler Y-1
  • 0.2 g white coupler W-1
  • 0.29 g tricresyl phosphate (CPM)
    • Layer 3:
    (Protective layer)
  • 1.1 g gelatin
  • 0.06 g 2,5-dioctyl hydroquinone
  • 0.06 g dibutyl phthalate (DBP)
    • Layer 4:
    (green sensitive layer)
    Green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.6 µm) from 0.45 g AgNO 3 with
  • 1.08 g gelatin
  • 0.40 g magenta coupler M-15
  • 0.16 g of ethyl α- (3-t-butyl-4-hydroxyphenoxy) myristic acid
  • 0.08 g 2,5-dioctyl hydroquinone
  • 0.34 g DBP
  • 0.04 g CPM
    • Layer 5:
    (UV protective layer)
  • 1.15 g gelatin
  • 0.6 g UV absorber of the formula
    Figure 00430001
  • 0.045g 2,5-dioctyl hydroquinone
  • 0.04 g CPM
    • Layer 6:
    (red sensitive layer)
    red-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 µm)
  • 0.3 g of AgNO 3 with
  • 0.75 g gelatin
  • 0.36 g cyan coupler C-1
  • 0.36 g CPM
    • Layer 7:
    (UV protective layer)
  • 0.35 g gelatin
  • 0.15 g UV absorber as in layer 5
  • 0.2 g CPM
    • Layer 8:
    (Protective layer)
  • 0.9 g gelatin
  • 0.3 g hardening agent carbamoylpyridinium salt (CAS Reg.No. 65411-60-1)
    • Figure 00440001
    Figure 00450001
    Figure 00450002
    Figure 00450003

    Proben 21 bis 27Samples 21 to 27

    Proben 21 bis 27 wurden in gleicher Weise hergestellt wie Probe 20 mit dem Unterschied, daß der 4. Schicht (grünempfindlich) ein erfindungsgemäßes Lichtschutzmittel der Formel I (Proben 21 bis 25) bzw. die Vergleichsverbindungen VP-1 und VP-2 (Proben 26 bzw. 27) zugesetzt wurden.

    Figure 00460001
    Samples 21 to 27 were produced in the same way as sample 20, with the difference that the 4th layer (sensitive to green) is a light stabilizer according to the invention of the formula I (samples 21 to 25) or the comparative compounds VP-1 and VP-2 (samples 26 or 27) were added.
    Figure 00460001

    Die erhaltenen Proben wurden hinter einem graduierten Graukeil und danach mit den nachfolgend aufgeführten Verarbeitungsbädern wie folgt verarbeitet:

  • a) Farbentwickler - 45 s - 35°C Triethanolamin 9,0 g NN-Diethylhydroxylamin 4,0 g Diethylenglykol 0,05 g 3-Methyl-4-amino-N-ethyl-N-methansulfonamidoethyl-anilin-sulfat 5,0 g Kaliumsulfit 0,2 g Triethylenglykol 0,05 g Kaliumcarbonat 22 g Kaliumhydroxid 0,4 g Ethylendiamintetraessigsäure di-Na-Salz 2,2 g Kaliumchlorid 2,5 g 1,2-Dihydroxybenzol-3,4,6-trisulfonsäure-trinatriumsalz 0,3 g auffüllen mit Wasser auf 1.000 ml; pH 10,0
  • b) Bleichfixierbad - 45 s - 35°C Ammoniumthiosulfat 75 g Natriumhydrogensulfit 13,5 g Ammoniumacetat 2,0 g Ethylendiamintetraessigsäure (Eisen-Ammonium-Salz) 57 g Ammoniak 25 %ig 9,5 g auffüllen mit Essig auf 1.000 ml; pH 5,5
  • c) Wässern - 2 min - 33°C
    • The samples obtained were processed behind a graduated gray wedge and then with the processing baths listed below as follows:
  • a) Color developer - 45 s - 35 ° C Triethanolamine 9.0 g NN-diethylhydroxylamine 4.0 g Diethylene glycol 0.05 g 3-methyl-4-amino-N-ethyl-N-methanesulfonamidoethyl aniline sulfate 5.0 g Potassium sulfite 0.2 g Triethylene glycol 0.05 g Potassium carbonate 22 g Potassium hydroxide 0.4 g Ethylenediaminetetraacetic acid di-Na salt 2.2 g Potassium chloride 2.5 g 1,2-Dihydroxybenzene-3,4,6-trisulfonic acid trisodium salt 0.3 g make up to 1,000 ml with water; pH 10.0
  • b) bleach-fix bath - 45 s - 35 ° C Ammonium thiosulfate 75 g Sodium bisulfite 13.5 g Ammonium acetate 2.0 g Ethylenediaminetetraacetic acid (iron ammonium salt) 57 g 25% ammonia 9.5 g fill up to 1,000 ml with vinegar; pH 5.5
  • c) Soak - 2 min - 33 ° C

    • Danach wurde die maximale Farbdichte gemessen (Tabelle 3); die Proben wurden dem Licht eine für Tageslicht normierten Xenonlampe ausgesetzt und mit 9.6 x 106 lx·h belichtet; anschließend wurde die prozentuale Dichteabmahme gemessen.

    Figure 00480001
    The maximum color density was then measured (Table 3); the samples were exposed to the light of a xenon lamp standardized for daylight and exposed to 9.6 x 10 6 lx · h; the percentage decrease in density was then measured.
    Figure 00480001

    Das Beispiel zeigt eine deutliche Verbesserung der Lichtstabilität der Bildfarbstoffe durch die erfindungsgemäßen Verbindungen in Gegensatz zu den als Vergleich eingesetzten Verbindungen VP-1 und VP-2.The example shows a significant improvement in Light stability of the image dyes by the invention Connections as opposed to those for comparison used connections VP-1 and VP-2.

    Beispiel 4Example 4

    Ein für die Umkehrverarbeitung geeignetes farbfotografisches Aufzeichnungsmaterial wurde hergestellt, indem auf einen mit einer Haftschicht versehenen transparenten Schichtträger aus Cellulosetriacetat die folgenden Schichten in der angegebenen Reihenfolge aufgetragen wurden. Die Mengenangaben beziehen sich jeweils auf 1 m2. Für den Silberhalogenidauftrag werden die entsprechenden Mengen AgNO3 angegeben.A color photographic recording material suitable for reversal processing was produced by applying the following layers in the order given to a transparent layer support made of cellulose triacetate provided with an adhesive layer. The quantities given relate to 1 m 2 . The corresponding amounts of AgNO 3 are given for the silver halide application.

    Probe 28Sample 28

    Schicht 1
    (Antihaloschicht)
    schwarzes kolloidales Silbersol mit
  • 0,25 g Ag
  • 1,60 g Gelatine
  • 0,24 g UV-Absorber UV-1
    •
    Schicht 2
    (Zwischenschicht)
    0,64 g Gelatine
    Schicht 3
    (1. rotempfindliche Schicht)
    rotsensibilisierte Silberbromidiodidemulsion
    (2,5 mol-% Iodid;
    mittlerer Korndurchmesser 0,25 µm) aus 0,60 g AgNO3, mit
  • 0,59 g Gelatine
  • 0,24 g Cyankuppler C-2
  • 0,12 g TKP
    •
    Schicht 4
    (2. rotempfindliche Schicht)
    rotsensibilisierte Silberbromidiodidemulsion
    (3,0 mol-% Iodid;
    mittlerer Korndurchmesser 0,43 µm) aus 0,95 g AgNO3, mit
  • 1,96 g Gelatine
  • 0,95 g Cyankuppler C-2
  • 0,48 g TKP
    •
    Schicht 5
    (Zwischenschicht)
  • 1,78 g Gelatine
  • 0,24 g Verbindung SC-1
  • 0,12 g TKP
    •
    Schicht 6
    (1. grünempfindliche Schicht)
    Mischung 3:1 aus einer Silberbromidiodidemulsion
    (1,0 mol-% Iodid; mittlerer Korndurchmesser 0,26 µm)
    und einer Silberbromidiodidemulsion
    (4,0 mol-% Iodid; mittlerer Korndurchmesser 0,21 µm),
    beide grünsensibilisiert,
    aus 0,67 g AgNO3, mit
  • 1,13 g Gelatine
  • 0,14 g Magentakuppler M-16
  • 0,10 g TKP
    •
    Schicht 7
    (2. grünempfindliche Schicht)
    grünsensibilisierte Silberbromidiodidemulsion
    (1,5 mol-% Iodid;
    mittlerer Korndurchmesser 0,42 µm) aus
  • 1,05 g AgNO3, mit
  • 2,72 g Gelatine
  • 0,68 g Magentakuppler M-16
  • 0,45 g TKP
    •
    Schicht 8
    (Zwischenschicht)
  • 0,55 g Gelatine
  • 0,10 g Verbindung SC-1
    •
    Schicht 9
    (Gelbfilterschicht)
    gelbes kolloidales Silbersol mit
  • 0,11 g Ag,
  • 0,45 g Gelatine
    •
    Schicht 10
    (Zwischenschicht)
    0,71 g Gelatine
    Schicht 11
    (1. blauempfindliche Schicht)
    blausensibilisierte Silberbromidiodidemulsion
    (4,0 mol-% Iodid;
    mittlerer Korndurchmesser 0,28 µm) aus
  • 0,58 g AgNO3, mit
  • 1,31 g Gelatine
  • 0,24 g Gelbkuppler Y-2
  • 0,12 g TKP
    •
    Schicht 12
    (2. blauempfindliche Schicht)
    blausensibilisierte Silberbromidiodidemulsion
    (3,0 mol-% Iodid;
    mittlerer Korndurchmesser 0,66 µm) aus
  • 0,66 g AgNO3, mit
  • 2,04 g Gelatine
  • 0,83 g Gelbkuppler Y-2
  • 0,41 g TKP
    •
    Schicht 13
    (Zwischenschicht)
  • 0,76 g Gelatine
  • 0,54 g Verbindung SC-1
  • 0,50 g UV-Absorber UV-2
  • 0,02 g TKP
    •
    Schicht 14
    (Zwischenschicht)
    Mikrat-Silberbromidiodidemulsion
    (4,0 mol-% Iodid;
    mittlerer Korndurchmesser 0,15 µm) aus
  • 0,20 g AgNO3, mit
  • 0,57 g Gelatine
    •
    Schicht 15
    (Härtungsschicht)
  • 0,25 g Gelatine
  • 0,87 g Härtungsmittel
    Carbamoylpyridiniumsalz
    (CAS Reg. No. 65411-60-1)
    •
    Figure 00530001
    Figure 00530002
    Figure 00530003
    Figure 00530004
    Figure 00540001
    Figure 00540002
    Layer 1
    (Antihalation layer)
    black colloidal silver sol with
  • 0.25 g Ag
  • 1.60 g gelatin
  • 0.24 g UV absorber UV-1
    • Layer 2
    (Intermediate layer)
    0.64 g gelatin
    Layer 3
    (1st red sensitive layer)
    red-sensitized silver bromoiodide emulsion
    (2.5 mol% iodide;
    average grain diameter 0.25 µm) from 0.60 g AgNO 3 , with
  • 0.59 g gelatin
  • 0.24 g cyan coupler C-2
  • 0.12 g CPM
    • Layer 4
    (2nd red sensitive layer)
    red-sensitized silver bromoiodide emulsion
    (3.0 mol% iodide;
    average grain diameter 0.43 µm) from 0.95 g AgNO 3 , with
  • 1.96 g gelatin
  • 0.95 g cyan coupler C-2
  • 0.48 g CPM
    • Layer 5
    (Intermediate layer)
  • 1.78 g gelatin
  • 0.24 g of compound SC-1
  • 0.12 g CPM
    • Layer 6
    (1st green sensitive layer)
    Mixture 3: 1 from a silver bromide iodide emulsion
    (1.0 mol% iodide; average grain diameter 0.26 µm)
    and a silver bromoiodide emulsion
    (4.0 mol% iodide; average grain diameter 0.21 µm),
    both sensitized to green,
    from 0.67 g AgNO 3 , with
  • 1.13 g gelatin
  • 0.14 g M-16 magenta coupler
  • 0.10 g CPM
    • Layer 7
    (2nd green sensitive layer)
    green-sensitized silver bromoiodide emulsion
    (1.5 mol% iodide;
    average grain diameter 0.42 µm)
  • 1.05 g AgNO 3 , with
  • 2.72 g gelatin
  • 0.68 g M-16 magenta coupler
  • 0.45 g CPM
    • Layer 8
    (Intermediate layer)
  • 0.55 g gelatin
  • 0.10 g compound SC-1
    • Layer 9
    (Yellow filter layer)
    yellow colloidal silver sol with
  • 0.11 g Ag,
  • 0.45 g gelatin
    • Layer 10
    (Intermediate layer)
    0.71 g gelatin
    Layer 11
    (1st blue sensitive layer)
    blue-sensitized silver bromoiodide emulsion
    (4.0 mol% iodide;
    average grain diameter 0.28 µm)
  • 0.58 g AgNO 3 , with
  • 1.31 g gelatin
  • 0.24 g yellow coupler Y-2
  • 0.12 g CPM
    • Layer 12
    (2nd blue sensitive layer)
    blue-sensitized silver bromoiodide emulsion
    (3.0 mol% iodide;
    average grain diameter 0.66 µm)
  • 0.66 g AgNO 3 , with
  • 2.04 g gelatin
  • 0.83 g yellow coupler Y-2
  • 0.41 g CPM
    • Layer 13
    (Intermediate layer)
  • 0.76 g gelatin
  • 0.54 g compound SC-1
  • 0.50 g UV absorber UV-2
  • 0.02 g CPM
    • Layer 14
    (Intermediate layer)
    Mikrat-silver bromide iodide emulsion
    (4.0 mol% iodide;
    average grain diameter 0.15 µm)
  • 0.20 g AgNO 3 , with
  • 0.57 g gelatin
    • Layer 15
    (Hardening layer)
  • 0.25 g gelatin
  • 0.87 g hardener
    Carbamoylpyridinium salt
    (CAS Reg.No. 65411-60-1)
    • Figure 00530001
    Figure 00530002
    Figure 00530003
    Figure 00530004
    Figure 00540001
    Figure 00540002

    Proben 29-33Samples 29-33

    Die Proben 29-33 werden in der gleichen Weise hergestell wie die Probe 28 mit dem Unterschied, daß der 6. und der 7. Schicht (grünempfindliche Schichten) eine erfindungsgemäße Verbindung der Formel I (Proben 29-32) bzw. die Verbindung VP-2 (Probe 33) zugesetzt wird.Samples 29-33 are made in the same manner like sample 28 with the difference that the 6th and the 7th layer (green-sensitive layers) according to the invention Compound of formula I (samples 29-32) or the Compound VP-2 (sample 33) is added.

    Die auf diese Weise hergestellten Proben wurden unter einem graduierten Graukeil belichtet und einer Colorumkehrentwicklung unterzogen, wie beschrieben in "Manual for PROCESSING Kodak Ektachrome Film using Process E7", Eastman Kodak Company, 1977 (vgl. Kodak Publikation Nr. 7-119).The samples prepared in this way were taken under exposed to a graduated gray wedge and a color reversal development subjected as described in "Manual for PROCESSING Kodak Ektachrome Film using Process E7 ", Eastman Kodak Company, 1977 (see Kodak Publication No. 7-119).

    Anschließend wurde die maximale Farbdichte gemessen (Tab. 4) und die Proben dem Licht einer für Tageslicht normierten Xenonlampe ausgesetzt und mit 7.2 x 106 lx·h belichtet; danach wurde die prozentuale Dichteabnahme gemessen.

    Figure 00550001
    The maximum color density was then measured (Tab. 4) and the samples were exposed to the light of a xenon lamp standardized for daylight and exposed to 7.2 x 10 6 lx · h; the percentage decrease in density was then measured.
    Figure 00550001

    Das Beispiel zeigt, daß die erfindungsgemäßen Verbindungen die Lichtstabilität der Bildfarbstoffe verbessern. Die als Vergleich eigensetzte Verbindung VP-2 bewirkt eine geringere Verbesserung.The example shows that the compounds according to the invention improve the light stability of the image dyes. The connection VP-2 set as a comparison causes less improvement.

    Claims (2)

    1. Colour photographic recording material having at least one silver halide emulsion layer and a colour coupler associated therewith, characterised in that it contains, associated with at least one photosensitive silver halide emulsion layer, a combination of a pyrazoloazole coupler and a compound of the general formula I or of the formulae VI-X:
      Figure 00610001
      Figure 00610002
      Figure 00610003
      Figure 00610004
      Figure 00620001
      Figure 00620002
      in which
      R1
      means H, a residue eliminable under alkaline conditions, alkyl or aryl;
      R2
      means -OH, alkyl, aryl, alkoxy or
      Figure 00620003
      R3, R4, R5 and R6
      mean H, -OH, -COOH, -SO3H, -SO2H, alkyl, aryl, alkoxy, alkylsulphonyl, arylsulphonyl, optionally substituted sulphamoyl, acylamino or
      Figure 00630001
      in which at least one of the residues R2, R3, R4, R5 and R6 is a residue of the formula
      Figure 00630002
      A
      means alkylene having 1-6 C atoms;
      n
      means 0 or 1;
      R7
      means H or alkyl optionally substituted with, for example, -COOH or -SO3H, for example carboxymethyl;
      R8
      means alkyl, cycloalkyl or aryl having 4 to 20 C atoms optionally mono- or polysubstituted by a group of the formula
      Figure 00630003
      in which R1 to R7, A and n have the above-stated meanings; or unsubstituted alkyl, cycloalkyl or aryl having 4 to 20 C atoms;
      R1 and R3
      may form a 5- or 6-membered ring, wherein R2 = -OH or alkoxy;
      R2 and R4
      may form a 5- or 6-membered carbocyclic ring.
    2. Recording material according to claim 1, characterised in that the pyrazoloazole coupler is of one of the formulae IV and V
      Figure 00640001
      in which
      X
      means H or a group releasable under colour development conditions;
      R1, R2
      mean H, alkyl, aralkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, carbamoyl, sulphamoyl, wherein these residues may be further substituted.
    EP93103858A 1992-03-23 1993-03-10 Photographic recording material Expired - Lifetime EP0563638B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE4209346A DE4209346A1 (en) 1992-03-23 1992-03-23 Photographic recording material
    DE4209346 1992-03-23

    Publications (2)

    Publication Number Publication Date
    EP0563638A1 EP0563638A1 (en) 1993-10-06
    EP0563638B1 true EP0563638B1 (en) 1998-06-17

    Family

    ID=6454766

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP93103858A Expired - Lifetime EP0563638B1 (en) 1992-03-23 1993-03-10 Photographic recording material

    Country Status (4)

    Country Link
    US (1) US5340709A (en)
    EP (1) EP0563638B1 (en)
    JP (1) JPH0643614A (en)
    DE (2) DE4209346A1 (en)

    Families Citing this family (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE10111655A1 (en) * 2001-03-12 2002-10-02 Agfa Gevaert Ag Inkjet ink
    JP5892327B2 (en) 2012-03-15 2016-03-23 Ｊｆｅスチール株式会社 Method for producing non-oriented electrical steel sheet

    Citations (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0542053A1 (en) * 1991-11-11 1993-05-19 Agfa-Gevaert AG Photographic recording material

    Family Cites Families (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE3435443A1 (en) * 1984-09-27 1986-04-03 Agfa-Gevaert Ag, 5090 Leverkusen PHOTOGRAPHIC RECORDING MATERIAL
    DE3501722A1 (en) * 1985-01-19 1986-07-24 Agfa-Gevaert Ag, 5090 Leverkusen LIGHT SENSITIVE, STABILIZED PHOTOGRAPHIC RECORDING MATERIAL
    JPH0762759B2 (en) * 1986-01-22 1995-07-05 コニカ株式会社 Silver halide photographic light-sensitive material
    JPH0648372B2 (en) * 1986-11-13 1994-06-22 富士写真フイルム株式会社 Silver halide color photographic light-sensitive material

    Patent Citations (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0542053A1 (en) * 1991-11-11 1993-05-19 Agfa-Gevaert AG Photographic recording material

    Also Published As

    Publication number Publication date
    EP0563638A1 (en) 1993-10-06
    US5340709A (en) 1994-08-23
    JPH0643614A (en) 1994-02-18
    DE4209346A1 (en) 1993-09-30
    DE59308679D1 (en) 1998-07-23

    Similar Documents

    Publication Publication Date Title
    DE4323512A1 (en) Photographic recording material
    DE3633364C2 (en)
    EP0409019B1 (en) Colour photographic recording material with improved hue reproduction
    EP0401612B1 (en) Colour photographic recording material with a DIR coupler
    DE69212548T2 (en) Color photographic materials containing a magenta coupler, a DIR coupler and a carbonamide compound
    EP0648761A2 (en) Quinazolinyl yellow coupler for photographic recording material
    EP0415056B1 (en) Colour photographic recording material with a coupler liberating a photographically useful compound
    EP0257451B1 (en) Colour-photographic recording material
    EP0871066B1 (en) Colour photographic silver halide material
    EP0401613B1 (en) Colour photographic recording material with a DIR coupler
    EP0421221B1 (en) Colour photographic recording material with a DIR coupler
    EP0254151B1 (en) Colour photographic material containing couplers
    EP0563638B1 (en) Photographic recording material
    EP0585546B1 (en) Photographic recording material
    DE3622007C2 (en) Color photographic recording material with 2-equivalent magenta couplers
    EP0572894B1 (en) Color photographic recording material with a cyan-DIR-coupler
    EP0542053B1 (en) Photographic recording material
    DE3613974C2 (en) Color photographic recording material
    DE69205087T2 (en) Photographic coupler compositions containing carbonamides and methods.
    DE3835202A1 (en) COLOR PHOTOGRAPHIC RECORDING MATERIAL
    DE19503885A1 (en) Colour photographic material contains acrylic copolymer as solvent
    EP0489333A1 (en) Colour photographic recording material with a pyrazoloazole colour coupler
    DE3706202C2 (en) Color photographic recording material
    DE3823049A1 (en) Colour-photographic recording material
    DE4314669A1 (en) Photographic recording material

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): BE DE FR GB

    17P Request for examination filed

    Effective date: 19940331

    17Q First examination report despatched

    Effective date: 19970506

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): BE DE FR GB

    REF Corresponds to:

    Ref document number: 59308679

    Country of ref document: DE

    Date of ref document: 19980723

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 19980917

    ET Fr: translation filed
    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: 746

    Effective date: 19990330

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed
    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: D6

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: FR

    Payment date: 20000223

    Year of fee payment: 8

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: BE

    Payment date: 20000224

    Year of fee payment: 8

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20000313

    Year of fee payment: 8

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20000329

    Year of fee payment: 8

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20010310

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20010331

    BERE Be: lapsed

    Owner name: AGFA-GEVAERT A.G.

    Effective date: 20010331

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20010310

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: FR

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20011130

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: ST

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20020101