EP1014183B1 - Colour photographic recording material - Google Patents
Colour photographic recording material Download PDFInfo
- Publication number
- EP1014183B1 EP1014183B1 EP99124022A EP99124022A EP1014183B1 EP 1014183 B1 EP1014183 B1 EP 1014183B1 EP 99124022 A EP99124022 A EP 99124022A EP 99124022 A EP99124022 A EP 99124022A EP 1014183 B1 EP1014183 B1 EP 1014183B1
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- EP
- European Patent Office
- Prior art keywords
- layer
- base
- silver halide
- recording material
- halide emulsion
- 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
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Classifications
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- 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
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- 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
- G03C7/392—Additives
- G03C7/39208—Organic compounds
- G03C7/39236—Organic compounds with a function having at least two elements among nitrogen, sulfur or oxygen
-
- 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
- G03C7/3924—Heterocyclic
- G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
- G03C7/39248—Heterocyclic the nucleus containing only nitrogen as hetero atoms one nitrogen atom
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- 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
- G03C7/3924—Heterocyclic
- G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
- G03C7/39252—Heterocyclic the nucleus containing only nitrogen as hetero atoms two nitrogen atoms
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- 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
- G03C7/3924—Heterocyclic
- G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
- G03C7/39256—Heterocyclic the nucleus containing only nitrogen as hetero atoms three nitrogen atoms
-
- 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
- G03C7/3924—Heterocyclic
- G03C7/39268—Heterocyclic the nucleus containing only oxygen as hetero atoms
-
- 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
- G03C7/3924—Heterocyclic
- G03C7/39272—Heterocyclic the nucleus containing nitrogen and oxygen
Definitions
- DE 2 328 014 and DE 2 421 068 are color photographic recording materials known that contain color couplers in an additional silver halide emulsion layer, wherein the silver halide emulsion is fogged and the layer for Masking is used.
- a colored layer is installed, which is then referred to as a filter layer becomes.
- a filter layer usually a yellow one in color photographic materials Filter layer between the blue sensitive layer and the one below green sensitive and red sensitive layers arranged to the blue light to keep away from the green or red sensitive layers.
- the dyes must not have any adverse effects on the quality of the exercise photographic silver halide emulsion; you can e.g. not the Press sensitivity or cause fog.
- the Dyes in the material are diffusion resistant, but must be used during processing of the material completely and irreversibly discolored or washed out of the layer be so that no unwanted staining on the exposed and developed photographic material remains.
- the dyes be stable in storage and not change in the photographic material lead during storage.
- DE 196 46 402 includes condensation products of 3-alkylisoxazolones p-N, N-bis-carbalkoxymethylaminobenzaldehydes or N-carbalkoxyethylcarbazole-3-aldehydes (Arylidene dyes), the suitable absorption as yellow filter dyes exhibit and are completely discolored in the layer during development.
- the object of the present invention is a color photographic recording material, containing a decolourable yellow filter layer, with improved To provide storage stability.
- polyester-based materials should be improved in terms of storage stability. At the same time, it should be a good one Color separation from blue-green can be achieved.
- the yellow filter dyes known in the art in particular those from the DE 196 46 402 known dyes can be achieved by at least one Layer between the base and the photosensitive closest to the base Layer a compound of formula (I) is added. This could a stable green sensitivity can be achieved with normal storage. simultaneously it was also possible to improve the latent image stability.
- the compound of formula (I) is preferably used in an amount of 0.01 to 10 mmol / m 2 , in particular 0.1 to 2 mmol / m 2 .
- the compound of formula (I) is preferably used in an amount of 0.01 to 10 mmol / m 2 , in particular 0.1 to 2 mmol / m 2 .
- only one compound and also a mixture of different compounds of the formula (I) can be used.
- Electron- withdrawing groups within the meaning of the present invention are, for example, R'CO-, R'R'NCO-, NC-, R'SO 2 - R'OCO-, R'R''NSO 2 in a preferred embodiment according to formula (Ia ) (in the following, the formula (Ia) is also to be understood to mean the tautomeric form of the formula (Ib))
- X stands for -RCO and Y for an electron-withdrawing group R 'and R "can independently of one another the abovementioned radicals for R.
- Further groups preferred in the sense of the present application are described in March, Advanced Organic Chemistry, 3rd Ed., p.17 and p. 238.
- R and Y form according to formula Ia or Ib together a group to complete a 5 or 6 ring.
- Ring systems preferably formed are, for example Pyrazolones, isoxazolones and pyrazolidinediones.
- Alkyl in the sense of the present application is understood to mean linear or branched, cyclic or straight-chain, substituted or unsubstituted hydrocarbons.
- these are alkyl groups with 1 to 12 carbon atoms, such as, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, neopentyl and 2-ethylhexyl groups.
- these can be further substituted, particularly preferably with a carboxycarbonyl group.
- Aryl for the purposes of the present application is to be understood as meaning aromatic hydrocarbon groups, which are preferably 5- to 6-membered ring systems, which can also be present as monocyclic but also as condensed ring systems. It can be both substituted and unsubstituted ring systems.
- aryl should also be understood to mean hetaryls. These are aromatic systems which contain at least one heteroatom. These are also preferably 5- and 6-membered ring systems, which can be monocyclic but also as condensed ring systems. It can be both substituted and unsubstituted ring systems. N, S and O are particularly suitable as heteroatoms.
- a ring system can preferably have between 1 and 3 heteroatoms, which can be the same or different heteroatoms.
- heteroatoms can be the same or different heteroatoms.
- several identical or different heterocyclic systems can be condensed, including hetaryls with aryls.
- Aryloxy in the sense of the present application is understood to mean the groups already defined under aryl by an oxygen atom attached to the rest.
- Alkoxy in the sense of the present application is understood to mean the groups already defined under alkyl which are bonded to the rest via an oxygen atom.
- alkylamino is to be understood as the groups already defined under alkyl which are bonded to the remainder via an amino group.
- Arylamino in the sense of the present application are to be understood as the groups already defined under aryl by an amino group attached to the rest.
- Typical compounds of the formula (I) which can preferably be used according to the invention are the compounds A listed below:
- radicals R 1 , R 2 , R 3 and R 4 each independently represent an alkyl group, an aryl group, a heterocyclic group or an alkenyl group.
- the radicals R 5 , R 6 and R 7 likewise each independently represent a hydrogen atom or a substituent.
- Preferred substituents in the sense of the application are alkyl groups with 1 to 40 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, hexyl, octyl, 2-hydroxyethyl groups, and furthermore alkoxy groups with 1 to 40 C atoms such as methoxy, ethoxy or butoxy, and a halogen atom, for example only chlorine, bromine or fluorine, furthermore a mono- or dialkylamine group with a total of 1 to 20 carbon atoms in the alkyl groups, where the alkyl groups can be substituted, such as dimethylamino, diethylamino , Cyanoethylamino, an ester group with 2 to 20 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, an amido group such as acetylamino, benzamino,
- the alkyl group represented by R 1 , R 2 , R 3 and R 4 can be an alkyl group having 1 to 20 carbon atoms, such as, for example, methyl, ethyl, benzyl, phenethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl or nonyl, which can optionally carry substituents, these may be the substituents already mentioned.
- the radicals R 1 , R 2 , R 3 and R 4 can preferably represent an aryl group having 6 to 10 carbon atoms, such as, for example, phenyl or naphthyl, which can also be substituted by the previously mentioned substituents.
- a heterocyclic group represented by R 1 , R 2 , R 3 or R 4 can preferably be a 5- or 6-membered ring, this being, for example, an oxazole ring, benzoxazole ring, thiazole ring, imidazole ring, pyridine ring, furan ring, thiophene ring, sulforane ring, Pyrazole ring, pyrrole ring, chroman ring or coumarin ring can act, which can also be substituted with the previously mentioned substituents.
- R 1 , R 2 , R 3 or R 4 can preferably represent an alkenyl group having 2 to 10 carbon atoms, such as vinyl, allyl, 1-propenyl, 2-pentenyl, or 1,3-butadienyl.
- 2 of the substituents R 1 to R 7 can be bonded to one another and thereby form a ring system. It is preferably a 5- or 6-membered ring system, such as a pyrrolidine ring, a piperidine ring, a morpholine ring or a benzene ring.
- Particularly preferred compounds are:
- the compounds of formula (I) can preferably at least in any light-insensitive layer between the base and the Contain the support closest to the photosensitive emulsion layer his.
- the compounds of the formula (I) can be used to form an existing one Layer can be added as well as in a separate layer in the material be introduced. When it is introduced in the form of a separate layer usually around a layer consisting of a hydrophilic colloid, preferably Gelatin. The introduction can, for example, in high-boiling organic solvents take place as a finely divided solid dispersion or as a loaded latex known methods are carried out.
- the compounds are according to the invention of the formula (I) contained in at least one layer. It is located preferably directly on the surface.
- At least one layer means in the sense of present application that the compounds of formula (I) also in several Layers, maximum of all layers between the base and the base on next located light-sensitive layer, as well as possibly in additional existing layers can be included.
- the compounds are added to two or three layers.
- the Connections are a layer that is preferably directly on the base is located below the layer structure and / or a layer that is further from the base is added as any light sensitive layer and / or a layer added is on the back of the pad
- the photographic recording materials consist of a support on which at least one photosensitive silver halide emulsion layer is applied. Thin films and foils are particularly suitable as supports.
- An overview of Backing materials and auxiliary layers applied to their front and back is presented in Research Disclosure 37254, Part 1 (1995), p. 285.
- Various Polyester bases are in EP 0 601 501 A1 and US 5,719,015 described. Cellulose triacetate is preferred in the context of the present invention and in particular polyester used. Polyester in the sense of the present Invention are, for example, in EP 0601 501.A1 and US 5,719,015 described, particularly preferred are polyethylene glycol 2,6-naphthalate (PEN) and Polyethylene glycol terephthalate (PET).
- PEN polyethylene glycol 2,6-naphthalate
- PET Polyethylene glycol terephthalate
- color photographic recording materials are color negative films and Color positive films.
- An overview of typical color photographic recording materials as well as preferred embodiments and processing processes can be found in Research Disclosure 37038 (February 1995).
- the color photographic recording materials usually contain at least one red sensitive, one green sensitive and one blue sensitive silver halide emulsion layer and, if necessary, intermediate layers and protective layers.
- Color photographic films such as colomegative films show in the below Order on the carrier 2 or 3 red-sensitive, cyan-green domes Silver halide emulsion layers, 2 or 3 green-sensitive, purple-coupling silver halide emulsion layers and 2 or 3 blue sensitive, yellow coupling silver halide emulsion layers on.
- the layers of the same spectral sensitivity differ in their photographic sensitivity, the less sensitive sub-layers are usually arranged closer to the carrier than that higher sensitive sub-layers.
- Deviations in the number and arrangement of the photosensitive layers can occur to achieve certain results. For example, you can all highly sensitive layers in one layer package and all low-sensitive layers Layers combined into another layer package in a photographic film be to increase sensitivity (DE 25 30 645).
- Essential components of the photographic emulsion layers are binders, Silver halide grains and color couplers.
- Photographic materials with camera sensitivity usually contain silver bronze iodide emulsions, which may also contain small amounts of silver chloride can.
- Photographic copying materials contain either silver chloride bromide emulsions with up to 80 mol% of AgBr or silver chloride bromide emulsions over 95 mol% AgCl.
- the emulsions used are in a preferred embodiment around tab grain emulsions. among them are to be understood as emulsions with silver halide crystals, which have a tabular Have habit with an aspect ratio> 2, the aspect ratio being Ratio of the diameter of the circle of the same area of the projection area to the Thickness of the crystal is.
- the photographic emulsions can be made using methine dyes or other dyes are spectrally sensitized.
- Particularly suitable dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes.
- Such compounds, especially merocyanines, can also be used as Stabilizers are used.
- Pentamethine cyanines with naphthothiazole, naphthoxazole or benzothiazole as basic end groups can also be used as red sensitizers, which can be substituted with halogen, methyl or methoxy groups and bridged by 9,11-alkylene, in particular 9,11-neopentylene, as in GB 604 217 and BE 660 948.
- the N, N 'substituents can also be C 4 -C 8 alkyl groups as described in EP 0 532 042.
- the methine chain can additionally carry substituents as mentioned in EP 0 532 042.
- Pentamethines with only one methyl group on the cyclohexene ring can also be used, as described in EP 0 532 042.
- the red sensitizer can be supersensitized and stabilized by adding heterocyclic mercapto compounds.
- the red-sensitive layer can additionally between 390 and 590 nm, preferably at 500 nm be spectrally sensitized in order to improve the differentiation of the To cause red tones according to EP 0 304 297, US 806 460 and US 5 084 374.
- Such compounds can also act as stabilizers be used.
- the spectral sensitizers can be in dissolved form or as a disperse of the photographic Emulsion can be added. Both solution and dispersate can be additives such as wetting agents, dispersants or buffers.
- the spectral sensitizer or a combination of spectral sensitizers can before, during or after the emulsion preparation.
- the maximum absorption of that from the couplers and the color developer oxidation product Dyes formed are preferably in the following areas: Yellow coupler 430 to 460 nm, purple coupler 540 to 560 nm, cyan coupler 630 up to 700 nm.
- the color photographic recording material according to the invention can also be compounds contain, for example, a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, set an antifoggant or antifoggant free can, for example so-called DIR hydroquinones or other compounds, as for example in US-A 4,636,546, US-A 4,345,024, US-A 4,684,604 and in DE-A 24 47 079, DE-A 25 15 213 and DE-A 31 45 640 or in EP-A 198 438 are described. These connections perform the same function as DIR, DAR or FAR couplers, except that they do not form coupling products.
- High molecular weight color couplers are described, for example, in DE-C 1 297 417, DE-A 24 07 569, DE-A 31 48 125, DE-A 32 17 200, DE-A 33 20 079, DE-A 33 24 932, DE-A 33 31 743, DE-A 33 40 376, EP-A 27 284 and US-A 4 080 211.
- the high molecular weight color couplers are usually polymerized by produced ethylenically unsaturated color coupler monomers. But you can too can be obtained by polyaddition or polycondensation.
- the incorporation of the color coupler in silver halide emulsion layers can be done in the Way that first of the compound in question a solution or Dispersion prepared and then added to the casting solution for the layer in question becomes.
- the choice of the appropriate solvent or dispersant depends on the Solubility of the compound.
- the mostly hydrophobic color coupler, but also other hydrophobic components of the Layers are usually dissolved in high-boiling organic solvents or dispersed. These solutions or dispersions are then in an aqueous Binder solution (usually gelatin solution) emulsified and lie after Drying the layers as fine droplets (0.05 to 0.8 ⁇ m diameter) in the Layers before.
- aqueous Binder solution usually gelatin solution
- the compounds can also be in the form of so-called loaded latices Pouring solution are introduced. Reference is made, for example, to DE-A 25 41 230, DE-A25 41 274, DE-A 28 35 856, EP-A 0 014 921, EP-A 0 069 671, EP-A 0 130 115, US-A 4,291,113.
- the diffusion-resistant storage of anionic water-soluble Connections e.g. from couplers or dyes
- Suitable oil formers are e.g. Alkyl phthalates, phosphoric esters, phosphonic esters. Citric acid esters, lactic acid esters, benzoic acid esters, fatty acid esters, Amides, alcohols, phenols, sulfonamides, aniline derivatives and hydrocarbons.
- Yellow filter dyes are usually between the green sensitive and blue sensitive Layers applied, they prevent blue light in the below to reach lying layers.
- all yellow filter dyes known from the prior art can be used. However, they are preferably compounds as disclosed in DE 196 46 402.
- the usually arranged between layers of different spectral sensitivity non-photosensitive intermediate layers can contain agents which an undesirable diffusion of developer oxidation products from a photosensitive in another light-sensitive layer with different spectral Prevent awareness.
- Suitable connections can be found in Research Disclosure 37254, Part 7 (1995), p. 292 and in Research Disclosure 37038, Part III (1995), p. 84.
- the photographic recording material can also contain UV light-absorbing compounds, whiteners, spacers, other filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives to improve the stability of dyes, couplers and whites and to reduce the color fog, plasticizers (latices). , Biocide and others included.
- Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), p. 292 and in Research Disclosure 37038, Parts IV, V, VI, VII, X, XI and XIII (1995), P. 84 ff.
- the layers of color photographic materials are usually hardened, i.e., that Binder used, preferably gelatin, is replaced by suitable chemical Process networked.
- Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), P. 294 and in Research Disclosure 37038, Part XII (1995), p. 86.
- a color photographic recording material for color negative color development was produced (layer structure 1) by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities given relate to 1 m 2 .
- the corresponding amounts of AgNO 3 are given for the silver halide application; the silver halides were stabilized with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of AgNO 3 .
- the total layer structure had a swelling factor ⁇ 3.5 after curing.
- the structures 2 to 13 differ from structure 1 as indicated in the table.
- the additional layer 1 a is located between the base and layer 1.
- the materials according to the invention show good Normal storage stability, good latent image stability, good decolorization of the Filter yellow dye (small Dmin gb) with good color separation blue-green.
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
Die Erfindung betrifft ein farbfotografisches Aufzeichnungsmaterial, das in mindestens einer Schicht zwischen Unterlage und der zur Unterlage am nächsten befindlichen lichtempfindlichen Emulsionsschicht eine Verbindung der Formel (I) in der
- X und Y
- jeweils unabhängig von einander fiir eine elektronenziehende Gruppe stehen, und X und Y zusammen eine zur Vervollständigung eines 5- oder 6-Ringes notwendige Gruppe bilden können,
- X and Y
- each independently represent an electron-withdrawing group, and X and Y together can form a group necessary to complete a 5 or 6 ring,
Aus DE 2 328 014 und DE 2 421 068 sind farbfotografische Aufzeichnungsmaterialien bekannt, die in einer zusätzlichen Silberhalogenidemulsionsschicht Farbkuppler enthalten, wobei die Silberhalogenidemulsion verschleiert ist und die Schicht zur Maskierung dient.DE 2 328 014 and DE 2 421 068 are color photographic recording materials known that contain color couplers in an additional silver halide emulsion layer, wherein the silver halide emulsion is fogged and the layer for Masking is used.
Wenn die spektrale Zusammensetzung des auf eine lichtempfindliche fotografische Silberhalogenidemulsionsschicht auffallenden Lichtes kontrolliert bzw. gesteuert werden muß, kann in dem lichtempfindlichen fotografischen Aufzeichnungsmaterial zu diesem Zwecke eine gefärbte Schicht eingebaut werden, die dann als Filterschicht bezeichnet wird. So wird z.B. in farbfotografischen Materialien meist eine gelb gefärbte Filterschicht zwischen der blauempfindlichen Schicht und den darunter liegenden grünempfindlichen und rotempfindlichen Schichten angeordnet, um das blaue Licht von den grün- bzw. rotempfindlichen Schichten fern zu halten. If the spectral composition of the on a photosensitive photographic Silver halide emulsion layer of striking light can be controlled in the light-sensitive photographic material For this purpose, a colored layer is installed, which is then referred to as a filter layer becomes. For example, usually a yellow one in color photographic materials Filter layer between the blue sensitive layer and the one below green sensitive and red sensitive layers arranged to the blue light to keep away from the green or red sensitive layers.
An die in fotografischen Materialien verwendeten Farbstoffe sind hohe Anforderungen zu stellen. Sie müssen nicht nur eine dem Verwendungszweck entsprechende geeignete spektrale Absorption aufweisen, sondern sollen weiterhin fotochemisch inert sein. There are high demands on the dyes used in photographic materials to deliver. You don't just have to choose a suitable one for the intended use have spectral absorption, but should still be photochemically inert.
Insbesondere dürfen die Farbstoffe keine nachteiligen Einflüsse auf die Qualität der fotografischen Silberhalogenidemulsion ausüben; sie dürfen somit z.B. nicht die Empfindlichkeit drücken oder eine Schleierbildung verursachen. Außerdem sollten die Farbstoffe im Material zwar diffusionsfest sein, müssen aber während der Verarbeitung des Materials vollständig und irreversibel entfärbt oder aus der Schicht ausgewaschen werden, so daß keinerlei unerwünschte Anfärbung auf dem belichteten und entwickelten fotografischen Material zurückbleibt. Desweiteren sollten die Farbstoffe selber lagerstabil sein und auch im fotografischen Material zu keinerlei Veränderung während der Lagerung führen.In particular, the dyes must not have any adverse effects on the quality of the exercise photographic silver halide emulsion; you can e.g. not the Press sensitivity or cause fog. In addition, the Dyes in the material are diffusion resistant, but must be used during processing of the material completely and irreversibly discolored or washed out of the layer be so that no unwanted staining on the exposed and developed photographic material remains. Furthermore, the dyes be stable in storage and not change in the photographic material lead during storage.
Diese Anforderungen werden von den bekannten Farbstoffen nicht in befriedigendem Maße erfüllt. Das üblicherweise in Gelbfilterschichten verwendete kolloidale Silber führt leicht zu Schleierbildung in den benachbarten Emulsionsschichten. Wasserlösliche organische Farbstoffe, die durch Einführung langer Alkylketten diffusionsfest gemacht werden, wie sie z.B. in DE 22 59 746 genannt werden, werden in normalen fotografischen Verarbeitungsbädern .nicht oder nur unvollkommen entfärbt. Bei der Festlegung von Farbstoffen mit einer Beize, z.B. GB 1 034 044, US 3 740 228 oder DE-A-29 41 819, reicht im allgemeinen die Beizwirkung nicht aus, um den Farbstoff im erforderlichen Umfange in der Beizschicht festzulegen.These requirements are not satisfactory by the known dyes Dimensions met. The colloidal silver commonly used in yellow filter sheets easily leads to fog in the neighboring emulsion layers. water-soluble organic dyes diffusion resistant by introducing long alkyl chains be made as e.g. in DE 22 59 746 are mentioned in normal photographic processing baths. not or only incompletely discolored. In the Definition of dyes with a stain, e.g. GB 1 034 044, US 3 740 228 or DE-A-29 41 819, the pickling effect is generally not sufficient for the dye to the extent necessary in the pickling layer.
Aus der DE 196 46 402 sind Kondensationsprodukte von 3-Alkylisoxazolonen mit p-N,N-Bis-carbalkoxymethylaminobenzaldehyden bzw. N -Carbalkoxyethylcarbazol-3-aldehyden (Arylidenfarbstoffe) bekannt, die geeignete Absorption als Gelbfilterfarbstoffe aufweisen und in der Schicht bei Entwicklung völlig entfärbt werden.DE 196 46 402 includes condensation products of 3-alkylisoxazolones p-N, N-bis-carbalkoxymethylaminobenzaldehydes or N-carbalkoxyethylcarbazole-3-aldehydes (Arylidene dyes), the suitable absorption as yellow filter dyes exhibit and are completely discolored in the layer during development.
Es hat sich jedoch gezeigt, daß selbst bei den Filtergelbfarbstoffen gemäß der DE 196 46 402, die zwar eine gute Entfärbbarkeit aufweisen, die Lagerstabilität insbesondere auf Polyesterunterlagen bei Normallagerung unbefriedigend ist. Unter Normallagerung ist dabei eine Lagerung unter Lichtausschluß und Atmosphärenbedingungen bei einer Raumtemperatur (d.h. im Bereich von 15 bis 30°C) zu verstehen. Im Laufe der Lagerung konnte ein deutlicher Rückgang der Grünempfindlichkeit verzeichnet werden. However, it has been shown that even with the filter yellow dyes according to DE 196 46 402, which have good decolourability, the storage stability in particular on polyester pads is unsatisfactory with normal storage. Under normal storage is storage under exclusion of light and atmospheric conditions at a Room temperature (i.e. in the range of 15 to 30 ° C). During storage there was a significant decline in green sensitivity.
Häufig tritt auch eine unzureichende Latentbildstabilität auf. Diese äußert sich durch Änderung der sensitometrischen Eigenschaften des Materials während der Lagerung nach Belichtung im Vergleich zu einem Material, das direkt nach der Belichtung entwickelt wird. So können beispielsweise Änderungen in der Empfindlichkeit, im Kontrast, in der Farbabstimmung und in der Farbwiedergabe eintreten. Da bei fotografischen Filmaufnahmematerialien in der Regel mehrere Tage bis Wochen zwischen der Belichtung des Materials und dessen Entwicklung liegen, ist eine gute Latentbildstabilität bei diesen Materialien wichtig.Inadequate latent image stability often occurs. This manifests itself through Change in the sensitometric properties of the material during storage after exposure compared to a material that develops immediately after exposure becomes. For example, changes in sensitivity, contrast, occur in the color matching and in the color rendering. As for photographic Film footage usually takes several days to weeks between the exposure of the material and its development is good latent image stability important with these materials.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde ein farbfotografisches Aufzeichnungsmaterial, enthaltend eine gut entfärbbare Gelbfilterschicht, mit verbesserter Lagerstabilität zur Verfügung zu stellen. Insbesondere Materialien auf Polyesterbasis sollten bezüglich der Lagerstabilität verbessert werden. Gleichzeitig sollte eine gute Farbtrennung von Blau-Grün erreicht werden.The object of the present invention is a color photographic recording material, containing a decolourable yellow filter layer, with improved To provide storage stability. Especially polyester-based materials should be improved in terms of storage stability. At the same time, it should be a good one Color separation from blue-green can be achieved.
Überraschenderweise wurde gefunden, daß eine verbesserte Lagerstabilität mit aus dem Stand der Technik bekannten Gelbfilterfarbstoffen insbesondere jenen aus der DE 196 46 402 bekannten Farbstoffen erreicht werden kann, indem mindestens einer Schicht zwischen Unterlage und der zur Unterlage am nächsten befindlichen lichtempfindlichen Schicht eine Verbindung der Formel (I) zugesetzt wird. Dadurch konnte bei Normallagerung eine stabile Grünempfindlichkeit erreicht werden. Gleichzeitig konnte damit auch die Verbesserung der Latentbildstabilität erreicht werden.Surprisingly, it has been found that improved storage stability is also possible the yellow filter dyes known in the art, in particular those from the DE 196 46 402 known dyes can be achieved by at least one Layer between the base and the photosensitive closest to the base Layer a compound of formula (I) is added. This could a stable green sensitivity can be achieved with normal storage. simultaneously it was also possible to improve the latent image stability.
Gegenstand der vorliegenden Anmeldung ist ein farbfotografisches Aufzeichnungsmaterial, das auf einem Schichtträger mindestens eine rotempfindliche Silberhalogenidemulsionsschicht mit einem Blaugrünkuppler, mindestens eine grünempfindliche Silberhalogenidemulsionsschicht mit einem Purpurkuppler, mindestens eine blauempfindliche Silberhalogenidemulsionsschicht mit einem Gelbkuppler und mindestens eine gelb gefärbte nicht lichtempfindliche Schicht enthält, die unterhalb einer blauempfindlichen Silberhalogenidemulsionsschicht und oberhalb einer grünempfindlichen Silberhalogenidemulsionsschicht angeordnet ist (Gelbfilterschicht), dadurch gekennzeichnet, daß das Material mindestens in einer Schicht zwischen Unterlage und der zur Unterlage am nächsten befindlichen lichtempfindlichen Emulsionsschicht eine Verbindung der Formel (I) in der
- X und Y
- jeweils unabhängig von einander für eine elektronenziehende Gruppe, stehen, und X und Y zusammen eine zur Vervollständigung eines 5- oder 6-Ringes notwendige Gruppe bilden können,
- X and Y
- each independently represent an electron-withdrawing group, and X and Y together can form a group necessary to complete a 5 or 6 ring,
Bevorzugt handelt es sich dabei um offenkettige oder (hetero)cyclische Ketomethylenverbindungen der allgemeinen Formel (Ia) bzw. der entsprechenden tauto-meren Formel (Ib). in der
- Y
- für eine elektronenziehende Gruppe und
- R
- für Alkyl, Aryl, Alkoxy, Aryloxy, Alkylamino, Arylamino oder zusammen mit Y eine Gruppe zur Vervollständigung eines 5- oder 6-Ring(hetero)cyclus,
- Y
- for an electron-withdrawing group and
- R
- for alkyl, aryl, alkoxy, aryloxy, alkylamino, arylamino or together with Y a group to complete a 5- or 6-ring (hetero) cycle,
Die Verbindung der Formel (I) wird vorzugsweise in einer Menge von 0,01 bis 10 mmol/m2, insbesondere von 0,1 bis 2 mmol/m2 eingesetzt. Es kann dabei im Sinne der vorliegenden Anmeldung sowohl ausschließlich eine Verbindung als auch eine Mischung verschiedener Verbindungen der Formel (I) eingesetzt werden.The compound of formula (I) is preferably used in an amount of 0.01 to 10 mmol / m 2 , in particular 0.1 to 2 mmol / m 2 . For the purposes of the present application, only one compound and also a mixture of different compounds of the formula (I) can be used.
Die erfindungsgemäß einzusetzenden Verbindungen sowie deren Synthese sind aus der Literatur bekannt.The compounds to be used according to the invention and their synthesis are from known in literature.
Elektronenziehende Gruppe im Sinne der vorliegenden Erfindung sind beispielsweise R'CO-, R'R''NCO-, NC-, R'SO2- R'OCO-, R'R''NSO2 in einer bevorzugten Ausführungsform gemäß Formel (Ia) (im folgenden soll unter der Formel (Ia) auch jeweils die tautomere Form gemäß Formel (Ib) verstanden werden) steht X für -RCO und Y fiir eine elektronenziehende Gruppe R' und R" können dabei unabhängig voneinander die oben genannten Reste für R darstellen. Weitere im Sinne der vorliegenden Anmeldung bevorzugte Gruppen sind beschrieben in March, Advanced Organic Chemistry, 3rd Ed., S.17 und S. 238. Electron- withdrawing groups within the meaning of the present invention are, for example, R'CO-, R'R''NCO-, NC-, R'SO 2 - R'OCO-, R'R''NSO 2 in a preferred embodiment according to formula (Ia ) (in the following, the formula (Ia) is also to be understood to mean the tautomeric form of the formula (Ib)) X stands for -RCO and Y for an electron-withdrawing group R 'and R "can independently of one another the abovementioned radicals for R. Further groups preferred in the sense of the present application are described in March, Advanced Organic Chemistry, 3rd Ed., p.17 and p. 238.
In einer weiteren bevorzugten Ausführungsform bilden R und Y gemäß Formel Ia bzw. Ib gemeinsam eine Gruppe zur Vervollständigung eines 5 oder 6-Ringes.In a further preferred embodiment, R and Y form according to formula Ia or Ib together a group to complete a 5 or 6 ring.
Dabei kann es sich sowohl um einen Heterocyclus als auch um einen Cyclus ohne Heteroatome handeln. Vorzugsweise gebildete Ringsysteme sind beispielsweise Pyrazolone, Isoxazolone und Pyrazolidindione.This can be either a heterocycle or a cycle without Act heteroatoms. Ring systems preferably formed are, for example Pyrazolones, isoxazolones and pyrazolidinediones.
Unter Alkyl im Sinne der vorliegenden Anmeldung sind lineare oder verzweigte, cyclische oder geradkettige, substituierte oder nicht substituierte Kohlenwasserstoffe zu verstehen. Insbesondere handelt es sich dabei um Alkylgruppen mit 1 bis 12 C-Atomen, wie beispielsweise Methyl-, Ethyl-, Propyl-, Isopropyl-, Butyl-, t-Butyl-, Neopentyl- und 2-Ethylhexylgruppen. Diese können jedoch weiter substituiert sein, besonders bevorzugt mit einer Carboxycarbonylgruppe. Alkyl in the sense of the present application is understood to mean linear or branched, cyclic or straight-chain, substituted or unsubstituted hydrocarbons. In particular, these are alkyl groups with 1 to 12 carbon atoms, such as, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, neopentyl and 2-ethylhexyl groups. However, these can be further substituted, particularly preferably with a carboxycarbonyl group.
Unter Aryl im Sinne der vorliegenden Anmeldung sind aromatische Kohlenwasserstoffgruppen zu verstehen, wobei es sich vorzugsweise um 5- bis 6-gliedrige Ringsysteme handelt, welche monocyclisch aber auch als kondensierte Ringsysteme vorliegen können. Es kann sich dabei sowohl um substituierte als auch um nicht substituierte Ringsysteme handeln. Unter Aryl sollen im Sinne der vorliegenden Anmeldung auch Hetaryle verstanden werden. Dabei handelt es sich um aromatische Systeme welche mindestens ein Heteroatom enthalten. Es handelt sich auch hierbei vorzugsweise um 5- und 6-gliedrige Ringsysteme, welche monocyclisch aber auch als kondensierte Ringsysteme vorliegen können. Es kan dabei sowohl um substituierte als auch um nicht substituierte Ringsysteme handen. Als Heteroatome kommen dabei insbesondere N, S und O in Frage. Ein Ringsystem kann vorzugsweise zwischen 1 und 3 Heteroatome aufweisen, wobei es um die gleichen oder verschiedene Heteroatome handeln kann. Bei den kondensierten Ringsystemen können mehrere gleiche oder verschiedene heterocyclische Systeme kondensiert sein, also auch Hetaryle mit Arylen. Aryl for the purposes of the present application is to be understood as meaning aromatic hydrocarbon groups, which are preferably 5- to 6-membered ring systems, which can also be present as monocyclic but also as condensed ring systems. It can be both substituted and unsubstituted ring systems. For the purposes of the present application, aryl should also be understood to mean hetaryls. These are aromatic systems which contain at least one heteroatom. These are also preferably 5- and 6-membered ring systems, which can be monocyclic but also as condensed ring systems. It can be both substituted and unsubstituted ring systems. N, S and O are particularly suitable as heteroatoms. A ring system can preferably have between 1 and 3 heteroatoms, which can be the same or different heteroatoms. In the case of the condensed ring systems, several identical or different heterocyclic systems can be condensed, including hetaryls with aryls.
Unter Aryloxy im Sinne der vorliegenden Anmeldung sind die bereits unter Aryl definierten über ein Sauerstoffatom an den Rest gebundenen Gruppen zu verstehen. Aryloxy in the sense of the present application is understood to mean the groups already defined under aryl by an oxygen atom attached to the rest.
Unter Alkoxy im Sinne der vorliegenden Anmeldung sind die bereits unter Alkyl definierten über ein Sauerstoffatom an den Rest gebundenen Gruppen zu verstehen. Alkoxy in the sense of the present application is understood to mean the groups already defined under alkyl which are bonded to the rest via an oxygen atom.
Alkylamino im Sinne der vorliegenden Anmeldung sind die bereits unter Alkyl definierten über eine Aminogruppe an den Rest gebundenen Gruppen zu verstehen. For the purposes of the present application, alkylamino is to be understood as the groups already defined under alkyl which are bonded to the remainder via an amino group.
Arylamino im Sinne der vorliegenden Anmeldung sind die bereits unter Aryl definierten über eine Aminogruppe an den Rest gebundenen Gruppen zu verstehen. Arylamino in the sense of the present application are to be understood as the groups already defined under aryl by an amino group attached to the rest.
Typische Verbindungen der Formel (I) die erfindungsgemäß bevorzugt eingesetzt werden können sind die im folgenden aufgeführten Verbindungen A: Typical compounds of the formula (I) which can preferably be used according to the invention are the compounds A listed below:
In den vorangehenden Formeln A1 bis A33 stehen die Reste R1, R2, R3 und R4 jeweils unabhängig voneinander für eine Alkylgruppe, eine Arylgruppe, eine heterocyclische Gruppe oder eine Alkenylgruppe. Die Reste R5, R6 und R7 stehen ebenfalls unabhängig voneinander jeweils fiir ein Wasserstoffatom oder einen Substituenten. Bevorzugte Substituenten im Sinne der Anmeldung sind Alkylgruppen mit 1 bis 40 Kohlenstoffatomen wie beispielsweise Methyl-, Ethyl-, Propyl-, Isopropyl-, Butyl-, Tertiärbutyl-, Hexyl-, Octyl-, 2-Hydroxy-ethylgruppen, desweiteren Alkoxygruppen mit 1 bis 40 C Atomen wie beispielsweise Methoxy, Ethoxy oder Butoxy, sowie ein Halogenatom beispielsweise nur Chlor, Brom oder Fluor, weiterhin eine Mono- oder Dialkylamingruppe mit zusammen 1 bis 20 Kohlenstoffatomen in den Alkylgruppen, wobei die Alkylgruppen substituiert sein können, wie beispielsweise Dimethylamino, Diethylamino, Cyanoethylamino, eine Estergruppe mit 2 bis 20 Kohlenstoffatomen wie beispielsweise Methoxycarbonyl, Ethoxycarbonyl, Phenoxycarbonyl, eine Amidogruppe wie beispielsweise Acetylamino, Benzamino, eine Carbamylgruppe mit 1 bis 20 Kohlenstoffatomen wie beispielsweise Methylcarbamoyl, Ethylcarbamoyl, eine Sulfamoylgruppe mit 0 bis 20 Kohlenstoffatomen wie beispielsweise Methylsulfamoyl, Butylsulfamoyl, eine Arylgruppe mit 6 bis 10 Kohlenstoffatomen wie beispielsweise Phenyl, Napthyl, 4-Methoxyphenyl, 3-Methylphenyl, eine Acylgruppe mit 2 bis 20 Kohlenstoffatomen wie beispielsweise Acetyl, Benzoyl oder Propanoyl, eine Sulfonylgruppe mit 1-20 Kohlenstoffatomen wie beispielsweise Methansulfonyl oder Benzolsulfonyl, eine Ureidogruppe mit 1 bis 10 Kohlenstoffatomen wie beispielsweise Ureido oder Methylureido, eine Urethangruppe mit 2 bis 10 Kohlenstoffatomen wie beispielsweise Methoxycarbonylamino oder Ethoxycarbonylamino, eine Sulfonatgruppe wie beispielsweise Methoxysulfonyl oder Phenoxysulfonyl, eine Cyanogruppe, eine Hydroxylgruppe, eine Nitrogruppe und eine heterocyclische Gruppe wie beispielsweise Benzoxazol, Pyridin, oder Furan. Bei der durch R1, R2, R3 und R4 dargestellten Alkylgruppe kann es sich um eine Alkylgruppe mit 1 bis 20 Kohlenstoffatomen handeln, wie beispielsweise Methyl, Ethyl, Benzyl, Phenethyl, Propyl, Butyl, Isobutyl, Pentyl, Hexyl, Octyl oder Nonyl, welche gegebenenfalls Substituenten tragen können, es kann sich dabei um die bereits zuvor genannten Substituenten handeln. Als Arylgruppe können die Reste R1, R2, R3 und R4 vorzugsweise für eine Arylgruppe mit 6 bis 10 Kohlenstoffatomen stehen, wie beispielsweise Phenyl oder Naphtyl, welche ebenfalls durch die bereits zuvor erwähnten Substituenten substituiert sein können. Eine durch R1, R2, R3 oder R4 vertretene heterocyclische Gruppe kann vorzugsweise ein 5- oder 6-gliedriger Ring sein, wobei es sich beispielsweise um ein Oxazolring, Benzoxazolring, Thiazolring, Imidazolring, Pyridinring, Furanring, Thiophenring, Sulforanring, Pyrazolring, Pyrrolring, Chromanring oder Cumarinring handlen kann, welche ebenfalls mit den zuvor bereits erwähnten Substituenten substituiert sein können. Als Alkenylgruppen können R1, R2, R3 oder R4 vorzugsweise für eine Alkenylgruppe mit 2 bis 10 Kohlenstoffatomen stehen, wie beispielsweise Vinyl, Allyl, 1-propenyl, 2-pentenyl, oder 1,3-butadienyl. Wie bereits erwähnt können jeweils 2 der Substituenten R1 bis R7 aneinander gebunden sein und dabei ein Ringsystem ausbilden. Vorzugsweise handelt es sich um ein 5- oder 6-gliedriges Ringsystem, wie beispielsweise ein Pyrrolidinring, ein Piperidinring, einen Morpholinring oder einen Benzolring.In the preceding formulas A1 to A33, the radicals R 1 , R 2 , R 3 and R 4 each independently represent an alkyl group, an aryl group, a heterocyclic group or an alkenyl group. The radicals R 5 , R 6 and R 7 likewise each independently represent a hydrogen atom or a substituent. Preferred substituents in the sense of the application are alkyl groups with 1 to 40 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, hexyl, octyl, 2-hydroxyethyl groups, and furthermore alkoxy groups with 1 to 40 C atoms such as methoxy, ethoxy or butoxy, and a halogen atom, for example only chlorine, bromine or fluorine, furthermore a mono- or dialkylamine group with a total of 1 to 20 carbon atoms in the alkyl groups, where the alkyl groups can be substituted, such as dimethylamino, diethylamino , Cyanoethylamino, an ester group with 2 to 20 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, an amido group such as acetylamino, benzamino, a carbamyl group with 1 to 20 carbon atoms such as methylcarbamoyl, ethylcarbamoyl, a sulfamoyl group with 0 to 20 carbon atoms such as methylsulfamoyl Butylsulfamoyl, an aryl group m with 6 to 10 carbon atoms such as phenyl, naphthyl, 4-methoxyphenyl, 3-methylphenyl, an acyl group with 2 to 20 carbon atoms such as acetyl, benzoyl or propanoyl, a sulfonyl group with 1-20 carbon atoms such as methanesulfonyl or benzenesulfonyl, an ureido group with 1 to 10 carbon atoms such as ureido or methylureido, a urethane group with 2 to 10 carbon atoms such as methoxycarbonylamino or ethoxycarbonylamino, a sulfonate group such as methoxysulfonyl or phenoxysulfonyl, a cyano group, a hydroxyl group, a nitro group and a heterocyclic group such as benzoxazole, pyridine, furan. The alkyl group represented by R 1 , R 2 , R 3 and R 4 can be an alkyl group having 1 to 20 carbon atoms, such as, for example, methyl, ethyl, benzyl, phenethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl or nonyl, which can optionally carry substituents, these may be the substituents already mentioned. As the aryl group, the radicals R 1 , R 2 , R 3 and R 4 can preferably represent an aryl group having 6 to 10 carbon atoms, such as, for example, phenyl or naphthyl, which can also be substituted by the previously mentioned substituents. A heterocyclic group represented by R 1 , R 2 , R 3 or R 4 can preferably be a 5- or 6-membered ring, this being, for example, an oxazole ring, benzoxazole ring, thiazole ring, imidazole ring, pyridine ring, furan ring, thiophene ring, sulforane ring, Pyrazole ring, pyrrole ring, chroman ring or coumarin ring can act, which can also be substituted with the previously mentioned substituents. As alkenyl groups, R 1 , R 2 , R 3 or R 4 can preferably represent an alkenyl group having 2 to 10 carbon atoms, such as vinyl, allyl, 1-propenyl, 2-pentenyl, or 1,3-butadienyl. As already mentioned, 2 of the substituents R 1 to R 7 can be bonded to one another and thereby form a ring system. It is preferably a 5- or 6-membered ring system, such as a pyrrolidine ring, a piperidine ring, a morpholine ring or a benzene ring.
Besonders bevorzugt im Sinne der vorliegenden Erfindung sind A-8, A-11, A-12, A-13, A-15 und A-31.For the purposes of the present invention, particular preference is given to A-8, A-11, A-12, A-13, A-15 and A-31.
Insbesondere bevorzugte Verbindungen sind: Particularly preferred compounds are:
Erfindungsgemäß können die Verbindungen der Formel (I) vorzugsweise mindestens in einer beliebigen lichtunempfindlichen Schicht zwischen Unterlage und der zur Unterlage am nächsten befindlichen lichtempfindlichen Emulsionsschicht enthalten sein. Die Verbindungen der Formel (I) können dabei sowohl zu einer bereits vorhandenen Schicht hinzugefügt werden als auch in einer eigenen Schicht in das Material eingebracht werden. Bei Einbringung in Form einer eigenen Schicht handelt es sich üblicherweise um eine Schicht bestehend aus einem hydrophilen Kolloid, vorzugsweise Gelatine. Die Einbringung kann beispielsweise in hochsiedenden organische Lösungsmitteln erfolgen, als feinteilige Feststoffdispersion oder als beladener Latex gemäß aus dem Stand der Technik bekannter Verfahren erfolgen. Erfindungsgemäß sind die Verbindungen der Formel (I) in mindestens einer Schicht enthalten. Diese befindet sich vorzugsweise direkt auf der Unterlage. Mindestens eine Schicht bedeutet im Sinne der vorliegenden Anmeldung, daß die Verbindungen der Formel (I) auch in mehreren Schichten, maximal allen Schichten zwischen Unterlage und der zur Unterlage am nächsten befindlichen lichtempfindlichen Schicht, sowie in weiteren eventuell zusätzlich vorhandenen Schichten enthalten sein können. In einer weiteren bevorzugten Ausführungsform werden die Verbindungen zwei oder drei Schichten zugesetzt. Die Verbindungen werden einer Schicht, die sich vorzugsweise direkt auf der Unterlage unterhalb des Schichtaufbaus befindet und/oder einer Schicht, die weiter von der Unterlage entfernt ist als jede licht-empfindliche Schicht und/oder einer Schicht zugesetzt, die sich auf der Rückseite der Unterlage befindetAccording to the invention, the compounds of formula (I) can preferably at least in any light-insensitive layer between the base and the Contain the support closest to the photosensitive emulsion layer his. The compounds of the formula (I) can be used to form an existing one Layer can be added as well as in a separate layer in the material be introduced. When it is introduced in the form of a separate layer usually around a layer consisting of a hydrophilic colloid, preferably Gelatin. The introduction can, for example, in high-boiling organic solvents take place as a finely divided solid dispersion or as a loaded latex known methods are carried out. The compounds are according to the invention of the formula (I) contained in at least one layer. It is located preferably directly on the surface. At least one layer means in the sense of present application that the compounds of formula (I) also in several Layers, maximum of all layers between the base and the base on next located light-sensitive layer, as well as possibly in additional existing layers can be included. In another preferred In one embodiment, the compounds are added to two or three layers. The Connections are a layer that is preferably directly on the base is located below the layer structure and / or a layer that is further from the base is added as any light sensitive layer and / or a layer added is on the back of the pad
Die fotografischen Aufzeichnungsmaterialien bestehen aus einem Träger, auf den wenigstens eine lichtempfindliche Silberhalogenidemulsionsschicht aufgebracht ist. Als Träger eignen sich insbesondere dünne Filme und Folien. Eine Übersicht über Trägermaterialien und auf deren Vorder- und Rückseite aufgetragene Hilfsschichten ist in Research Disclosure 37254, Teil 1 (1995), S. 285 dargestellt. Verschiedene Polyesterunterlagen sind in der EP 0 601 501 A1 sowie der US 5,719,015 beschrieben. Im Rahmen der vorliegenden Erfindung werden bevorzugt Cellulosetriacetat sowie insbesondere Polyester eingesetzt. Polyester im Sinne der vorliegenden Erfindung sind beispielsweise in der EP 0601 501.A1 sowie der US 5.719.015 beschrieben, besonders bevorzugt sind Polyethylenglykol-2,6-naphthalat (PEN) und Polyethylenglykolterephthalat (PET).The photographic recording materials consist of a support on which at least one photosensitive silver halide emulsion layer is applied. Thin films and foils are particularly suitable as supports. An overview of Backing materials and auxiliary layers applied to their front and back is presented in Research Disclosure 37254, Part 1 (1995), p. 285. Various Polyester bases are in EP 0 601 501 A1 and US 5,719,015 described. Cellulose triacetate is preferred in the context of the present invention and in particular polyester used. Polyester in the sense of the present Invention are, for example, in EP 0601 501.A1 and US 5,719,015 described, particularly preferred are polyethylene glycol 2,6-naphthalate (PEN) and Polyethylene glycol terephthalate (PET).
Beispiele fiir farbfotografischer Aufzeichnungsmaterialien sind Farbnegativfilme und Farbpositivfilme. Eine Übersicht über typische farbfotografische Aufzeichnungsmaterialien sowie bevorzugte Ausführungsformen und Verarbeitungsprozesse findet sich in Research Disclosure 37038 (Februar 1995). Examples of color photographic recording materials are color negative films and Color positive films. An overview of typical color photographic recording materials as well as preferred embodiments and processing processes can be found in Research Disclosure 37038 (February 1995).
Die farbfotografischen Aufzeichnungsmaterialien enthalten üblicherweise mindestens je eine rotempfindliche, grünempfindliche und blauempfindliche Silberhalogenidemulsionsschicht sowie gegebenenfalls Zwischenschichten und Schutzschichten.The color photographic recording materials usually contain at least one red sensitive, one green sensitive and one blue sensitive silver halide emulsion layer and, if necessary, intermediate layers and protective layers.
Je nach Art des fotografischen Materials können diese Schichten unterschiedlich angeordnet sein. Dies sei fiir die wichtigsten Produkte dargestellt:Depending on the type of photographic material, these layers can be arranged differently his. This is shown for the most important products:
Farbfotografische Filme wie Colomegativfilme weisen in der nachfolgend angegebenen Reihenfolge auf dem Träger 2 oder 3 rotempfindliche, blaugrünkuppelnde Silberhalogenidemulsionsschichten, 2 oder 3 grünempfindliche, purpurkuppelnde Silberhalogenidemulsionsschichten und 2 oder 3 blauempfindliche, gelbkuppelnde Silberhalogenidemulsionsschichten auf. Die Schichten gleicher spektraler Empfindlichkeit unterscheiden sich in ihrer fotografischen Empfindlichkeit, wobei die weniger empfindlichen Teilschichten in der Regel näher zum Träger angeordnet sind als die höher empfindlichen Teilschichten.Color photographic films such as colomegative films show in the below Order on the carrier 2 or 3 red-sensitive, cyan-green domes Silver halide emulsion layers, 2 or 3 green-sensitive, purple-coupling silver halide emulsion layers and 2 or 3 blue sensitive, yellow coupling silver halide emulsion layers on. The layers of the same spectral sensitivity differ in their photographic sensitivity, the less sensitive sub-layers are usually arranged closer to the carrier than that higher sensitive sub-layers.
Die Möglichkeiten der unterschiedlichen Schichtanordnungen und ihre Auswirkungen auf die fotografischen Eigenschaften werden in J. Inf. Rec. Mats., 1994, Vol. 22, Seiten 183 - 193 beschrieben.The possibilities of the different layer arrangements and their effects the photographic properties are described in J. Inf. Rec. Mats., 1994, Vol. 22, Pages 183-193.
Abweichungen von Zahl und Anordnung der lichtempfindlichen Schichten können zur Erzielung bestimmter Ergebnisse vorgenommen werden. Zum Beispiel können alle hochempfindlichen Schichten zu einem Schichtpaket und alle niedrigempfindlichen Schichten zu einem anderen Schichtpaket in einem fotografischen Film zusammengefaßt sein, um die Empfindlichkeit zu steigern (DE 25 30 645).Deviations in the number and arrangement of the photosensitive layers can occur to achieve certain results. For example, you can all highly sensitive layers in one layer package and all low-sensitive layers Layers combined into another layer package in a photographic film be to increase sensitivity (DE 25 30 645).
Wesentliche Bestandteile der fotografischen Emulsionsschichten sind Bindemittel, Silberhalogenidkörner und Farbkuppler. Essential components of the photographic emulsion layers are binders, Silver halide grains and color couplers.
Angaben über geeignete Bindemittel finden sich in Research Disclosure 37254, Teil 2 (1995), S.286.Information on suitable binders can be found in Research Disclosure 37254, Part 2 (1995), p.286.
Angaben über geeignete Silberhalogenidemulsionen, ihre Herstellung, Reifung, Stabilisierung und spektrale Sensibilisierung einschließlich geeigneter Spektralsensibilisatoren finden sich in Research Disclosure 36544 (Sept.1994) und Research Disclosure 37254, Teil 3 (1995), S. 286 und in Research Disclosure 37038, Teil XV (1995), S.89.Information about suitable silver halide emulsions, their preparation, maturation, stabilization and spectral sensitization including suitable spectral sensitizers can be found in Research Disclosure 36544 (Sept. 1994) and Research Disclosure 37254, Part 3 (1995), p. 286 and in Research Disclosure 37038, Part XV (1995), p.89.
Fotografische Materialien mit Kameraempfindlichkeit enthalten üblicherweise Silberbronüdiodidemulsionen, die gegebenenfalls auch geringe Anteile Silberchlorid enthalten können. Fotografische Kopiermaterialien enthalten entweder Silberchloridbromidemulsionen mit bis 80 mol-% AgBr oder Silberchloridbromidemulsionen mit über 95 mol-% AgCl.Photographic materials with camera sensitivity usually contain silver bronze iodide emulsions, which may also contain small amounts of silver chloride can. Photographic copying materials contain either silver chloride bromide emulsions with up to 80 mol% of AgBr or silver chloride bromide emulsions over 95 mol% AgCl.
Im Sinne der vorliegenden Erfindung handelt es sich bei den verwendeten Emulsionen in einer bevorzugten Ausführungsformen um Tab-Grain Emulsionen. Darunter sind Emulsionen mit Silberhalogenidkristallen zu verstehen, die einen tafelförmigen Habitus mit einem Aspektverhältnis >2 besitzen, wobei das Aspektverhältnis das Verhältnis von Durchmesser des flächengleichen Kreises der Projektionsfläche zur Dicke des Kristalls ist.For the purposes of the present invention, the emulsions used are in a preferred embodiment around tab grain emulsions. among them are to be understood as emulsions with silver halide crystals, which have a tabular Have habit with an aspect ratio> 2, the aspect ratio being Ratio of the diameter of the circle of the same area of the projection area to the Thickness of the crystal is.
Die fotografischen Emulsionen können unter Verwendung von Methinfarbstoffen oder anderen Farbstoffen spektral sensibilisiert werden. Besonders geeignete Farbstoffe sind Cyaninfarbstoffe, Merocyaninfarbstoffe, und komplexe Merocyaninfarbstoffe. Derartige Verbindungen, insbesondere Merocyanine, können auch als Stabilisatoren verwendet werden.The photographic emulsions can be made using methine dyes or other dyes are spectrally sensitized. Particularly suitable dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Such compounds, especially merocyanines, can also be used as Stabilizers are used.
Eine Übersicht über die als Spektralsensibilisatoren geeigneten Polymethinfabstoffe, über deren geeignete Kombinationen und insbesondere über supersensibilisierend wirkende Kombinationen enthält Research Disclosure 17643 (1978), Kapitel IV, und Research Disclosure 18716 (1979), S. 648 (rechte Spalte) bis S. 649 (rechte Spalte).An overview of the polymethine waste materials suitable as spectral sensitizers, about their suitable combinations and especially about supersensitizing effective combinations are contained in Research Disclosure 17643 (1978), Chapter IV, and Research Disclosure 18716 (1979), p. 648 (right column) to p. 649 (right column).
Als Rotsensibilisatoren können darüber hinaus Pentamethincyanine mit Naphthothiazol, Naphthoxazol oder Benzthiazol als basische Endgruppen verwendet werden, welche mit Halogen, Methyl- oder Methoxygruppen substituiert und 9,11-alkylen-, insbesondere 9,11-neopentylen-verbrückt sein können wie in GB 604 217 und BE 660 948 beschrieben wird.Die N,N'-Substituenten können wie in EP 0 532 042 beschrieben auch C4-C8-Alkylgruppen sein. Die Methinkette kann zusätzlich noch Substituenten tragen wie in EP 0 532 042 erwähnt wird. Es können auch Pentamethine mit nur einer Methylgruppe am Cyklohexenring verwendet werden wie in EP 0 532 042 beschrieben wird. Der Rotsensibilisator kann, wie in BE 660 948 beschrieben, durch Zusatz heterocyclischer Mercaptoverbindungen supersensibilisiert und stabilisiert werden.Pentamethine cyanines with naphthothiazole, naphthoxazole or benzothiazole as basic end groups can also be used as red sensitizers, which can be substituted with halogen, methyl or methoxy groups and bridged by 9,11-alkylene, in particular 9,11-neopentylene, as in GB 604 217 and BE 660 948. The N, N 'substituents can also be C 4 -C 8 alkyl groups as described in EP 0 532 042. The methine chain can additionally carry substituents as mentioned in EP 0 532 042. Pentamethines with only one methyl group on the cyclohexene ring can also be used, as described in EP 0 532 042. As described in BE 660 948, the red sensitizer can be supersensitized and stabilized by adding heterocyclic mercapto compounds.
Die rotempfindliche Schicht kann zusätzlich zwischen 390 und 590 nm, bevorzugt bei 500 nm spektral sensibilisiert sein, um so eine verbesserte Differenzierung der Rottöne zu bewirken, gemäß EP 0 304 297, US 806 460 und US 5 084 374.The red-sensitive layer can additionally between 390 and 590 nm, preferably at 500 nm be spectrally sensitized in order to improve the differentiation of the To cause red tones according to EP 0 304 297, US 806 460 and US 5 084 374.
Derartige Verbindungen, insbesondere Merocyanine, können auch als Stabilisatoren verwendet werden.Such compounds, especially merocyanines, can also act as stabilizers be used.
Die Spektralsensibilisatoren können in gelöster Form oder als Dispergat der fotografischen Emulsion zugesetzt werden. Sowohl Lösung als auch Dispergat können Zusätze wie beispielsweise Netzmittel, Dispergiermittel oder Puffer enthalten.The spectral sensitizers can be in dissolved form or as a disperse of the photographic Emulsion can be added. Both solution and dispersate can be additives such as wetting agents, dispersants or buffers.
Der Spektralsensibilisator oder eine Kombination von Spektralsensibilisatoren kann vor, während oder nach der Emulsionsbereitung zugesetzt werden.The spectral sensitizer or a combination of spectral sensitizers can before, during or after the emulsion preparation.
Angaben zu den üblichen Farbkupplern finden sich in Research Disclosure 37254, Teil 4 (1995), S. 288 und in Research Disclosure 37038, Teil II (1995), S. 80. Information on the usual color couplers can be found in Research Disclosure 37254, Part 4 (1995), p. 288 and in Research Disclosure 37038, Part II (1995), p. 80.
Die maximale Absorption der aus den Kupplern und dem Farbentwickleroxidationsprodukt gebildeten Farbstoffe liegt vorzugsweise in den folgenden Bereichen: Gelbkuppler 430 bis 460 nm, Purpurkuppler 540 bis 560 nm, Blaugrünkuppler 630 bis 700 nm.The maximum absorption of that from the couplers and the color developer oxidation product Dyes formed are preferably in the following areas: Yellow coupler 430 to 460 nm, purple coupler 540 to 560 nm, cyan coupler 630 up to 700 nm.
In farbfotografischen Filmen werden zur Verbesserung von Empfindlichkeit; Körnigkeit, Schärfe und Farbtrennung häufig Verbindungen eingesetzt, die bei der Reaktion mit dem Entwickleroxidationsprodukt Verbindungen freisetzen, die fotografisch wirksam sind, z.B. DIR-Kuppler, die einen Entwicklungsinhibitor abspalten.In color photographic films are used to improve sensitivity; graininess Sharpness and color separation are often used in the compounds in the reaction with the developer oxidation product release compounds that are photographically effective are, e.g. DIR couplers that release a development inhibitor.
Angaben zu solchen Verbindungen, insbesondere Kupplern, finden sich in Research Disclosure 37254, Teil 5 (1995), S. 290 und in Research Disclosure 37038, Teil XIV (1995), S. 86.Information on such compounds, in particular couplers, can be found in Research Disclosure 37254, Part 5 (1995), p. 290 and in Research Disclosure 37038, Part XIV (1995), p. 86.
Das erfindungsgemäße farbfotografische Aufzeichnungsmaterial kann weiterhin Verbindungen enthalten, die beispielsweise einen Entwicklungsinhibitor, einen Entwicklungsbeschleuniger, einen Bleichbeschleuniger, einen Entwickler, ein Silberhalogenidlösungsmittel, ein Schleiermittel oder ein Antischleiermittel in Freiheit setzten können, beispielsweise sogenannte DIR-Hydrochinone oder andere Verbindungen, wie sie beispielsweise in US-A 4,636.546, US-A 4,345.024, US-A 4,684.604 und in DE-A 24 47 079, DE-A 25 15 213 und DE-A 31 45 640 oder in EP-A 198 438 beschrieben sind. Diese Verbindungen erfüllen die gleiche Funktion wie DIR-, DARoder FAR-Kuppler, außer daß sie keine Kupplungsprodukte bilden.The color photographic recording material according to the invention can also be compounds contain, for example, a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, set an antifoggant or antifoggant free can, for example so-called DIR hydroquinones or other compounds, as for example in US-A 4,636,546, US-A 4,345,024, US-A 4,684,604 and in DE-A 24 47 079, DE-A 25 15 213 and DE-A 31 45 640 or in EP-A 198 438 are described. These connections perform the same function as DIR, DAR or FAR couplers, except that they do not form coupling products.
Hochmolekulare Farbkuppler sind beispielsweise 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 und US-A 4 080 211 beschrieben. Die hochmolekularen Farbkuppler werden in der Regel durch Polymerisation von ethylenisch ungesättigten Farbkupplermonomeren hergestellt. Sie können aber auch durch Polyaddition oder Polykondensation erhalten werden. 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 and US-A 4 080 211. The high molecular weight color couplers are usually polymerized by produced ethylenically unsaturated color coupler monomers. But you can too can be obtained by polyaddition or polycondensation.
Die Einarbeitung der Farbkuppler in Silberhalogenidemulsionsschichten kann in der Weise erfolgen, daß zunächst von der betreffenden Verbindung eine Lösung oder eine Dispersion hergestellt und dann der Gießlösung fiir die betreffende Schicht zugefügt wird. Die Auswahl des geeigneten Lösungs- oder Dispersionsmittels hängt von der Löslichkeit der Verbindung ab.The incorporation of the color coupler in silver halide emulsion layers can be done in the Way that first of the compound in question a solution or Dispersion prepared and then added to the casting solution for the layer in question becomes. The choice of the appropriate solvent or dispersant depends on the Solubility of the compound.
Methoden zum Einbringen von in Wasser im wesentlichen unlöslichen Verbindungen durch Mahlverfahren sind beispielsweise in DE-A 26 09 741 und DE-A 26 09 742 beschrieben.Methods for introducing compounds which are essentially insoluble in water by grinding processes are, for example, in DE-A 26 09 741 and DE-A 26 09 742 described.
Die meist hydrophoben Farbkuppler, aber auch andere hydrophobe Bestandteile der Schichten, werden üblicherweise in hochsiedenden organischen Lösungsmitteln gelöst oder dispergiert. Diese Lösungen oder Dispersionen werden dann in einer wäßrigen Bindemittellösung (üblicherweise Gelatinelösung) emulgiert und liegen nach dem Trocknen der Schichten als feine Tröpfchen (0,05 bis 0,8µm Durchmesser) in den Schichten vor.The mostly hydrophobic color coupler, but also other hydrophobic components of the Layers are usually dissolved in high-boiling organic solvents or dispersed. These solutions or dispersions are then in an aqueous Binder solution (usually gelatin solution) emulsified and lie after Drying the layers as fine droplets (0.05 to 0.8 µm diameter) in the Layers before.
Geeignete hochsiedende organische Lösungsmittel, Methoden zur Einbringung in die Schichten eines fotografischen Materials und weitere Methoden, chemische Verbindungen in fotografische Schichten einzubringen, finden sich in Research Disclosure 37254, Teil 6 (1995), S. 292.Suitable high-boiling organic solvents, methods for incorporation into the Layers of photographic material and other methods, chemical compounds To be incorporated into photographic layers can be found in Research Disclosure 37254, Part 6 (1995), p. 292.
Die Verbindungen können auch in Form sogenannter beladener Latices in die Gießlösung eingebracht werden. Verwiesen wird beispielsweise auf DE-A 25 41 230, DE-A25 41 274, DE-A 28 35 856, EP-A 0 014 921, EP-A 0 069 671, EP-A 0 130 115, US-A 4,291.113. Die diffusionsfeste Einlagerung anionischer wasserlöslicher Verbindungen (z.B. von Kupplern oder Farbstoffen) kann auch mit Hilfe von kationischen Polymeren, sogenannten polymeren Beizmitteln, erfolgen. The compounds can also be in the form of so-called loaded latices Pouring solution are introduced. Reference is made, for example, to DE-A 25 41 230, DE-A25 41 274, DE-A 28 35 856, EP-A 0 014 921, EP-A 0 069 671, EP-A 0 130 115, US-A 4,291,113. The diffusion-resistant storage of anionic water-soluble Connections (e.g. from couplers or dyes) can also be made using cationic polymers, so-called polymeric mordants.
Geeignete Ölformer sind z.B. Phthalsäurealkylester, Phosphorsäureester, Phosphonsäureester. Zitronensäureester, Milchsäureester, Benzoesäureester, Fettsäureester, Amide, Alkohole, Phenole, Sulfonamide, Anilinderivate und Kohlenwasserstoffe.Suitable oil formers are e.g. Alkyl phthalates, phosphoric esters, phosphonic esters. Citric acid esters, lactic acid esters, benzoic acid esters, fatty acid esters, Amides, alcohols, phenols, sulfonamides, aniline derivatives and hydrocarbons.
Gelbfilterfarbstoffe werden üblicherweise zwischen den grünempfindlichen und blauempfindlichen Schichten angebracht, sie hindern blaues Licht daran in die darunter liegenden Schichten zu gelangen.Yellow filter dyes are usually between the green sensitive and blue sensitive Layers applied, they prevent blue light in the below to reach lying layers.
Erfindungsgemäß können alle aus dem Stand der Technik bekannten Gelbfilterfarbstoffe eingesetzt werden. Bevorzugt handelt es sich jedoch um Verbindungen wie sie in der DE 196 46 402 offenbart sind.According to the invention, all yellow filter dyes known from the prior art can be used. However, they are preferably compounds as disclosed in DE 196 46 402.
Die in der Regel zwischen Schichten unterschiedlicher Spektralempfindlichkeit angeordneten nicht lichtempfindlichen Zwischenschichten können Mittel enthalten, die eine unerwünschte Diffusion von Entwickleroxidationsprodukten aus einer lichtempfindlichen in eine andere lichtempfindliche Schicht mit unterschiedlicher spektraler Sensibilisierung verhindern.The usually arranged between layers of different spectral sensitivity non-photosensitive intermediate layers can contain agents which an undesirable diffusion of developer oxidation products from a photosensitive in another light-sensitive layer with different spectral Prevent awareness.
Geeignete Verbindungen (Weißkuppler, Scavenger oder EOP-Fänger) finden sich in Research Disclosure 37254, Teil 7 (1995), S. 292 und in Research Disclosure 37038, Teil III (1995), S. 84.Suitable connections (white coupler, scavenger or EOP catcher) can be found in Research Disclosure 37254, Part 7 (1995), p. 292 and in Research Disclosure 37038, Part III (1995), p. 84.
Das fotografische Aufzeichnungsmaterial kann weiterhin UV-Licht absorbierende Verbindungen, Weißtöner, Abstandshalter, weitere Filterfarbstoffe, Formalinfänger, Lichtschutzmittel, Antioxidantien, DMin-Farbstoffe, Zusätze zur Verbesserung der Farbstoff-, Kuppler- und Weißenstabilität sowie zur Verringerung des Farbschleiers, Weichmacher (Latices), Biocide und anderes enthalten.The photographic recording material can also contain UV light-absorbing compounds, whiteners, spacers, other filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives to improve the stability of dyes, couplers and whites and to reduce the color fog, plasticizers (latices). , Biocide and others included.
Geeignete Verbindungen finden sich in Research Disclosure 37254, Teil 8 (1995), S. 292 und in Research Disclosure 37038, Teile IV, V, VI, VII, X, XI und XIII (1995), S. 84 ff. Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), p. 292 and in Research Disclosure 37038, Parts IV, V, VI, VII, X, XI and XIII (1995), P. 84 ff.
Die Schichten farbfotografischer Materialien werden üblicherweise gehärtet, d.h., das verwendete Bindemittel, vorzugsweise Gelatine, wird durch geeignete chemische Verfahren vernetzt.The layers of color photographic materials are usually hardened, i.e., that Binder used, preferably gelatin, is replaced by suitable chemical Process networked.
Geeignete Härtersubstanzen finden sich in Research Disclosure 37254, Teil 9 (1995), S. 294 und in Research Disclosure 37038, Teil XII (1995), Seite 86.Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), P. 294 and in Research Disclosure 37038, Part XII (1995), p. 86.
Nach bildmäßiger Belichtung werden farbfotografische Materialien ihrem Charakter entsprechend nach unterschiedlichen Verfahren verarbeitet. Einzelheiten zu den Verfahrensweisen und dafür benötigte Chemikalien sind in Research Disclosure 37254, Teil 10 (1995), S. 294 sowie in Research Disclosure 37038, Teile XVI bis XXIII (1995), S. 95 ff. zusammen mit exemplarischen Materialien veröffentlicht. After photographic exposure, color photographic materials become their character processed according to different processes. Details of the Procedures and chemicals required for this are in Research Disclosure 37254, Part 10 (1995), p. 294 and in Research Disclosure 37038, Parts XVI to XXIII (1995), p. 95 ff. Published together with exemplary materials.
Ein farbfotografisches Aufzeichnungsmaterial für die Colornegativfarbentwicklung wurde hergestellt (Schichtaufbau 1), indem auf einen transparenten Schichtträger aus Cellulosetriacetat die folgenden Schichten in der angegebenen Reihenfolge aufgetragen wurden. Die Mengenangaben beziehen sich jeweils auf 1 m2. Für den Silberhalogenidauftrag sind die entsprechenden Mengen AgNO3 angegeben; die Silberhalogenide wurden mit 0,5 g 4-Hydroxy-6-methyl-1,3,3a,7-tetraazainden pro mol AgNO3 stabilisiert.A color photographic recording material for color negative color development was produced (layer structure 1) by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities given relate to 1 m 2 . The corresponding amounts of AgNO 3 are given for the silver halide application; the silver halides were stabilized with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of AgNO 3 .
Der Gesamtschichtaufbau hatte nach der Härtung einen Quellfaktor ≤ 3,5.The total layer structure had a swelling factor ≤ 3.5 after curing.
Im Beispiel 1 verwendete Substanzen: Substances used in example 1:
Nach Aufbelichten eines Graukeils wurde die Entwicklung nach "The British Journal of Photography", 1974, Seiten 597 und 598 durchgeführt.After exposing a gray wedge, the development was carried out according to "The British Journal of Photography", 1974, pages 597 and 598.
Die Aufbauten 2 bis 13 unterscheiden sich von Aufbau 1 wie in der Tabelle angegeben. Die zusätzliche Schicht 1 a befindet sich zwischen der Unterlage und Schicht 1. The structures 2 to 13 differ from structure 1 as indicated in the table. The additional layer 1 a is located between the base and layer 1.
Wie aus der Tabelle ersichtlich zeigen die erfindungsgemäßen Materialien gute Normallagerstabilität, gute Latentbildstabilität, eine gute Entfärbbarkeit des Filtergelbfarbstoffs (kleines Dmin gb) bei guter Farbtrennung Blau-Grün.As can be seen from the table, the materials according to the invention show good Normal storage stability, good latent image stability, good decolorization of the Filter yellow dye (small Dmin gb) with good color separation blue-green.
Claims (10)
- A colour photographic recording material comprising on a film base at least one antihalation layer, a red-sensitive silver halide emulsion layer comprising a cyan-forming colour coupler, at least one green-sensitive silver halide emulsion layer comprising a magenta-forming colour coupler, at least one blue-sensitive silver halide emulsion layer comprising a yellow-forming colour coupler, and at least one yellow coloured, light-insensitive layer (yellow filter layer), which is disposed below a blue-sensitive silver halide emulsion layer and above a green-sensitive silver halide emulsion layer, characterised in that the material contains in at least one layer between the base and the antihalation layer a compound corresponding to formula (I) wherein
each of X and Y, independently one from the other, represents an electron-withdrawing group, and X and Y together may form a group that is necessary for completing a 5- or 6-membered ring. - A colour photographic recording material according to claim 1, characterised in that said compound is a compound corresponding to formula Ia or Ib wherein
- Y
- represents an electron-withdrawing group, and
- R
- represents alkyl, aryl, alkoxy, aryloxy, alkylamino, arylamino, or R together with Y represents a group for completing a 5- or 6-membered (hetero)cycle.
- A colour photographic recording material according to any of claims 1 to 3, characterised in that it contains said compounds corresponding to formula (I) in at least one layer directly adjacent to the base.
- A colour photographic recording material according to any of claims 1 to 4, characterised in that it further contains compounds corresponding to formula (I) in a layer more remote from the base than any light-sensitive layer and/or in layer present on the back of the base.
- A colour photographic recording material according to any of claims 1 to 5, characterised in that it contains said compounds corresponding to formula (I) in an additional layer on the face of the base that is turned away from the light-sensitive layer.
- A colour photographic recording material according to any of claims 1 to 6, characterised in that said compound corresponding to formula (I) is used in an amount from 0.1 to 2 mmole/m2.
- A colour photographic recording material according to any of claims 1 to 7, characterised in that a polyester base is used as a base.
- A colour photographic recording material according to any of claims 1 to 8, characterised in that said base is a polyethylene glycol 2,6-naphthalate base or a polyethylene glycol terephthalate base.
- A colour photographic recording material comprising on a film base at least one red-sensitive silver halide emulsion layer comprising a cyan-forming colour coupler, at least one green-sensitive silver halide emulsion layer comprising a magenta-forming colour coupler, at least one blue-sensitive silver halide emulsion layer comprising a yellow-forming colour coupler, and at least one yellow coloured, light-insensitive layer (yellow filter layer), which is disposed below a blue-sensitive silver halide emulsion layer and above a green-sensitive silver halide emulsion layer, characterised in that the material contains in at least one layer between the base and the light-sensitive emulsion layer situated nearest to the base a compound corresponding to the formula (I) wherein
each of X and Y, independently one from the other, represents an electron-withdrawing group, and X and Y together may form a group that is necessary for completing a 5- or 6-membered ring,
and said film base being a polyester-based base.
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DE19858999 | 1998-12-21 | ||
DE19858999A DE19858999A1 (en) | 1998-12-21 | 1998-12-21 | Color photographic recording material |
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US2927019A (en) * | 1954-11-12 | 1960-03-01 | Du Pont | Photographic elements and processes of photography |
DE2328014A1 (en) * | 1973-06-01 | 1974-12-19 | Agfa Gevaert Ag | Colour photographic material with automatic masking - using fogged emulsion contg. mask-forming coupler |
DE2421068C2 (en) * | 1974-05-02 | 1982-11-25 | Agfa-Gevaert Ag, 5090 Leverkusen | Color photographic multilayer recording material |
DE19646402A1 (en) * | 1996-01-12 | 1997-10-23 | Agfa Gevaert Ag | Yellow filter layer for silver halide colour photographic recording materials |
US5776667A (en) * | 1996-01-12 | 1998-07-07 | Agfa Ag | Color photographic recording material having a yellow filter layer which contains an arylidene dye of isoxazolone as the yellow filter dye |
DE19710611C2 (en) * | 1997-03-14 | 2003-04-03 | Agfa Gevaert Ag | Color photographic silver halide material |
DE19742040C2 (en) * | 1997-09-24 | 1999-07-29 | Agfa Gevaert Ag | Color photographic silver halide material |
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1998
- 1998-12-21 DE DE19858999A patent/DE19858999A1/en not_active Withdrawn
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1999
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- 1999-12-08 EP EP99124022A patent/EP1014183B1/en not_active Expired - Lifetime
- 1999-12-14 JP JP11354658A patent/JP2000181035A/en active Pending
- 1999-12-14 US US09/461,476 patent/US6228568B1/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
US6228568B1 (en) | 2001-05-08 |
EP1014183A3 (en) | 2000-11-22 |
DE19858999A1 (en) | 2000-06-29 |
EP1014183A2 (en) | 2000-06-28 |
DE59907279D1 (en) | 2003-11-13 |
JP2000181035A (en) | 2000-06-30 |
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