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
  • G03C7/39296—Combination of additives
• • 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
  • G03C7/39212—Carbocyclic
  • G03C7/39216—Carbocyclic with OH groups

Definitions

• the invention relates to a color photographic recording material with improved dye stability.
• Color photographic materials usually contain at least one yellow coupler, at least one purple coupler and at least one cyan coupler, from which the corresponding dyes are formed by exposure and development.
• These dyes in particular the dyes that are constantly exposed to light, are said to have high color stability, with particular emphasis being placed on ensuring that the color stability of all three colors is as good as possible, so that there is no color distortion with a slight fading.
• Yellow dyes in particular which are produced from couplers with an open-chain ketomethylene grouping, require both stabilization against light and against fading in the dark (dark fading).
• Suitable bridge members R1 are e.g. Alkylene, alkylidene or sulfonyl groups and heteroatoms such as 0 and S.
• Examples of R are methyl, ethyl, propyl, tert-butyl, n-butyl, cyclohexyl, dodecyl, hexadecyl and benzyl.
• R and R1 have the meaning given above and the alkyl and aryl radicals can be further substituted.
• Suitable compounds of formula I are: The compounds are preferably used in a layer containing a color coupler in an amount of 0.1 to 2 mol / mol of color coupler, in particular in an amount of 0.1 to 0.5 mol / mol of color coupler.
• the radicals R51 and R52 can also form a 5- to 8-membered ring.
• alkyl or aryl radicals can be substituted, for example by hydroxy, alkyl, aryl, hetaryl, alkoxy, aryloxy, acyloxy, alkoxycarbonyl, acylamino, carbamoyl, sulfonamino, sulfamoyl, sulfonyl and halogen.
• An acyl radical can be derived from a carboxylic acid (e.g. acetyl, acrylic), a carbamic acid (e.g. dodecylaminocarbonyl, butylaminocarbonyl) or a carbonic acid semi-ester (e.g. ethoxycarbonyl, hexyldecyloxycarbonyl).
• a carboxylic acid e.g. acetyl, acrylic
• a carbamic acid e.g. dodecylaminocarbonyl, butylaminocarbonyl
• a carbonic acid semi-ester e.g. ethoxycarbonyl, hexyldecyloxycarbonyl.
• the compounds III, IV and V can also be bonded to a polymer chain via one of the substituents.
• the compounds according to the invention are preferably used in combination with yellow couplers. Dye stabilization of the photographic materials is also achieved with other couplers, magenta and cyan couplers. Yellow couplers are preferably used in an amount of 0.1 to 1 mmol / m2 material.
• the yellow couplers which are preferably used in one layer with the dye stabilizers according to the invention, are preferably 2-equivalent pivaloyl yellow couplers, the leaving group of which is connected to the coupling position of the coupler either via oxygen or via nitrogen.
• AgBr, AgBrCl, AgBrClI and AgCl are suitable as silver halides of the color coupler-containing and the color coupler-free silver halide emulsion layers.
• the silver halides of all light-sensitive layers preferably contain at least 80 mol% of chloride, in particular 95 to 100 mol% of chloride. 0 to 5 mol% bromide and 0 to 1 mol% iodide.
• the silver halide emulsions can be directly positive-working or preferably negative-working emulsions.
• the silver halide can be predominantly compact crystals. for example the regular cubic or octahedral are transitional forms. However, twinned, for example platelet-shaped crystals can also preferably be present, the average ratio of diameter to thickness of which is preferably at least 5: 1. wherein the diameter of 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 in which the ratio of diameter to thickness is greater than 5: 1, for example 12: 1 to 30: 1.
• the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. Doping of the individual grain areas are different.
• the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be either homodisperse or heterodisperse.
• the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.
• Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
• the photographic emulsions can be prepared by various methods (e.g. P. Glafkides. Chimie et Pysique Photographique, Paul Montel, Paris (1967), GF Duffin.
• Gelatin is preferably used as the binder for the silver halides. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers.
• the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
• functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
• the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
• Azaindenes are particularly suitable, preferably tetra and pentaazaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are from Birr, for example. Z. Wiss. Phot. 47 (1952), pp. 2-58. Can continue as Antifoggant salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, (subst.) Benzotriazoles or benzothiazolium salts are used.
• metals such as mercury or cadmium
• aromatic sulfonic or sulfinic acids such as benzenesulfinic acid
• nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, (subst.) Benzotriazoles or benzothiazolium salts are used.
• Heterocycles containing mercapto groups for example mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
• mercaptobenzothiazoles for example mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines
• these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
• a water-solubilizing group for example a carboxyl group or sulfo group.
• the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
• the compounds can also be added to other photographic layers which are assigned to a silver halide layer.
• the silver halide emulsions are usually chemically ripened, for example by the action of gold compounds or compounds of divalent sulfur.
• the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
• Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromide iodides.
• the differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it.
• cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.
• Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type.
• Color couplers for producing the purple partial color image are generally couplers of the pyrazolazole, 5-pyrazolone or indazolone type.
• Color couplers for producing the yellow partial color image are usually couplers with an open-chain ketomethylene grouping, in particular couplers of the type ⁇ -acylacetamids; suitable examples are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers. As already mentioned, the latter are preferred.
• the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
• the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point, which is split off during the coupling.
• the couplers usually contain a ballast residue to prevent diffusion within the material, i.e. both within a layer or from layer to layer, to make impossible.
• a ballast residue instead of couplers with a ballast residue, high molecular weight couplers can also be used.
• High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211.
• the high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
• the incorporation of the couplers or other compounds in silver halide emulsion layers can be carried out by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it to the casting solution for the layer in question.
• the selection of the suitable solvent or dispersing agent depends on the respective solubility of the compound.
• Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-0 043 037.
• oligomers or polymers instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
• the compounds can also be introduced into the casting solution in the form of loaded latices.
• anionic water-soluble compounds e.g. dyes
• pickling polymers e.g. acrylic acid
• Suitable oil formers are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives, hydrocarbons, sulfones and sulfoxides.
• oil formers are dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert-amylphenol, dioctylacetate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-doxy-5-butyl-2-. -o
• the photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (Latices). Contain biocides and others.
• intermediate layers can contain so-called white couplers and other compounds that react with the developer oxidation product (scavenger).
• the layers of the photographic material can be hardened with the usual hardening agents.
• Suitable curing agents include formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen contain (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207) divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5 triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 732 316 and US
• the hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened, or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.
• Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry and the swelling of the layer structure occurs as a result of the crosslinking reaction .
• Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
• hardening agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which are able to react with free carboxyl groups of the gelatin, so that the latter with free amino groups of the gelatin react to form peptide bonds and crosslink the gelatin.
• the color photographic materials according to the invention are usually processed by developing, bleaching, fixing and washing or stabilizing without subsequent washing, wherein bleaching and fixing can be combined into one processing step.
• All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound.
• Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, N-ethyl-N-3-hydroxypropyl-3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
• Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.
• the material is usually bleached and fixed after color development.
• bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used.
• Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaessioic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
• Persulfates and peroxides e.g. Hydrogen peroxide.
• the bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.
• the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent.
• this stabilizing bath also acts as a final bath.
• the UV protective film was produced as follows: A layer of 1.5 g of gelatin, 0.65 g of UV absorber of the following formula was applied to a transparent cellulose triacetate film provided with an adhesive layer 0.07 g dioctyl hydroquinone and 0.36 g tricresyl phosphate applied. The quantities refer to 1 m2. Table 1 sample stabilizer Density decrease in% at density 0.5 1.0 D max 1 comparison - 75 74 77 2nd comparison X-1 63 57 53 3rd comparison X-2 65 59 50 4th comparison X-3 62 56 49 5 invention I-4 41 25th 33 6 invention I-6 44 26 37 7 invention I-14 45 27 36 8th invention I-21 46 27 37 9 invention I-25 42 24th 32
• the compounds according to the invention achieve improved light stability of the yellow dyes, especially at medium and high densities.
• a color photographic recording material suitable for a rapid processing process was produced by placing the following layers on a support made of paper coated on both sides with polyethylene were applied in the order given.
• the quantities given relate to 1 m2.
• the corresponding amounts of AgNO3 are given.
• Samples 2 to 13 were produced in the same manner as sample 1, with the difference that 0.2 g / m 2 of a stabilizer shown in table 2 was added to layer 2.
• Samples 9 to 13 were additionally added in layer 2 with 0.1 g / m 2 of a costabilizer of the formulas III, IV or V given in Table 2.
• Example 2 The samples were then exposed according to Example 1, processed and irradiated with a xenon lamp. The measured percentage decreases in density are shown in Table 2.
• Table 2 shows that the light stability of the yellow dye is significantly improved by the compounds according to the invention compared to X-1 and X-2. With the addition of co-stabilizers of formulas III, IV and V, the light stability can be further improved.
• Table 3 sample veil % Decrease in density gb pp bg 1 (compare) 22 15 11 11 2 " 21 14 11 10th 3 " 23 16 12th 12th 4 (req.) 16 12th 10th 6 5 " 17th 13 10th 7 6 " 18th 13 10th 7 7 " 18th 13 11 7 8th " 17th 12th 10th 6 9 (compare) 21 14 11 10th 10 (req.) 15 12th 20th 5 11 " 13 10th 8th 3rd 12 " 16 12th 9 6 13 " 13 10th 9 3rd

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• 1993
  • 1993-06-21 DE DE4320444A patent/DE4320444A1/de not_active Withdrawn
• 1994
  • 1994-06-08 DE DE59407757T patent/DE59407757D1/de not_active Expired - Fee Related
  • 1994-06-08 EP EP94108788A patent/EP0631184B1/fr not_active Expired - Lifetime
  • 1994-06-09 US US08/257,532 patent/US5466569A/en not_active Expired - Fee Related
  • 1994-06-16 JP JP6156383A patent/JPH0713311A/ja active Pending

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