EP0254151B1 - Matériau photographique couleur contenant des coupleurs - Google Patents

Matériau photographique couleur contenant des coupleurs Download PDF

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Publication number
EP0254151B1
EP0254151B1 EP87109964A EP87109964A EP0254151B1 EP 0254151 B1 EP0254151 B1 EP 0254151B1 EP 87109964 A EP87109964 A EP 87109964A EP 87109964 A EP87109964 A EP 87109964A EP 0254151 B1 EP0254151 B1 EP 0254151B1
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EP
European Patent Office
Prior art keywords
color
couplers
alkyl
layer
silver halide
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.)
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EP87109964A
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German (de)
English (en)
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EP0254151A2 (fr
EP0254151A3 (en
Inventor
Hans Dr. Langen
Erich Dr. Wolff
Heinz Wiesen
Jürgen Dr. Plamper
Erwin Dr. Ranz
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C7/32—Colour coupling substances
    • G03C7/34—Couplers containing phenols
    • G03C7/342—Combination of phenolic or naphtholic couplers

Definitions

  • the invention relates to a color photographic material with an emulsified phenolic cyan couplers with a phenylureido structure.
  • Naphtholic or phenolic cyan couplers are usually used to produce the cyan partial image.
  • the former has so far been preferred because of the more favorable absorption (at approx. 700 nm) of the image dyes produced from them in the chromogenic development.
  • the phenolic cyan couplers generally provide dyes with an absorption maximum at shorter wavelengths.
  • the naphtholic cyan couplers are ideal from a spectral point of view, particularly when used in color negative films, there is a serious disadvantage in the inadequate stability properties of the dyes, in particular in the poor stability to moisture and heat.
  • the phenolic ones are preferable to the naphtholic teal couplers;
  • the dyes produced from them absorb too short-wave and therefore have an undesirable secondary density in the green spectral range which is too high. This leads to desaturated color reproduction in the copying material, unless the excessively high secondary density in the green spectral range in the color negative film is compensated for by additional measures, for example the use of increased amounts of mask coupler.
  • EP-A-O 028 099 and EP-A-0 067 689 describe phenolic cyan couplers which contain a phenylureido group substituted in the benzene ring in the 2-position of the phenol ring.
  • these couplers provide dyes with good stability and a comparatively long-wave absorption maximum; however, the absorption maximum for these dyes is generally well below 700 nm, so that in this respect they cannot be compared with the dyes obtained from naphtholic cyan couplers. Rather, these dyes still have too high a secondary absorption in the green spectral range.
  • EP-A-0 184 057 also describes cyan couplers of the 2-phenylureidophenol type which contain a fluorosulfonyl group in the phenylureido group. Although these color couplers represent an optimum with regard to the long-wave absorption of the dyes made from them, there is a disadvantage that the fluorosulfonyl group can apparently react under certain climatic conditions with uncrosslinked amino groups of the gelatin, which can result in a flattening of the gradation.
  • the invention is based on the object of specifying a color photographic recording material which contains color couplers which, in the chromogenic development, provide a stable blue-green partial color image with an absorption maximum at approximately 700 nm and a low secondary density.
  • a releasable group represented by X is, for example, a halogen atom such as F, CI or Br, or an organic group linked via an oxygen atom, a sulfur atom or a nitrogen atom.
  • An alkyl group contained in R2 or R3 can be straight-chain or branched and contain, for example, 1-18 C atoms.
  • Couplers of the general formula can be prepared by methods which are known in principle, e.g. B. by reacting 3,4-dicyanophenyl isocyanate or phenyl-3,4-dicyanophenyl carbamate with a suitable 2-aminophenol; Such methods are described, for example, in EP-A-0 028 099, EP-A-0 067 689, EP-A-0 175 573 and EP-A-0 184 057.
  • the 3,4-dicyanophenyl isocyanate required as an intermediate can, for example, be like are produced as follows:
  • the yield determined by volumetric NCO determination, is 93-94% of theory.
  • Couplers of the general formula 11 are described, for example, in EP-A-0 028 099, EP-A-0 067 689, EP-A-O 175 573 and EP-A-0 184 057.
  • the combination of the diffusion-resistant cyan couplers of the present invention can be incorporated in the casting solution of the silver halide emulsion layers or other colloid layers in a known manner.
  • the preferably oil-soluble or hydrophobic couplers can be added to a hydrophilic colloid solution from a solution in a suitable coupler solvent (oil former), if appropriate in the presence of a wetting or dispersing agent.
  • the hydrophilic casting solution can of course contain other conventional additives in addition to the binder.
  • the solution of the couplers need not be directly dispersed in the casting solution for the silver halide emulsion layer or other water permeable layer; Rather, it can also be advantageously first dispersed in an aqueous, non-photosensitive solution of a hydrophilic colloid, whereupon the mixture obtained, after removal of the low-boiling organic solvents used, may be mixed with the coating solution for the photosensitive silver halide emulsion layer or another water-permeable layer before application.
  • Suitable light-sensitive silver halide emulsions are emulsions of silver chloride, silver bromide or mixtures thereof, possibly with a low silver iodide content of up to 10 mol% in one of the commonly used hydrophilic binders.
  • Gelatin is preferably used as a binder for the photographic layers. However, this can be replaced in whole or in part by other natural or synthetic binders.
  • the emulsions can be chemically and spectrally sensitized in the usual way, and the emulsion layers as well as other non-light-sensitive layers can be hardened in the usual way with known hardening agents.
  • Color photographic recording materials usually contain at least one silver halide emulsion layer for recording light from the three spectral ranges red, green and blue.
  • the light-sensitive layers are spectrally sensitized in a known manner by means of suitable sensitizing dyes.
  • Blue-sensitive silver halide emulsion layers do not necessarily have to contain a spectral sensitizer, since in many cases the intrinsic sensitivity of the silver halide is sufficient for the recording of blue light.
  • Each of the light-sensitive layers mentioned can consist of a single layer or, in a known manner, for example in the case of the so-called double-layer arrangement, also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
  • red-sensitive silver halide emulsion layers are arranged closer to the layer support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, a yellow filter layer which is not sensitive to light generally being located between green-sensitive layers and blue-sensitive layers.
  • a layer which is not sensitive to light is generally arranged between layers of different spectral sensitivity and can contain means for preventing the incorrect diffusion of developer oxidation products.
  • silver halide emulsion layers with the same spectral sensitivity can these are directly adjacent to one another or be arranged such that a light-sensitive layer with a different spectral sensitivity is located between them (DE-A-1 958 709, DE-A-2 530 645, DE-A-2 622 922).
  • Color photographic recording materials for producing multicolored images usually contain, in spatial and spectral assignment to the silver halide emulsion layers of different spectral sensitivity, coloring compounds, here in particular color couplers, for producing the different partial color images cyan, purple and yellow.
  • Spatial assignment is understood to mean that the color coupler is in such a spatial relationship with the silver halide emulsion layer that an interaction between them is possible which allows an image-wise match between the silver image formed during development and the color image generated from the color coupler. This is usually achieved by the fact that the color coupler is contained in the silver halide emulsion layer itself or in a possibly non-light-sensitive binder layer adjacent to it.
  • Spectral assignment is understood to mean that the spectral sensitivity of each of the light-sensitive silver halide emulsion layers and the color of the partial color image generated from the spatially assigned color coupler are in a specific relationship to one another, with each of the spectral sensitivities (red, green, blue) having a different color of the relevant partial color image (e.g. teal, purple, yellow) is assigned.
  • One or more color couplers can be assigned to each of the differently spectrally sensitized silver halide emulsion layers. If there are several silver halide emulsion layers of the same spectral sensitivity, each of them can contain a color coupler, which color couplers need not necessarily be identical. They should only result in at least approximately the same color during color development, normally a color that is complementary to the color of the light, for which the silver halide emulsion layers in question are predominantly sensitive.
  • red-sensitive silver halide emulsion layers are therefore assigned at least one non-diffusing color coupler for producing the blue-green partial color image, in the present case at least one coupler of the formulas I and 11.
  • Green-sensitive silver halide emulsion layers are assigned at least one non-diffusing color coupler for producing the purple partial color image, usually color couplers of the type 5-pyrazolone, indazolone or pyrazoloazole can be used.
  • blue-sensitive silver halide emulsion layers are assigned at least one non-diffusing color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
  • Color couplers of this type are known in large numbers and are described in a large number of patents. Examples include the publications “Farbkuppler” by W. PELZ in “Mitanderen aus der Anlagenslaboratorien der Agfa, Leverkusen / Ober", volume 111, page 111 (1961) and by K. VENKATARAMAN in “The Chemistry of Synthetic Dyes", Vol 4, 341 to 387, Academic Press (1971).
  • the color couplers can be either conventional 4-equivalent couplers or 2-equivalent couplers, which require a smaller amount of silver halide to produce the color.
  • 2-equivalent couplers are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point which is split off during the coupling.
  • the 2-equivalent couplers include both those that are practically colorless and those that have an intense inherent color that disappears when the color is coupled or is replaced by the color of the image dye produced.
  • the latter couplers can also be present in the light-sensitive silver halide emulsion layers and serve there as mask couplers to compensate for the undesired secondary densities of the image dyes.
  • the known white couplers are also to be counted among the 2-equivalent couplers, but they do not give any dye on reaction with color developer oxidation products.
  • the 2-equivalent couplers are also the known DIR couplers, which are couplers which contain a detachable residue in the coupling point, which is released as a diffusing development inhibitor when reacted with color developer oxidation products.
  • Other photographically active compounds e.g. Development accelerators or fogging agents can be released from such couplers during development.
  • the color photographic recording material of the present invention can contain further additives, for example antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties.
  • further additives for example antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties.
  • UV-absorbing compounds in one or more of the layers contained in the recording material, preferably in one of the upper layers to use. Suitable UV absorbers are described for example in US-A-3 253 921, DE-C-2 036 719 and EP-A-1 057 160.
  • hydrophilic film-forming agents for example proteins, in particular gelatin, are suitable as protective colloids or binders for the layers of the recording material.
  • Casting aids and Plasticizers can be used. Reference is made to the compounds indicated in Research Disclosure 17,643 above in Sections IX, XI and XII.
  • the layers of the photographic material can be hardened in the usual manner, for example with hardeners of the epoxy type, the heterocyclic ethylene imine and the acryloyl type. Furthermore, it is also possible to harden the layers in accordance with the process of German Offenlegungsschrift 2 218 009 in order to obtain color photographic materials which are suitable for high-temperature processing. It is also possible to harden the photographic layers with hardeners of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type. Further suitable hardening agents are known from German Offenlegungsschriften 2,439,551, 2,225,230, 2,317,672 and from Research Disclosure 17,643, Section XI, given above.
  • the color photographic recording material according to the invention is developed with a color developer compound.
  • All developer compounds which have the ability in the form of their oxidation product to react with color couplers to form azomethine 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-methylsulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl-3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
  • N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-eth
  • the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together.
  • the usual compounds can be used as bleaching agents, for example Fe 3 + salts and Fe 3 + complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes, etc.
  • Particularly preferred are iron III complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediamine triacetic acid, alkyliminodicarboxylic acids and of corresponding phosphonic acids.
  • Persulphates are also suitable as bleaching agents.
  • Table 1 shows that not only can the desired absorption maximum of 700 ⁇ 2 nm be set fairly accurately with the combination according to the invention, but also much lower secondary densities are obtained.
  • a color photographic recording material for color negative development was prepared 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 AgN0 3 are given. All silver halide emulsions per 100 g of AgNO 3 were stabilized with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
  • coupler 100 g were dissolved together with 80 g of dibutyl phthalate in 300 ml of ethyl acetate and at 50 ° C. in 1.3 l of 7.5% gelatin, likewise heated to 50 ° C., which was additionally mixed with 10 g of sodium dodecylbenzene sulfonate. emulsified. The low-boiling solvent was then removed in vacuo and the remaining dispersion solidified at 6 ° C.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (2)

1. Support d'enregistrement pour la photographie en couleur, comprenant au moins une couche d'émulsion à l'halogénure d'argent sensibilisée pour la région spectrale du rouge, auquel est associé un copulant cyan du type du 2-phényluréidophénol, caractérisé par l'association à la couche d'émulsion à l'halogénure d'argent sensibilisée à la région spectrale du rouge, d'au moins un copulant cyan de formule 1 et au moins un copulant cyan de formule Il:
Figure imgb0041
Figure imgb0042
formules dans lesquelles
R1 est un groupe ballast
X représente H ou un groupe différent de l'hydrogène, pouvant être libéré au moment de la copulation
R2, R3 représentent H, F, CI, -CN, -CFs ou -S02-R4, où R4 représente le fluor, un radical alkyle ou alkylamino, R2 et R3 ne pouvant toutefois pas représenter tous deux en même temps H ou -CN, et les copulants des formules 1 et II sont utilisés dans des rapports quantitatifs compris entre 1:4 et 4:1.
2. Support d'enregistrement suivant la revendication 1, caractérisé en ce qu'au moins l'un des copulants cyan de formules 1 et II porte un groupe ballast R1 de formule III
Figure imgb0043
dans laquelle
Z représente 0 ou S;
R5 est un groupe méthylène ou un groupe alkylidène ayant 2 à 20 atomes de carbone, de formule
Figure imgb0044
dans laquelle R7 représente H ou un radical alkyle et la portion alkyle peut être à chaîne droite ou à chaîne ramifiée;
R6 est un halogène, un radical hydroxy, carboxy, alkyle, cycloalkyle, aryle, aralkyle, alkoxy, aryloxy, alkylsulfamoyle, arylsulfamoyle, alkylsulfonamido, arylsulfonamido, alkylsulfonyle, arylsulfonyle, alkoxycarbonyle ou acyloxy, dont la partie alkyle contient 1 à 20 atomes de carbone, et les radicaux alkyle, aryle et aralkyle peuvent aussi être substitués à volonté avec un substituant alkyle, hydroxy, carboxy, alkoxycarbonyle ou acyloxy,
m et 2 a une valeur de 1 à 3.
EP87109964A 1986-07-22 1987-07-10 Matériau photographique couleur contenant des coupleurs Expired - Lifetime EP0254151B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3624777 1986-07-22
DE3624777A DE3624777A1 (de) 1986-07-22 1986-07-22 Fotografisches farbkupplerhaltiges material

Publications (3)

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EP0254151A2 EP0254151A2 (fr) 1988-01-27
EP0254151A3 EP0254151A3 (en) 1988-12-14
EP0254151B1 true EP0254151B1 (fr) 1990-12-05

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EP87109964A Expired - Lifetime EP0254151B1 (fr) 1986-07-22 1987-07-10 Matériau photographique couleur contenant des coupleurs

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JP (1) JPS6333745A (fr)
DE (2) DE3624777A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2681162B2 (ja) * 1988-07-04 1997-11-26 コニカ株式会社 ハロゲン化銀カラー写真感光材料
IT1229993B (it) * 1989-03-09 1991-09-20 Minnesota Mining & Mfg Materiali fotografici a colori agli alogenuri d'argento.
DE3933899A1 (de) * 1989-10-11 1991-04-18 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial mit farbkupplern, die thermostabile farbstoffe liefern
US5399472A (en) * 1992-04-16 1995-03-21 Eastman Kodak Company Coupler blends in color photographic materials
US5585230A (en) * 1995-03-23 1996-12-17 Eastman Kodak Company Cyan coupler dispersion with improved stability
US5789146A (en) * 1995-08-21 1998-08-04 Eastman Kodak Company Blends of couplers with homologous ballasts
US5726003A (en) * 1996-08-15 1998-03-10 Eastman Kodak Company Cyan coupler dispersion with increased activity

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5460924A (en) * 1977-10-24 1979-05-16 Konishiroku Photo Ind Co Ltd Silver halide color photographic emulsion
JPS5898731A (ja) * 1981-12-07 1983-06-11 Fuji Photo Film Co Ltd カラ−写真感光材料
JPS5969754A (ja) * 1982-10-14 1984-04-20 Fuji Photo Film Co Ltd ハロゲン化銀カラ−感光材料
US4609619A (en) * 1984-09-17 1986-09-02 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide color photographic material
DE3443700A1 (de) * 1984-11-30 1986-06-05 Agfa-Gevaert Ag, 5090 Leverkusen Fotografisches farbkupplerhaltiges material

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Publication number Publication date
DE3624777A1 (de) 1988-01-28
EP0254151A2 (fr) 1988-01-27
DE3766558D1 (de) 1991-01-17
EP0254151A3 (en) 1988-12-14
JPS6333745A (ja) 1988-02-13

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