EP0254151A2 - Matériau photographique couleur contenant des coupleurs - Google Patents

Matériau photographique couleur contenant des coupleurs Download PDF

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Publication number
EP0254151A2
EP0254151A2 EP87109964A EP87109964A EP0254151A2 EP 0254151 A2 EP0254151 A2 EP 0254151A2 EP 87109964 A EP87109964 A EP 87109964A EP 87109964 A EP87109964 A EP 87109964A EP 0254151 A2 EP0254151 A2 EP 0254151A2
Authority
EP
European Patent Office
Prior art keywords
color
alkyl
couplers
coupler
layer
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.)
Granted
Application number
EP87109964A
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German (de)
English (en)
Other versions
EP0254151A3 (en
EP0254151B1 (fr
Inventor
Hans Dr. Langen
Erich Dr. Wolff
Heinz Wiesen
Jürgen Dr. Plamper
Erwin Dr. Ranz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert AG
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Agfa Gevaert AG
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Filing date
Publication date
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0254151A2 publication Critical patent/EP0254151A2/fr
Publication of EP0254151A3 publication Critical patent/EP0254151A3/de
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Publication of EP0254151B1 publication Critical patent/EP0254151B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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. So far, the former was preferred in color photographic recording materials the more favorable absorption (at approx. 700 nm) of the image dyes produced from them in the chromogenic development. In contrast, 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-AO 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; but With these dyes the absorption maximum 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.
  • the invention relates to a color photographic recording material having at least one silver halide emulsion layer sensitized to the red spectral range, to which a cyan coupler of the 2-phenylureidophenol type is assigned, characterized in that the silver halide emulsion layer sensitized to the red spectral range has at least one cyan coupler of the formula I and at least one cyan coupler are assigned to Formula II in what mean R1 is a ballast group XH or a group other than hydrogen that can be released on color coupling R2, R3 H, F, Cl, -CN, -CF3 or -SO2-R4, where R4 is F, alkyl or alkylamino, but R2 and R3 are not both H or -CN at the same time.
  • R1 is a ballast group XH or a group other than hydrogen that can be released on color coupling R2, R3 H, F, Cl, -CN, -CF3 or -SO2-R4, where R4 is F
  • a releasable group represented by X is, for example, a halogen atom such as F, Cl 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 carbon atoms.
  • the ballast group represented by R 1 preferably corresponds to Formula III in which mean: ZO or S;
  • R5 is a methylene group or an alkylidene group having 2 to 20 carbon atoms of the formula , where R7 is H or alkyl and where alkyl can be straight-chain or branched;
  • R6 halogen, hydroxy, carboxy, alkyl, cycloalkyl, aryl, aralkyl, alkoxy, aryloxy, alkylsulfamoyl, arylsulfamoyl, alkylsulfonamido, arylsulfonamides, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl or acyloxy, in which alkyl contains 1 to 20 carbon atoms, in which aryl, preferably one, preferably arenones is substituted phenyl group and in which alkyl, aryl and aralkyl can
  • R1 can also be a segment from the backbone of a polymer which is formed by polymerizing a monomeric coupler of one of the formulas I and II, in which R1 is a radical which contains a polymerizable group.
  • R1 need not necessarily be the same in both cyan couplers of a particular combination of cyan couplers of formula I and II.
  • Couplers of the general formula I 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 II 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 the recording of light in 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 two or more silver halide emulsion sublayers (DE-C-1 121 470).
  • Red-sensitive silver halide emulsion layers are usually arranged closer to the 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 of the same spectral sensitivity can be immediately adjacent to one another or arranged in such a way 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 a Interaction between them is possible, which allows an image-like correspondence 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 consequently assigned at least one non-diffusing color coupler for producing the blue-green partial color image, in the present case at least per coupler of the formulas I and II 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 "Color Coupler" by W.
  • the color couplers can be both conventional 4-equivalent couplers and 2-equivalent couplers in which a smaller amount of silver halide is required to produce the color.
  • 2-equivalent couplers are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site, which is split off during the coupling.
  • the 2-equivalent couplers include both: are practically colorless, as well as those that have an intense intrinsic 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 for example development accelerators or fogging agents, can also be released during the development from such couplers.
  • 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.
  • 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 are suitable as protective colloid or binder for the layers of the recording material, e.g. Proteins, especially gelatin. 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 laid-open specification 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 laid-open documents 2 439 551, 2 225 230, 2 317 672 and from Research Disclosure 17 643, section XI, specified 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 Fe3+ salts and Fe3+ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes etc.
  • Iron-III complexes of are particularly preferred Aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediamine triacetic acid, alkyliminodicarboxylic acids and 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 produced by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities given relate to 1 m2. For the silver halide application, the corresponding amounts of AgNO3 are given. All silver halide emulsions were stabilized per 100 g of AgNO3 with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
  • red-sensitized silver chloride bromide iodide emulsion (5 mol% iodide; 2 mol% chloride; average grain diameter 0.5 ⁇ m) 2.4 g AgNO3, 0.9 mmol cyan coupler (Table 3) 0.06 g MR-1 red mask 0.025 g DIR coupler DC-1 1.2 g gelatin
  • Silver bromide iodide emulsion (3 mol% iodide; average grain diameter 0.3 ⁇ m) 0.95 g AgNO3, 0.96 g yellow coupler Y-1 1.4 g gelatin
  • Silver bromide iodide emulsion (8 mol% iodide; average grain diameter 0.8 ⁇ m) 1.0 g AgNO3, 0.22 g yellow coupler Y-1 1.6 g gelatin
  • 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)
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
DE3624777A DE3624777A1 (de) 1986-07-22 1986-07-22 Fotografisches farbkupplerhaltiges material
DE3624777 1986-07-22

Publications (3)

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

Family

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Family Applications (1)

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

Country Status (3)

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EP (1) EP0254151B1 (fr)
JP (1) JPS6333745A (fr)
DE (2) DE3624777A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0389817A1 (fr) * 1989-03-09 1990-10-03 Minnesota Mining And Manufacturing Company Matériaux photographiques couleur à halogénure d'argent
EP0422462A3 (en) * 1989-10-11 1991-05-22 Agfa-Gevaert Ag Colour photographic recording material with couplers which release heat-stable dyes
US5399472A (en) * 1992-04-16 1995-03-21 Eastman Kodak Company Coupler blends in color photographic materials
GB2304422A (en) * 1995-08-21 1997-03-19 Eastman Kodak Co Blends of couplers with homologous ballasts

Families Citing this family (3)

* 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
US5585230A (en) * 1995-03-23 1996-12-17 Eastman Kodak Company Cyan coupler dispersion with improved stability
US5726003A (en) * 1996-08-15 1998-03-10 Eastman Kodak Company Cyan coupler dispersion with increased activity

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0389817A1 (fr) * 1989-03-09 1990-10-03 Minnesota Mining And Manufacturing Company Matériaux photographiques couleur à halogénure d'argent
EP0476710A1 (fr) * 1989-03-09 1992-03-25 Minnesota Mining And Manufacturing Company Matériau pour photographie en couleurs à halogénure d'argent
EP0422462A3 (en) * 1989-10-11 1991-05-22 Agfa-Gevaert Ag Colour photographic recording material with couplers which release heat-stable dyes
US5399472A (en) * 1992-04-16 1995-03-21 Eastman Kodak Company Coupler blends in color photographic materials
GB2304422A (en) * 1995-08-21 1997-03-19 Eastman Kodak Co Blends of couplers with homologous ballasts
US5789146A (en) * 1995-08-21 1998-08-04 Eastman Kodak Company Blends of couplers with homologous ballasts
GB2304422B (en) * 1995-08-21 1999-03-10 Eastman Kodak Co Blends of couplers with homologous ballasts

Also Published As

Publication number Publication date
JPS6333745A (ja) 1988-02-13
DE3766558D1 (de) 1991-01-17
EP0254151A3 (en) 1988-12-14
EP0254151B1 (fr) 1990-12-05
DE3624777A1 (de) 1988-01-28

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