US3705035A - Diffusion-fast color-forming developing agents - Google Patents

Diffusion-fast color-forming developing agents Download PDF

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Publication number
US3705035A
US3705035A US43939A US3705035DA US3705035A US 3705035 A US3705035 A US 3705035A US 43939 A US43939 A US 43939A US 3705035D A US3705035D A US 3705035DA US 3705035 A US3705035 A US 3705035A
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United States
Prior art keywords
dye
color
layer
compound
alkyl
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Expired - Lifetime
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US43939A
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English (en)
Inventor
Hans Vetter
Justus Danhauser
Karlheinz Kabitzke
Paul Marx
Arnfried Melzer
Willibald Pelz
Walter Puschel
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers
    • G03C7/4136—Developers p-Phenylenediamine or derivatives thereof
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/42—Developers or their precursors

Definitions

  • Photographic images are obtained by developing an imagewise exposed light-sensitive photographic material comprising at least one silver halide emulsion layer, which contains diffusion fast p-phenylene diamine type developing agents in the formula wherein R represents hydrogen, alkyl or alkoxy;
  • R represents hydrogen or alkyl
  • R represents alkyl from 8 to 20 carbon atoms
  • X represents hydrogen, sulfo, carboxyl, hydroxyl or sulfonamide
  • n 1 to 4.
  • the development is preferably carried out in the presence of a pyrazolidone-3 compound.
  • the invention relates to a photographic material which contains a developer, and more particularly the invention relates to a photographic material comprising at least one silver halide emulsion layer which contains a developer of the p-phenylene diamine type which is incorporated in a form which is fast to diffusion.
  • Photographic developing agents are relatively sensitive to oxidation, both when they are present in the form of an aqueous solution in the developer bath, and when they are present in the photographic layer. Their activity deteriorates considerably on prolonged storage in air. Moreover, the stability on storage of silver halide emulsion layers which contain photographic developing agents is unsatisfactory because such layers readily tend to fog. It has, therefore already been proposed to incorporate socalled masked developing agents in emulsion layers. These masked developers are characterized in that the photographically active groups, e.g. phenolic hydroxyl groups or aromatic amino groups are substituted with groups, e.g. by acylation or esterification, which remove the photographic activity of the compounds and hence also their 3,705,035 Patented Dec.
  • the photographically active groups e.g. phenolic hydroxyl groups or aromatic amino groups
  • a photographic light-sensitive material comprising at least one silver halide emulsion layer containing a pphenylene diamine type developing agent and optionally containing a color-forming coupler or a dye-giving compound has now been found wherein the p-phenylene diamine type developing agent incorporated in the silver halide emulsion layer or in a hydrophilic colloid layer adjacent thereto is resistant to dififusion and has the formula:
  • R represents a hydrogen atom, an alkyl group, preferably a short chained alkyl group containing up to 5 carbon atoms, in particularly methyl or ethyl, or an alkoxy group, particularly a short chained alkoxy group containing up to 3 carbon atoms, such as methoxy or eth- Y;
  • 'R represents a hydrogen atom or an alkyl group, preferably a short chained alkyl group containing up to 5 carbon atoms, in particular methyl or ethyl;
  • R represents a long chained alkyl radical containing from 8 to 20 carbon atoms, preferably from 12 to 18 carbon atoms, for example dodecyl, heptadecyl or octadecyl;
  • X represents a hydrogen atom or a sulto, carboxyl, hy-
  • amide group in which the amide group may be substituted with alkyl radicals, in particular short chained alkyl radicals such as methyl or ethyl, and
  • n an integer from 1 to 4.
  • HZNQ-N a The preparation of developer 1 is described below.
  • the other developers are prepared in an analogous manner.
  • N-dodecylaniline is prepared as follows:
  • the diffusion fast p-phenylene diamine derivatives to be used according to the invention have little or no effect as photographic developers even in an alkaline medium. It has now surprisingly been found that in the presence of small quantities of developers of the pyrozolidone-3 type they are extremely active developers. They then have at least the same activity as the conventionally used color-forming developers of the phenylene diamine series.
  • tPyrazolidone-3 derivatives of the following formula are suitable for use in combination with the p-phenylene diamine type developing agents to be used according to the invention:
  • R represents a hydrogen atom
  • R R R and R each represents a hydrogen atom, an allayl or aryl group or a substituted alkyl or aryl group, an
  • R represents a hydrogen atom or an alkyl or aryl group which may be substituted, for example with lower alkyl or alkoxy groups or halogen atoms.
  • the p-phenylene diamine type developing agents to be used according to the invention are added to the casting solutions, for example for the silver halide emulsion layers or for other hydrophilic colloid layers in the form of solutions e.g. in water or in organic solvents which are miscible with water such as short chained aliphatic alcohols or dimethyl formamide, preferably shortly before casting.
  • concentration of the developers in the layer may vary within wide limits. It depends on the effect required and on the nature of the reproduction process and the type of silver halide. Quantities of between 1 and 30 g./mol of silver halide are generally sufficient. The optimum quantity can be found by a few simple laboratory tests. Concentrations of between 3 and 20 g./rnol of silver halide are preferred.
  • the phenylene diamine derivatives to be used according to the invention may be used in any silver halide emulsions.
  • Silver chloride, silver bromide or mixtures thereof optionally containing a small amount of silver iodide e.g. of up to 10 mols percent are suitable for use as silver halide.
  • the silver halides may be dispersed in the usual hydrophilic and water-permeable binders such as proteins, particularly gelatin, or cellulose derivatives such as carboxymethylcellulose or hydroxyethyl cellulose, either alone or in admixture-with gelatin, or synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate and polyvinyl pyrrolidone. These compounds can also be used as binders in non-light sensitive interlayers which do not contain silver halide.
  • binders such as proteins, particularly gelatin, or cellulose derivatives such as carboxymethylcellulose or hydroxyethyl cellulose, either alone or in admixture-with gelatin, or synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate and polyvinyl pyrrolidone.
  • the phenylene diamine developers to be used according to the invention are color-forming developers. They are, therefore, preferably used for color photographic processes. For this purpose they are particularly suitable for silver halide emulsions which contain the usual colorforming couplers which are described e.g. in the publication by W. P'elz in Mitteilungen aus den Anlagenslaboratorien der Agfa, volume 3, publishers Springer- Verlag, Berlin, 1961, pages 111-175.
  • color-forming couplers may be either colorless or colored. They react with the oxidation products of the color-forming developers, which are produced on development of the exposed silver halide, to form the image dye.
  • the p phenylene diamine type developing agents to be used according to the invention are particularly suitable for color photographic diffusion transfer processes.
  • the silver halide emulsion layer of the light-sensitive photographic materials for this process contains compounds which are also capable of reacting with the oxidation products of the p-phenylene diamine type developing agents. In this reaction, the dyes are split off and are then diffu'sible and can be transferred to an image receiv ing layer. Processes of this type are described in US. Patent No. 3,227,550.
  • the p-phenylene diamine type developing agents are used in silver halide emulsions containing dye-giving compounds of the type described in U.S. Patent No. 3,628,952.
  • These dye-giving compounds are capable of reacting with the oxidation products of the developing agents to release a dififusible dye which subsequently can be transferred to a receiving layer.
  • the p-phenylene diamine type developing agents according to the present invention can also be incorporated in a hydrophilic colloid layer which is adjacent to the silver halide emulsion layer. If, however, the developing agents are to react in their oxidized form with color-forming couplers or dye-giving compounds, these latter mentioned reaction components should be incorporated in the same layer as also the p-phenylene diamine type developing agents.
  • the diffusion fast phenylene diamine developers of the present type may also be used in spectrally sensitized emulsions, e.g. those which have been sensitized with the usual monomethine or polymethine dyes such as cyanines, hemicyanines, streptocyanines, merocyanines, oxonoles, hemioxonoles, styryl dyes or other methine dyes which also contain three or more nuclei, for example, rhodacyanines or neocyanines.
  • monomethine or polymethine dyes such as cyanines, hemicyanines, streptocyanines, merocyanines, oxonoles, hemioxonoles, styryl dyes or other methine dyes which also contain three or more nuclei, for example, rhodacyanines or neocyanines.
  • sensitizers are described by F. M. Hamer in the
  • the emulsions may also contain chemical sensitizers e.g. reducing agents such as stannous salts, polyamines such as diethylene triamine and sulfur compounds as described in US. Patent No. 1,574,944.
  • the emulsions may also contain salts of noble metals such as ruthenium, rhodium, palladium, iridium, platinum or gold for chemical sensitization, as described in the article by R. Koslowsky, Z. Wiss. Phot. 46, 65 to 72 (1951).
  • the emulsions may also contain compounds of the polyalkylene oxide type, e.g. polyethylene oxide and derivatives thereof, as chemical sensitizers.
  • the emulsions may also contain the usual stabilizers.
  • the photographic materials according to the invention are in principle processed in a known manner.
  • exposure is immediately followed by color-forming development.
  • the color-forming development bath used is a so-called activator solution which contains mainly alkalies and according to a preferred embodiment contains a pyrazolidone-3-derivative, in particular l-phenylpyrazolidone.
  • the pyrazolidone-3-compound may, however, be partly or entirely contained in the photographic material, for example, in the light-sensitive silver halide emulsion layer or in an adjacent hydrophilic colloid layer.
  • Bleaching and fixing or combined bleach fixing is carried out with baths of the usual composition.
  • the photographic material according to the invention may also be used for the production of positive colored images by color photographic reversal processes, for example, by the silver salt diffusion process as described in the US. Patent No. 2,673,800.
  • the diffusion-fast developing agents are incorporated in a hydrophilic colloid layer together with color-forming couplers or together with the dye-giving compounds of the U.S. Patent No. 3,628,952 and together with nuclei for the physical development.
  • Onto this layer there is coated a light-sensitive silver halide emulsion layer.
  • an activator bath containing a silver salt solvent and a 3-pyrazolidone compound a positive color image is obtained.
  • the activator baths preferably have a pH of from 8 to 14.
  • the pyrazolidone content is e.g. from 10 mg. to 1 g. per liter.
  • Other conventional additives may also be present, e.g. stabilizing agents such as alkali metal bromides.
  • EXAMPLE 1 Preparation of the photographic material The following layers are applied to a layer support of baryta-coated paper g./m.
  • a silver bromide gelatin emulsion layer which contains in 500 g. of emulsion, 6 g. of the coupler of the formula l -SO3H 6 g. of compound 1, 0.3 g. of saponine and 0.25 g. of N,N, N-trisacryloylhexahydrotriazine as hardener.
  • 1-phenyl-3-pyrazolidone 3 g. of anhydrous sodium sulfite, 25 g. of anhydrous soda, 1 g. of KBr, water up to 1000 ml.
  • a magenta wedge which is opposite in gradation to the original and has low fog and high color saturation is obtained.
  • the emulsion also contains the following additives per kg.:
  • Image receiving material A 10% aqueous gelatin 63 i g g g g i i 20 solution which contains 20 g. of polyvinyl pyridine per kg.
  • o ver 5 1? 51 ver 10 1 e an is applied to a layer support of white pigmented cellulose g. of gelatin.
  • the following additives are also added to triacetate
  • the thickness of the dried layer is from 5 the casting solution for the emulsion layer: to 8% mg. of a greemsensitizer of the formula: Processing.-The exposed photographic material and the image receiving material are dipped for seconds /s ⁇ CH3 into a developer bath of the following composition:
  • a 5% aqueous gelatin solution which contains per 5 g. of a compound of the following formula which on r kg. 20 g. of trimethyloctadecyl ammonium sulfate, 0.4 g. reaction with the oxidation product of the color-formof saponine and 4 ml. of a 5% aqueous formaldehyde ing developer splits off a diffusible yellow dye: solution. The thickness of the layer is 6n.
  • a silver halide gelatin' emulsion which contains 0.2 g. of saponine and per kg. 63.5 g. of silver bromide, 3.3 g. of silver iodide 0.3 g. of N,N,N"-trisacryloylhexahydrotriazine as hardand 80 g. of gelatin.
  • the following substances 5 ener are added per kg. to the casting solution for this layer: silver application about 0.8 g.
  • the material is removed from the developer bath and after about 2 minutes it is treated with a strong jet of water. The emulsion layers are thus dissolved away.
  • a green-sensitized silver bromoiodide emulsion as de- 5 g. of a compound of the following formula which on scribed in Example 2, which however, did not contain a reaction with the oxidation product of a color-forming dye-giving compound and a developing agent; silver coatdeveloper splits ofi a yellow dye: ing 1.6 g./m.
  • R represents alkyl containing from 8 to 20 carbon atoms
  • X represents hydrogen or a sulfo, carboxyl, hydroxyl or sulfonamide group, and n represents an integer from 1 to 4
  • R represents hydrogen, and R R R R R and R represent hydrogen, alkyl or aryl.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US43939A 1969-06-19 1970-06-05 Diffusion-fast color-forming developing agents Expired - Lifetime US3705035A (en)

Applications Claiming Priority (1)

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DE1931057A DE1931057C2 (de) 1969-06-19 1969-06-19 Verfahren zur Herstellung farbphotographischer Bilder

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US (1) US3705035A (enrdf_load_stackoverflow)
JP (1) JPS4926585B1 (enrdf_load_stackoverflow)
BE (1) BE752150A (enrdf_load_stackoverflow)
CA (1) CA940364A (enrdf_load_stackoverflow)
CH (1) CH560914A5 (enrdf_load_stackoverflow)
DE (1) DE1931057C2 (enrdf_load_stackoverflow)
FR (1) FR2052844A5 (enrdf_load_stackoverflow)
GB (1) GB1309133A (enrdf_load_stackoverflow)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4066456A (en) * 1974-12-10 1978-01-03 Gaf Corporation Incorporated carboxy substituted p-phenylenediamine color developer
US4066457A (en) * 1974-12-10 1978-01-03 Gaf Corporation Color developer for diffusion transfer
US4157915A (en) * 1977-05-02 1979-06-12 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material containing development precursor
US4269924A (en) * 1978-01-27 1981-05-26 Agfa-Gevaert N.V. Photographic material suited for the production of multicolor images by means of diffusion transfer of complexed silver halide
US4310623A (en) * 1979-12-14 1982-01-12 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US4390617A (en) * 1980-03-18 1983-06-28 Konishiroku Photo Industry Co., Ltd. Method for the formation of photographic images
US4465762A (en) * 1981-03-03 1984-08-14 Fuji Photo Film Co., Ltd. Method for color developing color photographic silver halide light-sensitive material
US4517286A (en) * 1982-12-02 1985-05-14 Fuji Photo Film Co., Ltd. Color diffusion transfer light-sensitive element with amine solvent
US5215875A (en) * 1990-06-23 1993-06-01 Agfa Gevaert Aktiengesellschaft Color photographic recording material
US5238797A (en) * 1991-08-26 1993-08-24 Konica Corporation Silver halide color photographic light-sensitive material containing a 1-pentahalogenophenyl-substituted 5-pyrazolone colored magenta coupler
US5328812A (en) * 1992-02-18 1994-07-12 Fuji Photo Film Co., Ltd. Method of forming a silver/halide color image using a particular acylacetamide yellow coupler and particular color developers
US5380625A (en) * 1992-02-05 1995-01-10 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic materials comprising particular dye couplers using particular developers

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5166737U (enrdf_load_stackoverflow) * 1974-11-20 1976-05-26
JPS53124472U (enrdf_load_stackoverflow) * 1977-03-11 1978-10-03
JPS5484601U (enrdf_load_stackoverflow) * 1977-11-28 1979-06-15
JPS60164499A (ja) * 1984-02-07 1985-08-27 Kyowa Medetsukusu Kk 酵素活性測定法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1101954B (de) * 1958-08-22 1961-03-09 Eastman Kodak Co Farbphotographisches Diffusions-uebertragungsverfahren und zugehoeriges photographisches Material
US3342597A (en) * 1964-06-08 1967-09-19 Eastman Kodak Co Color developer precursor

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4066456A (en) * 1974-12-10 1978-01-03 Gaf Corporation Incorporated carboxy substituted p-phenylenediamine color developer
US4066457A (en) * 1974-12-10 1978-01-03 Gaf Corporation Color developer for diffusion transfer
US4157915A (en) * 1977-05-02 1979-06-12 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material containing development precursor
US4269924A (en) * 1978-01-27 1981-05-26 Agfa-Gevaert N.V. Photographic material suited for the production of multicolor images by means of diffusion transfer of complexed silver halide
US4310623A (en) * 1979-12-14 1982-01-12 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US4390617A (en) * 1980-03-18 1983-06-28 Konishiroku Photo Industry Co., Ltd. Method for the formation of photographic images
US4465762A (en) * 1981-03-03 1984-08-14 Fuji Photo Film Co., Ltd. Method for color developing color photographic silver halide light-sensitive material
US4517286A (en) * 1982-12-02 1985-05-14 Fuji Photo Film Co., Ltd. Color diffusion transfer light-sensitive element with amine solvent
US5215875A (en) * 1990-06-23 1993-06-01 Agfa Gevaert Aktiengesellschaft Color photographic recording material
US5238797A (en) * 1991-08-26 1993-08-24 Konica Corporation Silver halide color photographic light-sensitive material containing a 1-pentahalogenophenyl-substituted 5-pyrazolone colored magenta coupler
US5380625A (en) * 1992-02-05 1995-01-10 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic materials comprising particular dye couplers using particular developers
US5328812A (en) * 1992-02-18 1994-07-12 Fuji Photo Film Co., Ltd. Method of forming a silver/halide color image using a particular acylacetamide yellow coupler and particular color developers

Also Published As

Publication number Publication date
JPS4926585B1 (enrdf_load_stackoverflow) 1974-07-10
CA940364A (en) 1974-01-22
BE752150A (nl) 1970-12-18
DE1931057A1 (de) 1971-03-11
DE1931057C2 (de) 1982-05-13
CH560914A5 (enrdf_load_stackoverflow) 1975-04-15
FR2052844A5 (enrdf_load_stackoverflow) 1971-04-09
GB1309133A (en) 1973-03-07

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