US3201246A - Photographic developers containing calcium precipitation inhibitors - Google Patents

Photographic developers containing calcium precipitation inhibitors Download PDF

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Publication number
US3201246A
US3201246A US101663A US10166361A US3201246A US 3201246 A US3201246 A US 3201246A US 101663 A US101663 A US 101663A US 10166361 A US10166361 A US 10166361A US 3201246 A US3201246 A US 3201246A
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Prior art keywords
acid
developer
photographic
calcium
developing
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US101663A
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Charles F H Allen
John A Ford
Richard W Henn
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to BE616004D priority Critical patent/BE616004A/xx
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Priority to US101663A priority patent/US3201246A/en
Priority to FR893776A priority patent/FR1319265A/fr
Priority to GB13709/62A priority patent/GB1006878A/en
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Publication of US3201246A publication Critical patent/US3201246A/en
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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers
    • G03C5/3053—Tensio-active agents or sequestering agents, e.g. water-softening or wetting agents

Definitions

  • This invention relates to photographic developing compositions containing amino-N,N-dimethylenephosphonic acids and their watensoluble derivatives.
  • Most silver halide photographic developing solutions contain anions, such as carbonate, sulfite, or borate, which form very sparingly soluble alkaline earth salts.
  • Calcium for example, may enter the developing solution from the photographic emulsion, particularly if gelatin is used as the silver halide peptizer, or calcium and magnesium may be present in the water used to prepare the developing solution.
  • the resulting precipitates of, for example, calcium and magnesium carbonates, sulfites, and borates form sludge or scum on the photographic materials and scale on the equipment, and, therefore, may have an adverse effect on the quality of the photographic film being processed.
  • alkali hexametaphosphates and polyphosphates e.g., alkali tetraphosphates
  • alkali tetraphosphates have been used in developing solutions to reduce the formation of the calcium sulfite scum on the films, and precipitation of calcium in the developer.
  • these phosphates stand in aqueous solutions, they gradually hydrolyze to the orthophosphates which do not inhibit calcium precipitation and may precipitate the calcium in the form of calcium phosphate.
  • orthophosphate is carried over to an alum fixing bath, there is the possibility of the precipitation of aluminum phosphate.
  • Some oxygen acids such as citric, tartaric, gluconic, cliglycolic, etc.
  • citric, tartaric, gluconic, cliglycolic, etc. have proved to have some usefulness as calcium sequestering agents in photographic developing solutions, but the sequestering potency of these acids is comparatively Weak and it may be necessary to supplement their effect, e.g., by adding polyphosphates, such as sodium tetraphosphate.
  • One object of our invention is to produce photographic developers having improved properties.
  • Another object of our invention is to provide developer compositions which contain a calcium sequestering agent having good stability, high sequestering potency, low fogging ropensity, and having little or no tendency to promote developer oxidation even though traces of iron and other materials may be present.
  • a further object of our invention is to prevent the formation of calcium-containing sludges, scums, and scales in the developer solutions.
  • the use of our sequestering nits States atet agents is not limited to the developer; they may also be employed in other processing baths where calcium precipitates are a problem, including prebaths, toners, bleaches, activators, washing accelerators etc. Other objects of our invention will appear herein.
  • amino-N,N-dimethylcncphosphonic acids and their Water-soluble derivatives which can advantageously be employed in our invention include those represented by the following general formula:
  • M represents a hydrogen atom or a cation which imparts water solubility, such as an alkali metal atom (cg, sodium, potassium, etc.), ammonium, pyridinium, riethanol ammonium, triethyl ammonium etc.
  • R represents an allryl group, such as methyl, ethyl, propyl, isopropyl, butyl, etc.
  • an alkyl group containing from 1 to 4 carbon atoms e.g., an alkyl group containing from 1 to 4 carbon atoms
  • an aryl group such as phenyl, o-, mand p-tolyl, oand p-carboxyphenyl (and watersoluble salts thereof, such as sodium, potassium, etc)
  • an aralkyl group such as benzyl [i-phenethyl, o-acetamidobenzyl, etc. (e.g., an aralkyl group containing from 7 to 9 carbon atoms)
  • an alicyclic group such as cyclohexyl, cyclopentyl, etc.
  • R group of Formula I above can be further substituted (especially where R represents an alkyl group) with a radical, such as hydroxyl, -O M CH PO M or N(CH PO M Where M has the values given above, chlorine, alkoxyl (e.g., methoxyl, ethoxyl, etc.), etc.
  • the amino-N,N-dimethylenephosphonic acids used in our invention can be used in the form of the free acid, or they can be employed in the form of Water-soluble salts.
  • a Wateroluble salt of the acid inherently forms.
  • the sequestering agents of our invention can be prepared according to the procedures of Bersworth US. Patent 2,599,867, issued June 10, 1952. This method comprises reacting a chloromethylenephosphonic acid Withan organic amine.
  • these sequestering agents can be prepared as described by Westerbaclt and Martell in Nature, vol. 178, page 321 6).
  • Typical water-soluble sequestering agents which can be employed in our invention inslude the following:
  • ethylenediamine N,N,N,N' tetramethylenephosphonic acid (EDTMP). (Prepared from ethylenediamine and chloromethylenephosphonic acid.)
  • nitrilo N ,N,N-trin1ethylenephosphonic acid (Prepared from ammonia and chloromethylenephosphonic acid.)
  • COOI-I Carboxyanilino N,N dimethylenephosphonic acid. (Prepared from anthranilic acid and chloromethylenephosphonic acid.)
  • 1,3 propanediamine N,N,N,N tetramethylenephosphonic acid Prepared from 1,3-propanediamine and chlorornethylenephosphonic acid.
  • 1,6 hexanediamine-N,N,N,N'-tetramethylenephosphonic acid Prepared from 1,6-hexanediamine and chloromethylenephosphonic acid.
  • NHCOCHs 0 Acetamidobenzylamino N,N-dimethylenephosphonic acid. (Prepared from o-acetamidobenzylamine and chloromethylenephosphonic acid.)
  • the phosphonic sequestering agents of our invention can be employed in photographic developing solutions of the type normally employed in black-and-white photography, or in color photography. They can also be employed in other photographic solutions Where it is desired to remove unexposed silver halide, such as fixing or stabilizing solutions, or they can be added to wash baths or toning baths.
  • Typical black-and-White developing agents which produce a negative silver image, include the polyhydroxy benzenes, such as hydroquinone, chlorohydroquinone, 2,5 (dihydroxyethylamino)-hydroquinone, methylhydroquinone, etc., monoalkylaminophenols, such as N-rnethylp-aminophenol (sulfate or hydrochloride), etc., 3-pyrazolidones, such as 1-phenyl-3-pyrazolidone, 4,4-dimethyl- 1-phenyl-3-pyrazolidone, 4,4-diethyl 1 phenyl-3-pyrazolidone, etc.
  • polyhydroxy benzenes such as hydroquinone, chlorohydroquinone, 2,5 (dihydroxyethylamino)-hydroquinone, methylhydroquinone, etc.
  • monoalkylaminophenols such as N-rnethylp-aminophenol (sulfate
  • color-forming developers useful in our invention have been previously described in the prior art and our invention is not restricted to the use of any particular color-forming developer.
  • Particularly useful color-forming developers are the phenylenediarnines and substituted derivatives thereof.
  • Typical of such color-forming developers are the sulfonamidosubstituted p-phenylenediarnines disclosed in Weissberger et al. US. Patent 2,548,574, issued April 10, 1951, the substituted p-phenylenediarnines disclosed in Weissberger et al. US. Patents 2,552,24-02, issued May 8, 1951, and the substituted pphenylenediamines disclosed in Weissberger et al. US. Patent 2,566,271, issued August 28, 1951.
  • Other phenylenediarnine color-forming developing agents can be employed to like advantage in the developing solutions of our invention.
  • alkaline agents such as carbonate, alkali, etc.
  • other ingredients such as antifoggants, e.g., benzotriazole, 6-nitrobenzotriazole, etc.
  • development restrainers e.g., potassium bromide, sodium iodide, etc.
  • preservatives such as alkali metal sulfites, e.g., sodium sulfite, etc.
  • couplers for forming the color image by coupling with the oxidation products of the color developer.
  • concentration of the sequestering agents of our invention can be varied widely in photographic developing solutions, depending upon the molecular weight of the particular sequestering agent, concentration of undesired calcium ions, etc. In general, we have found that from about 0.1 to 50 grams per liter of solution of the amino- N,N-dimethylenephosphonic acid or its derivative is quite satisfactory. A particularly useful range is from about 0.5 to 10 grams per liter of solution.
  • EXAMPLE 1 CALCIUM SEQUESTERING ABILITY The eifectiveness of ethylenediamine-N,N,N,N-tetramethylenephosphonic acid (EDTMP) as a sequestering agent against carbonate ion was determined by employing a 2.5 percent solution of sodium sesquicarbonate,
  • EXAMPLE 2.-DEVELOPER OXIDATION The addition of iron to a photographic developer will somewhat reduce its aeration life, for example, by 10 to 30 percent. However, the further addition of an aminocarboxylic acid complexing agent, such as ethylenediaminetetracetic acid (EDTA), will cause rapid oxidation,
  • EDTA ethylenediaminetetracetic acid
  • composition of Kodak Developer D-76 is as follows:
  • EXAMPLE 3 The photographic activity of the developer was not impaired by the addition of EDTMP sequestering agent. This is shown in the table below in which Kodak 13-76 developer is compared with the same developer modified by the addition of 2 g. of the EDTMP, heptasodiurn salt, per liter. A negative speed bromoiodide emulsion was exposed to a step wedge and developed in the two developers for minutes at 68 F. Substantially equal values of speed, fog, and contrast were obtained.
  • EXAMPLE 4- One of the disadvantages of EDTA as a sequestering agent is a propensity to cause an increase in developer fog, particularly with very high speed films.
  • the following data apply to a negative speed bromoiodide emulsion, for example, developed for 10 minutes at 68 F, in Kodak Developer DK-SO. It will be seen that while the addition of the EDTA caused bad fog, the addition of EDTMP caused no increase in fog.
  • composition of Kodak Developer DK5O is as follows: Monomethyl-p-aminophenol sulfate grams 2.5 Sodium sulfite, dessicated do 30.0 flydroquinonenus do 2.5 Sodium metaborate-8H O do 10.0 Potassium bromide do 0.5 Water to make liter 1.0
  • EXAMPLE s.- 1,s-prarvnnoraorAnorrnranmnrnrrisnnrnosrnonrc ACID orrr This material was prepared by reacting 1,3-diaminopropanol with chloromethylenephosphonic acid.
  • the reaction product contained about SOpercent by weight of the octasodium salt of the sequestrant and about 50 percent of' the sodium chloride. It proved to be an effective sequestering agent when employed under the conditions of Example 1, sequestering mg. of calcium chloride per gram, or 1.0 mole per mole of the DPTP. Used under the conditions of Example 2., it was found free from propensity to promote developer oxidation.
  • EXAMPLE 6 -1,3-FROPANEDIAMINE-PLNJJQN- TETRAMETHYLENEPHOSPHONIC ACID This compound was prepared by the methods described previously and obtained as a polysodium salt with sodium chloride as a diluent. It proved a very effective sequestering agent in borate-containing developers. Whereas unmodified Kodak Developer D76 precipitated on the addition of 40 mg. of calcium to a liter of the developer, the addition of 2 grams of the above agent per liter of 11-76 prevented the formation of a precipitate even when 400 mg. of calcium were added per liter, or 1100 mg. of calcium chloride. This concentration of calcium is in excess of that found even in very hard watersupplies.
  • EXAMPLE 7.-1,@EEXANEDIAMINENNN,N- TETRAMETHYLENEPHCSPhONIC ACID This compound was preparedby the methods described previously and obtained as a polysodium salt with sodium chloride as a diluent.
  • the calcium sequestering action was determined in a solution containing sulfate and borate as the precipitating ions in the proportions of 5 grams of anhydroussodium suitite, 0.75 gram of sodium bisulfite, and 2 grams of sodium metaborate octah'ydrate per 100 .ml.
  • the sequestering agents of our invention can be incorporated in drydeveloper compositionsof the type described by Kridel et al. US. Patents 2,666,702 and 2,666,- 703, issued January 19, 1954; Wiitala et al. US. Patents 2,682,464, and 2,682,465, issued June 29, 1954; Henn et al. US. Patent 2,685,513, issued August 3, 1954, and Baxendale et al. US. Patent 2,816,026, issued December 10, 1957.
  • Our dry developer compositions contain developing agents commonly used for developing exposed silver halide in emulsion layers used for black-and-white photography, such as p-aminophenol derivatives, e.g., monomethyl-paminophenol sulfate, ascorbic acid, hydroquinone, substituted hydroquinone, or a B-pyrazolidone developer.
  • Our dry compositions contain an alkali, for example,
  • Our dry compositions can contain an alkali sulfite, for example, sodium sulfite, potassium sulfite, etc.; analkali bisulfite, for example, sodium bisulfite, potassium bisulfite, etc.; an alkali metabisulfite, for example, sodium metabisultite, potassium metabisulfite, etc. Sufiicient amounts of these dry materials are used to provide in a solution prepared from the composition from 0.1 to 50 grams per liter of the amino-N,N-dimethylenephosphonic acid sequestering agent.
  • the fol-lowing composition is packaged ready for dissolving in one liter of water to make a photographic developing solution:
  • Compartment A Grams Monomethyl-paminophenol sulfate 5.0 Hydroquinone 2.5
  • the EDTMP can be placed in Compartment A rather than in Compartment B.
  • dry developer compositions can be added to the dry developer compositions, such as antifoggants, e.g., benzotriazole, development restrainers, e.g., alkali bromides, etc.
  • antifoggants e.g., benzotriazole
  • development restrainers e.g., alkali bromides, etc.
  • Developing compositions containing the calcium sequestrants of this invention can be combined developingand fixing solutions or combined developing and stabilizing baths, e.g., monobaths, such as those disclosed in Haist et al. U.S. Patent 2,875,048, issued February 24, 1959, Drey- Wood U.S. Patent 2,525,532, issued October 10, 1950, King U.S. Patent 2,397,016, issued March 19, 1946, Goldharnmer U.S. Patents 2,782,121 and 2,901,350, issued February 19, 1957 and August 25, 1959, respectively, and Goldhammer et a1.
  • U.S. Patent 2,782,120 issued February 19, 1957.
  • the incorporation of the amino-N,N-dimethylenephosphonic acid sequestering agent in the developer can be accomplished by adding the sequestrant to the emulsion layer or to a gelatin interlayer of a photographic element, and, as a result of treating the layer or interlayer with developing solution, the amino-N,N-dimethylenephosphonic acid will be thereby introduced into the photographic developer composition.
  • the sequestrants of our invention are not only useful for removing calcium ions, but also for magnesium or any other hard Water cations which may be present in a developer solution.
  • a photographic developer comprising an aqueous alkaline solution of a developing agent for photoexposed silver halide and a water-soluble salt of an acid selected from the class consisting of ethylenediamine-N,N,N',N'-
  • tetramethylenephosphonic acid nitrilo-N,N,N-trimethylenephosphonic acid, l,2-cyclohexanediamine-N,N,N',N'- tetramethylenephosphonic acid, o-carboXyanilino-N,N- dimethylenephosphonic acid, l,3-diaminopropanol-N,N, N,N-tetramethylenephosphonic acid, 1,3-propanediamine-N,N,N',N-tetramethylenephosphonic acid, 1,6-heX- anediamine N,N,N,N'-tetramethylenephosphonic acid, 2-pyridylamino-N,N'-dimethylenephosphonic acid and a compound represented by the following general formula:
  • R represents a group selected from the class consisting of alkyl containing from 1 to 4 carbon atoms, aryl containing from 6 to 7 carbon atoms, aralkyl con- 0 taining from 7 to 9 carbon atoms, cycloheXyl, cyclopentyl,
  • a photographic developer comprising an aqueous alkaline solution of a developing agent for photoexposed silver halide and a water-soluble salt of ethylenediamine- N,N,N,N-tetramethy1enephosphonic acid.
  • a photographic developer comprising an aqueous alkaline solution of a developing agent for photoexposed silver halide and a water-soluble salt of 1,3-diamino-2- propanol-N,N,N,N-tetramethylene-phosphonic acid.
  • a photographic developer comprising an aqueous alkaline solution of a developing agent for photoexposed silver halide and a water-soluble salt of nitrilo-N,N,N- trimethylenephosphonic acid.
  • a photographic developer comprising an aqueous alkaline solution of a developing agent for photoexposed silver halide and a water-soluble salt of propylamino-N,N- dimethylenephosphonic acid.
  • a photographic developer comprising an aqueous alkaline solution of a developing agent for photoexposed silver halide and a water-soluble salt of o-carboxyanilino- N,N-dimethylenephosphonic acid.

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  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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US101663A US3201246A (en) 1961-04-10 1961-04-10 Photographic developers containing calcium precipitation inhibitors
FR893776A FR1319265A (fr) 1961-04-10 1962-04-09 Nouvelles compositions de traitement photographique
GB13709/62A GB1006878A (en) 1961-04-10 1962-04-10 Photographic developing and other processing compositions

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3477849A (en) * 1964-03-23 1969-11-11 Eastman Kodak Co Multi-color dye developer systems
US3647449A (en) * 1970-06-08 1972-03-07 Eastman Kodak Co Neutralizing bath for use in photographic processing
US3658527A (en) * 1966-08-30 1972-04-25 Eastman Kodak Co Oxidation inhibitors for photographic materials
US3839045A (en) * 1972-02-08 1974-10-01 Eastman Kodak Co Photographic color developer solution stabilized with lithium ions
US3994730A (en) * 1972-09-22 1976-11-30 Agfa-Gevaert, A.G. Photographic color developer mixture
DE2707989A1 (de) * 1976-02-24 1977-08-25 Fuji Photo Film Co Ltd Farbentwickler und verfahren zum entwickeln von belichtetem, silberhalogenidhaltigem colormaterial
US4046570A (en) * 1975-06-13 1977-09-06 Agfa-Gevaert N.V. Hardening fixer for photographic silver halide material
US4142895A (en) * 1977-01-12 1979-03-06 Agfa Gevaert Aktiengesellschaft Photographic color developer composition
US4146397A (en) * 1976-08-06 1979-03-27 Fuji Photo Film Co., Ltd. Method of forming a photographic image
USRE30064E (en) * 1976-02-24 1979-08-07 Fuji Photo Film Co., Ltd. Process for color photographic processing
US4264716A (en) * 1979-09-10 1981-04-28 Eastman Kodak Company Photographic color developer compositions
JPS5670549A (en) * 1979-11-14 1981-06-12 Konishiroku Photo Ind Co Ltd Method for processing silver halide photographic material
US4330616A (en) * 1980-07-31 1982-05-18 Konishiroku Photo Industry Co., Ltd. Method for processing silver halide color photographic material
US4551411A (en) * 1984-12-28 1985-11-05 Eastman Kodak Company Sequestrants used in diffusion transfer elements with metallizable dyes
JPS60247241A (ja) * 1985-03-25 1985-12-06 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
US4672025A (en) * 1984-07-30 1987-06-09 Fuji Photo Film Co., Ltd. Method for processing silver halide photographic material
US4873180A (en) * 1987-04-13 1989-10-10 Minnesota Mining And Manufacturing Company Developer compositions for silver halide photographic materials comprising cyclic amino methane diphosphonic acid compounds
US4912015A (en) * 1987-09-16 1990-03-27 Fuji Photo Film Co., Ltd. Silver salt diffusion transfer using organic phosphonic acid compounds
US4948710A (en) * 1984-06-26 1990-08-14 Fuji Photo Film Co., Ltd. Method of processing silver halide color photographic light-sensitive materials
US4956267A (en) * 1987-03-25 1990-09-11 Fuji Photo Film Co., Ltd. Method for forming a direct positive color image
JPH03129344A (ja) * 1979-11-14 1991-06-03 Konica Corp ハロゲン化銀カラー写真感光材料の処理方法
US5389502A (en) * 1994-02-08 1995-02-14 Eastman Kodak Company Hardening developer for silver halide photography and development method
US5391466A (en) * 1992-11-25 1995-02-21 Konica Corporation Chemical compositions and a processing method using the same for processing silver halide photographic light-sensitive material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2819487B2 (ja) * 1992-10-05 1998-10-30 富士写真フイルム株式会社 写真用処理組成物及び処理方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2599807A (en) * 1950-06-01 1952-06-10 Frederick C Bersworth Alkylene polyamine methylene phosphonic acids
GB703180A (en) * 1950-06-01 1954-01-27 Frederick Charles Bersworth Improvements in alkylene polyamino phosphonic acids and method of producing same
DE1045373B (de) * 1957-04-26 1958-12-04 Hoechst Ag Verwendung von Phosphonsaeuren

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2599807A (en) * 1950-06-01 1952-06-10 Frederick C Bersworth Alkylene polyamine methylene phosphonic acids
GB703180A (en) * 1950-06-01 1954-01-27 Frederick Charles Bersworth Improvements in alkylene polyamino phosphonic acids and method of producing same
DE1045373B (de) * 1957-04-26 1958-12-04 Hoechst Ag Verwendung von Phosphonsaeuren

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3477849A (en) * 1964-03-23 1969-11-11 Eastman Kodak Co Multi-color dye developer systems
US3658527A (en) * 1966-08-30 1972-04-25 Eastman Kodak Co Oxidation inhibitors for photographic materials
US3647449A (en) * 1970-06-08 1972-03-07 Eastman Kodak Co Neutralizing bath for use in photographic processing
US3839045A (en) * 1972-02-08 1974-10-01 Eastman Kodak Co Photographic color developer solution stabilized with lithium ions
US3994730A (en) * 1972-09-22 1976-11-30 Agfa-Gevaert, A.G. Photographic color developer mixture
US4046570A (en) * 1975-06-13 1977-09-06 Agfa-Gevaert N.V. Hardening fixer for photographic silver halide material
DE2707989A1 (de) * 1976-02-24 1977-08-25 Fuji Photo Film Co Ltd Farbentwickler und verfahren zum entwickeln von belichtetem, silberhalogenidhaltigem colormaterial
US4083723A (en) * 1976-02-24 1978-04-11 Fuji Photo Film Co., Ltd. Process for color photographic processing
USRE30064E (en) * 1976-02-24 1979-08-07 Fuji Photo Film Co., Ltd. Process for color photographic processing
US4146397A (en) * 1976-08-06 1979-03-27 Fuji Photo Film Co., Ltd. Method of forming a photographic image
US4142895A (en) * 1977-01-12 1979-03-06 Agfa Gevaert Aktiengesellschaft Photographic color developer composition
JPS5647038A (en) * 1979-09-10 1981-04-28 Eastman Kodak Co Aqueous solution for photography color development
US4264716A (en) * 1979-09-10 1981-04-28 Eastman Kodak Company Photographic color developer compositions
JPS5670549A (en) * 1979-11-14 1981-06-12 Konishiroku Photo Ind Co Ltd Method for processing silver halide photographic material
JPH03129344A (ja) * 1979-11-14 1991-06-03 Konica Corp ハロゲン化銀カラー写真感光材料の処理方法
US4330616A (en) * 1980-07-31 1982-05-18 Konishiroku Photo Industry Co., Ltd. Method for processing silver halide color photographic material
US4948710A (en) * 1984-06-26 1990-08-14 Fuji Photo Film Co., Ltd. Method of processing silver halide color photographic light-sensitive materials
US4672025A (en) * 1984-07-30 1987-06-09 Fuji Photo Film Co., Ltd. Method for processing silver halide photographic material
US4551411A (en) * 1984-12-28 1985-11-05 Eastman Kodak Company Sequestrants used in diffusion transfer elements with metallizable dyes
JPS60247241A (ja) * 1985-03-25 1985-12-06 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
US4956267A (en) * 1987-03-25 1990-09-11 Fuji Photo Film Co., Ltd. Method for forming a direct positive color image
US4873180A (en) * 1987-04-13 1989-10-10 Minnesota Mining And Manufacturing Company Developer compositions for silver halide photographic materials comprising cyclic amino methane diphosphonic acid compounds
US4912015A (en) * 1987-09-16 1990-03-27 Fuji Photo Film Co., Ltd. Silver salt diffusion transfer using organic phosphonic acid compounds
US5391466A (en) * 1992-11-25 1995-02-21 Konica Corporation Chemical compositions and a processing method using the same for processing silver halide photographic light-sensitive material
US5389502A (en) * 1994-02-08 1995-02-14 Eastman Kodak Company Hardening developer for silver halide photography and development method

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GB1006878A (en) 1965-10-06
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