EP0446457B1 - Révélateur photographique alcalin pour noir et blanc - Google Patents

Révélateur photographique alcalin pour noir et blanc Download PDF

Info

Publication number
EP0446457B1
EP0446457B1 EP90124427A EP90124427A EP0446457B1 EP 0446457 B1 EP0446457 B1 EP 0446457B1 EP 90124427 A EP90124427 A EP 90124427A EP 90124427 A EP90124427 A EP 90124427A EP 0446457 B1 EP0446457 B1 EP 0446457B1
Authority
EP
European Patent Office
Prior art keywords
developer
per liter
antifoggant
moles per
alkaline aqueous
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.)
Expired - Lifetime
Application number
EP90124427A
Other languages
German (de)
English (en)
Other versions
EP0446457A3 (en
EP0446457A2 (fr
Inventor
Carlo Marchesano
Carlo Illuminati
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.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0446457A2 publication Critical patent/EP0446457A2/fr
Publication of EP0446457A3 publication Critical patent/EP0446457A3/en
Application granted granted Critical
Publication of EP0446457B1 publication Critical patent/EP0446457B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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

  • the present invention relates to an alkaline black-and-white developer for processing a silver halide photographic material and, more particularly, to an alkaline black-and-white hardening developer for processing a silver halide radiographic material in an automatic processor.
  • the developer provides improved stability and excellent photographic properties.
  • Aqueous black-and white developers used for processing silver halide photographic materials comprise, as main components, hydroquinone and 3-pyrazolidone developing agents, an alkali agent, an organic antifoggant and a sulfite.
  • a problem that is frequently encountered with said hardening developers is the tendency of the developing agent to degrade during storage and use.
  • the higher the amount of the sulfite the longer the useful life of the developer.
  • high concentrations of sulfites in a developer cause a reduced activity and dark deposits in the developer tank.
  • the presence of metal ion traces (such as Fe ++ the developer causes the catalytic oxidation of the sulfites.
  • Sequestering agents such as ethylenediaminetetraacetic acid (EDTA), used to prevent the precipitation of calcium salts in the developers, in the presence of traces of iron ions cause the autoxidation of the hydroquinone developing agent at a higher rate than in the absence of the EDTA.
  • EDTA ethylenediaminetetraacetic acid
  • US Pat. NO. 4,672,025 describes a black-and-white developer comprising hydroquinone, a 3-pyrazolidone developing agent, a dialdehyde hardener, an organic antifoggant and a sequestering agent selected from the group consisting of diethylenetriaminepentaacetic acid (DTPA), triethylenetetraminehexa- acetic acid (TTHA) , 1,3-di-amino-2-propanoltetraacetic acid (DPTA), glycol ether diaminetetraacetic acid, ethylenediaminetetramethylenephosphonic acid (EDTP), aminotrimethylenephosphonic acid and alkali metal salts of said acids.
  • DTPA diethylenetriaminepentaacetic acid
  • TTHA triethylenetetraminehexa- acetic acid
  • DPTA 1,3-di-amino-2-propanoltetraacetic acid
  • EDTP ethylenediaminetetramethylenephosphonic acid
  • European Patent Application No. 286,874 describes the use of a dialkylaminomethane diphosphonic acid sequestering agent (including cyclicaminomethane diphosphonic acids) in aqueous alkaline photographic developers to increase the stability of the developers and inhibit deposit formation.
  • Said developers do not include hardeners and are intended for manual processing, preferably of silver halide color photographic materials.
  • US Pat. No. 4,810,622 describes a black-and-white developer having a pH value of 9.2 to 10 comprising hydroquinone, a 3-pyrazolidone developing agent, a dialdehyde hardener, an organic antifoggant, a chelating agent selected form the group consisting of diethylenetriaminepentaacetic acid (DTPA), triethylenetetramine-hexaacetic acid (TTHA), 1,3-diamino-2-propanoltetraacetic acid (DPTA), ethylenediaminetetramethylenephosphonic acid (EDTP), aminotrimethylenephosphonic acid and alkali metal salts of said acids, a silver halide solvent and a sulfite.
  • DTPA diethylenetriaminepentaacetic acid
  • TTHA triethylenetetramine-hexaacetic acid
  • DPTA 1,3-diamino-2-propanoltetraacetic acid
  • EDTP ethylenediaminet
  • Alkaline aqueous black-and-white photographic developers for processing of silver halide radiographic materials comprise (1) a hydroquinone, (2) a 3-pyrazolidone developing agent, (3) a dialdehyde hardener, (4) antifoggants, (5) a sequestering agent, (6) a sulfite antioxidant, and (7) a buffering agent, wherein said sequestering agent is a cyclicaminomethane diphosphonic acid compound, the molar ratio of the buffering agent to the sulfite antioxidant is at least 0.5:1 and the molar ratio of the sulfite antioxidant to hydroquinone is at least 1.5:1.
  • the antifoggants comprise a combination of a benzotriazole-type antifoggant, an indazole-type antifoggant and a mercaptotetrazole-type antifoggant.
  • the developer is stable over long periods of time and can provide excellent photographic properties when used in automatic processing machines.
  • the developer allows control of the photographic characteristics (fog and gradation) even when used at high temperature for rapid processing.
  • the present invention relates to an alkaline aqueous black-and-white photographic developer, for processing a silver halide photographic material, particularly a silver halide radiographic material, comprising (1) at least one of hydroquinones, (2) at least one of 3-pyrazolidone developing agents,(3) at least one of dialdehyde hardeners, (4) at least one antifoggant, (5) a sequestering agent, (6) a sulfite antioxidant, and (7) a buffering agent, characterized in that said sequestering agent is a cyclicaminomethane diphosphonic acid compound, the molar ratio of the buffering agent to the sulfite antioxidant is at least 0.5:1 and the molar ratio of the sulfite antioxidant to hydroquinone is at least 1.5:1.
  • the present invention relates to an alkaline developer as described above, wherein the antifoggant comprise a combination of a benzotriazole-type antifoggant, an indazole-type antifoggant and a mercaptotetrazole-type antifoggant.
  • cyclicaminomethane diphosphonic acid compounds used in the developer of this invention are those described in the European Patent Application No. 286,874.
  • said cyclicaminomethane diphosphonic acid compounds correspond to the following formula wherein R 1 , R 2 and R 3 , equal or different, each represent a hydrogen atom or a PO 3 M'M" group, wherein M' and M" represent a hydrogen atom, an alkaline metal such as Li, Na or K or a quaternary ammonium group such as ammonium, pyridinium, triethanolammonium or triethylammonium, and Q represents the atoms or chemical bonds necessary to complete a 3- to 6-membered ring such as aziridino, pyrrolidino, imidazolidino, piperidino, isoindolino or morpholino, with the proviso that at least two of R 1 , R 2 and R 3 substituents represent a PO 3 M'M" group.
  • Said sequestering agents can be advantageously used in amounts of about 0.0005 to about 0.5 moles per liter, preferably of about 0.008 to about 0.1 moles per liter of the developer.
  • sequestering agents can be used in combination with other sequestering agents known in the art such as, for example, aminopolycarboxylic acids (ethylenediaminotetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, diaminopropanoltetraacetic acid, etc.), aminopolyphosphonic acids (methylaminophosphonic acid, phosphonic acids described in Research Disclosure 18837 of December 1979, phosphonic acids described in US Pat. No.
  • aminopolycarboxylic acids ethylenediaminotetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, diaminopropanoltetraacetic acid, etc.
  • aminopolyphosphonic acids methylaminophosphonic acid, phosphonic acids described in Research Disclosure 18837 of December 1979, phosphonic acids described in US Pat. No.
  • polyphosphate compounds sodium hexametaphosphate, etc.
  • ⁇ -hydroxycarboxylic acid compounds lactic acid, tartaric acid, etc.
  • dicarboxylic acid compounds malonic acid, etc.
  • ⁇ -ketocarboxylic acid compounds pyruvic acid, etc.
  • alkanolamine compounds diethanolamine, etc.
  • the sequestering agents incorporated into the black-and-white hardening developer of the present invention have been found to increase the stability of the developer over a long period of time.
  • the developer composition of a present invention is suitable for obtaining black-and white images upon development of light-exposed silver halide photographic materials, in particular radiographic materials.
  • it comprises a black-and-white developing agent, a dialdehyde hardener, a sulfite antioxidant, an antifoggant agent, buffering agents and alkaline agents.
  • Black-and-white developing agents for use in the present invention include hydroquinone and hydroquinone derivatives (for example t-butylhydroquinone, methylhydroquinone, dimethylhydroquinone, chlorohydroquinone, dichlorohydroquinone, bromohydroquinone, 1,4-dihydronaphthalene, methoxyhydroquinone, ethoxyhydroquinone, hydroquinone monosulfonate, hydroquinone disulfonate, etc.). Hydroquinone, however, is preferred.
  • Said- black-and-white developing agents are generally used in amounts of from 0.075 to 0.75 moles per liter, preferably of from 0.10 to 0.50 moles per liter of developer.
  • Said black-and-white developing agents are used in combination with auxiliary developing agents which show a superadditive developing effect, such as p-aminophenol and p-aminophenol derivatives (such as N-methyl-p-aminophenol and 2,4-diaminophenol) and pyrazolidone compounds (such as 1-phenyl-3-pyrazolidone) and pyrazolidone derivatives (such as 4-methyl-1-phenyl-3-pyrazolidone and 4,4'-dimethyl-1-phenyl-3-pyrazolidone).
  • p-aminophenol and p-aminophenol derivatives such as N-methyl-p-aminophenol and 2,4-diaminophenol
  • pyrazolidone compounds such as 1-phenyl-3-pyrazolidone
  • pyrazolidone derivatives such as 4-methyl-1-phenyl-3-pyrazolidone and 4,4'-dimethyl-1-phenyl-3-pyrazolidone.
  • Said auxiliary developing agents are generally used in amounts of from 0.0003 to 0.15 moles per liter, preferably of form 0.003 to 0.1 moles per liter of developer.
  • Dialdehyde hardeners used in the developer of this invention include, for example, glutaraldehyde, ⁇ -methyl-glutaraldehyde, ⁇ -methylglutaraldehyde, maleic dialdehyde, succinic dialdehyde, methoxysuccininc dialdehyde, ⁇ --methoxy- ⁇ -ethoxyglutaraldehyde, ⁇ -n-butoxyglutaraldehyde, ⁇ , ⁇ -dimethoxysuccinic dialdehyde, ⁇ -isopropylsuccinic dialdehyde, ⁇ , ⁇ -diethylsuccinic dialdehyde, butylmaleic dialdehyde, and bisulfite adducts of these aldehydes.
  • dialdehyde hardeners are generally used in amounts of from 0.001 to 0.3 moles per liter, preferably of from 0.01 to 0.1 moles per liter of developer.
  • Antioxidants are generally sulfites.
  • sulfites we mean here those compounds known in the art as capable of generating sulfite ions (SO 3 -- ) in aqueous solutions and include sulfites, bisulfites, metabisulfites (1 mole of metabisulfite forming 2 moles of bisulfite in aqueous solution) and aldehyde bisulfite adducts.
  • sulfites, bisulfites, metabisulfites include sodium sulfite, sodium bisulfite, sodium metabisulfite, potassium sulfite, potassium bisulfite, potassium metabisulfite and ammonium metabisulfite.
  • the amount of the total sulfite ions is preferably not less than 0.05 moles, more preferably 0.1 to 1.25 moles, and most preferably 0.3 to 0.9 moles, per liter of developer.
  • the molar ratio of the sulfite ions with respect to the hydroquinone is at least 1.5:1, preferably exceeds 2:1 and, more preferably, is between 2.5:1 to 4:1.
  • Antifoggants which are known in the art to control the fog appearence in processed photographic materials, useful in the developer of the present invention include benzimidazole-, benzotriazole-, mercaptoazole-, indazole-and mercaptothiadiazole-type antifoggants.
  • Preferred antifoggants include 5-nitroindazole, benzimidazole nitrate, 5-methylbenzotriazole and 1-phenyl-5-mercaptotetrazole. Said compounds are used, alone or in combination, in amounts of from about 1x10 -6 to about 5x10 -1 moles per liter, preferably of from about 5x10 -4 to about 1x10 -1 moles per liter of the developer.
  • the developer comprises a combination of benzotriazole-, indazole- and mercaptoazole-type antifoggants, more preferably a combination of 5-methylbenzotriazole, 5-nitroindazole and l-phenyl-5-mercaptotetrazole.
  • said combination comprises from 7x10 -5 to 0.04 moles per liter of said benzotriazole-type antifoggant, from 6x10 -6 to 0.03 moles per liter of said indazole-type antifoggant and from 6x10 -6 to 0.02 moles per liter of said mercaptoazole type antifoggant. Examples of mercaptoazoles are described in US Pat. No.
  • the present invention relates to an alkaline aqueous black-and-white photographic developer, for processing a silver halide photographic material, particularly a silver halide radiographic material, comprising (1) at least one hydroquinone, (2) at least one 3-pyrazolidone developing agent, (3) at least one dialdehyde hardener, (4) at least one antifoggant, (5) a sequestering agent, (6) a sulfite antioxidant, and (7) a buffering agent, characterized in that said sequestering agent is a cyclicaminomethane diphosphonic acid compound, the molar ratio of the buffering agent to the sulfite antioxidant is at least 0.5:1, the molar ratio of the sulfite antioxidant to hydroquinone is at least 1.5:1 and the antifoggant comprises a combination of a benzotriazole-type antifoggant, an indazole-type antifoggant and a mercaptotetrazole
  • the developer in accordance with the present invention includes a buffer (e.g., carbonic acid salts, phosphoric acid salts, polyphosphates, metaborates, boric acid and boric acid salts).
  • a buffer e.g., carbonic acid salts, phosphoric acid salts, polyphosphates, metaborates, boric acid and boric acid salts.
  • the amount of the buffer with respect to the sulfite exceeds a molar ratio of 0.5:1 and, more preferably, is between 1:1 to 2:1.
  • inorganic alkaline agents to obtain the preferred pH which is usually higher than 10.
  • Said inorganic alkaline agents include KOH, NaOH, LiOH, sodium and potassium carbonate, etc.
  • adjuvants well known to the skilled in the art of developer formulation may be added to the developer of the present invention.
  • these include restrainers, such as the soluble halides (e.g., KBr), solvents (e.g., polyethylene glycols and esters thereof), development accelerators (e.g., polyethylene glycols and pyrimidinium compounds), preservatives, surface active agents, and the like.
  • the developer of the invention is prepared by dissolving the ingredients in water and adjusting the pH to the desired value.
  • the developer may also be prepared in a concentrated form and then diluted to a working strength just prior to use.
  • the developer may be prepared in two or more concentrated parts to be combined and diluted with water to the desired strength and placed in the developer tank of the automatic processing machine.
  • the developer of the present invention is particularly useful when processing is carried out in automatic processing machines.
  • Automatic processing machines may be of the type described in US Pat. No. 3,545,971, such as an "X-OMAT Processor” made by Eastman Kodak Company, of the series of "TRIMATIC” Processors made by 3M Company and of the type of "Model RK” made by Fuji Photo Film Company.
  • the developing temperature and the developing time are in relation to each other and are dependant on the total processing time. In general, they are about 20°C to 50°C, and 10 seconds to 1.5 minutes, respectively.
  • the silver halide material is fixed, preferably in an acid fixer, and washed and dried in the usual manner.
  • these steps are determined by the machine.
  • the silver halide photographic materials which can be used in the present invention comprise a support and at least one silver halide emulsion layer coated on the support.
  • the silver halide emulsion layer may be coated on one side of the support or on both sides thereof.
  • the silver halide photographic element can comprise other non light-sensitive layers, such as backing layers, antihalation layers, interlayers, filter layers, protective layers.
  • the silver halide emulsion comprise silver halide grains (such as silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide) dispersed in an hydrophilic colloid (such as gelatin, modified gelatins, albumin, casein, sodium alginate, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone and mixtures thereof).
  • the emulsion can contain cubic, octahedral, spherical and/or tabular silver halide grains.
  • the emulsion can be chemical and optical sensitized and added during its manufacture or before its coating various additives, such as stabilizers, antifoggants, hardeners, coating aids, etc.
  • the silver halide emulsion is coated on a support such as a cellulose acetate film, or a polyethylene terephthalate film using coating methods well known in the art, and dried.
  • the silver halide photographic materials to be used in the present invention are preferably black-and-white radiographic materials of high gradation (contrast) and particularly preferably materials which provide a gradation of 1.5 to 4.0.
  • a double layer coated radiographic film 3M type XD-A and a single layer coated radiographic film 3M type MS-3 were processed using developers 5 and 6, fresh and oxidized, for 20 seconds at 35°C, followed by fixing in 3M XAF/3 Fixer for 24 seconds at 30°C, washing in tap water for 22 seconds at 35°C and drying for 22 seconds at 35°C.
  • a green sensitive double layer coated radiographic film 3M type XD-A and a blue sensitive double layer coated radiographic film 3M type R-2 were processed using the developers above for 20 seconds at 39°C, followed by fixing in 3M XAF/3 Fixer for 24 seconds at 30°C, washing in tap water for 22 seconds at 35°C and drying for 22 seconds at 35°C.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photographic Processing Devices Using Wet Methods (AREA)

Claims (8)

  1. Révélateur photographique pour développement en noir et blanc aqueux alcalin comprenant
    (1) une hydroquinone,
    (2) un agent de développement 3-pyrazolidone,
    (3) un durcisseur dialdéhydique,
    (4) au moins un antivoile,
    (5) un agent séquestrant,
    (6) un antioxydant sulfite, et
    (7) un agent tampon,
    dans lequel l'agent séquestrant est un composé d'acide diphosphonique d'aminométhane cyclique, le rapport molaire de l'agent tampon à l'antioxydant sulfite est d'au moins 0,5/1 et le rapport molaire de l'antioxydant sulfite à l'hydroquinone est d'au moins 1,5/1.
  2. Révélateur aqueux alcalin suivant la revendication 1, dans lequel le rapport de l'agent tampon à l'antioxydant sulfite est dans la gamme de 1/1 à 2/1.
  3. Révélateur aqueux alcalin suivant la revendication 1, dans lequel le composé d'acide diphosphonique d'aminométhane cyclique correspond à la formule suivante :
    Figure imgb0009
     dans laquelle R1, R2 et R3, égaux ou différents, représentent chacun un atome d'hydrogène ou un groupe PO3M'M", dans lequel M' et M" représentent un atome d'hydrogène, un métal alcalin ou un groupe d'ammonium quaternaire et Q représente les atomes ou liaisons chimiques nécessaires pour former un cycle de 3 à 6 chaînons, à la condition qu'au moins deux des substituants R1, R2 et R3 représentent un groupe PO3M'M".
  4. Révélateur aqueux alcalin suivant la revendication 1, dans lequel l'agent séquestrant correspond à la formule :
    Figure imgb0010
  5. Révélateur aqueux alcalin suivant la revendication 1, dans lequel l'agent séquestrant est utilisé en une quantité de 5x10-4 à 5x10-1 mole par litre de révélateur.
  6. Révélateur aqueux alcalin suivant la revendication 5, dans lequel l'hydroquinone est présente dans le révélateur en une quantité allant de 0,075 à 0,75 mole par litre, l'agent de développement 3-pyrazolidone est présent en une quantité allant de 3x10-4 à 0,15 mole par litre, le durcisseur dialdéhydique est présent en une quantité allant de 1x10-3 à 0,3 mole par litre, les antivoiles sont présents en une quantité allant de 1x10-6 à 0,1 mole par litre, le rapport molaire de l'antioxydant sulfite à l'hydroquinone est d'au moins 1,5/1 et le rapport molaire de l'agent tampon à l'antioxydant sulfite est d'au moins 0,5/1.
  7. Révélateur aqueux alcalin suivant l'une quelconque des revendications 1 à 6, dans lequel les antivoiles comprennent une combinaison d'un antivoile du type benzotriazole, d'un antivoile du type indazole et d'un antivoile du type mercaptotétrazole.
  8. Révélateur aqueux alcalin suivant la revendication 7, dans lequel la combinaison d'antivoiles comprend de 7x10-5 à 0,04 mole par litre de l'antivoile du type benzotriazole, de 6x10-6 à 0,03 mole par litre de l'antivoile du type indazole et de 6x10-6 à 0,02 mole par litre de l'antivoile du type mercaptotétrazole.
EP90124427A 1990-03-12 1990-12-17 Révélateur photographique alcalin pour noir et blanc Expired - Lifetime EP0446457B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT1964590 1990-03-12
IT19645A IT1240596B (it) 1990-03-12 1990-03-12 Sviluppatore fotografico alcalino in bianco e nero

Publications (3)

Publication Number Publication Date
EP0446457A2 EP0446457A2 (fr) 1991-09-18
EP0446457A3 EP0446457A3 (en) 1992-02-26
EP0446457B1 true EP0446457B1 (fr) 1996-10-30

Family

ID=11160053

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90124427A Expired - Lifetime EP0446457B1 (fr) 1990-03-12 1990-12-17 Révélateur photographique alcalin pour noir et blanc

Country Status (4)

Country Link
EP (1) EP0446457B1 (fr)
JP (1) JP2989289B2 (fr)
DE (1) DE69029032T2 (fr)
IT (1) IT1240596B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5389502A (en) * 1994-02-08 1995-02-14 Eastman Kodak Company Hardening developer for silver halide photography and development method
JP3449128B2 (ja) * 1996-08-30 2003-09-22 信越半導体株式会社 単結晶成長方法
DE19644226A1 (de) * 1996-10-24 1998-04-30 Agfa Gevaert Ag Fixierbad
DE10257939A1 (de) * 2002-12-12 2004-06-24 Herbert Hafner Fotografisches Entwicklerbad

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0307867A2 (fr) * 1987-09-14 1989-03-22 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière ayant une finesse supérieure et utilisable pour un traitement ultra-rapide

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2246610C3 (de) * 1972-09-22 1980-01-03 Agfa-Gevaert Ag, 5090 Leverkusen Photographischer Farbentwickler
US4264716A (en) * 1979-09-10 1981-04-28 Eastman Kodak Company Photographic color developer compositions
IT1175017B (it) * 1983-09-20 1987-07-01 Minnesota Mining & Mfg Composizioni di sviluppo per materiali fotografici agli alogenuri d'argento
JPH0690455B2 (ja) * 1986-07-02 1994-11-14 富士写真フイルム株式会社 ハロゲン化銀写真感光材料の処理方法
IT1215423B (it) * 1987-04-13 1990-02-08 Minnesota Mining & Mfg Composizioni di sviluppo per materiali fotografici agli alogenuri d'argento.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0307867A2 (fr) * 1987-09-14 1989-03-22 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière ayant une finesse supérieure et utilisable pour un traitement ultra-rapide

Also Published As

Publication number Publication date
EP0446457A3 (en) 1992-02-26
DE69029032T2 (de) 1997-03-06
JPH04219753A (ja) 1992-08-10
IT9019645A0 (it) 1990-03-12
DE69029032D1 (de) 1996-12-05
EP0446457A2 (fr) 1991-09-18
IT9019645A1 (it) 1991-09-12
JP2989289B2 (ja) 1999-12-13
IT1240596B (it) 1993-12-17

Similar Documents

Publication Publication Date Title
US4310622A (en) Photographic development process
JPH08248583A (ja) アルカリ性ヒドロキノン・フリー水性黒白放射線写真用現像液
US4672025A (en) Method for processing silver halide photographic material
US4371610A (en) Process for development-processing silver halide light-sensitive material
US3994729A (en) Method for processing photographic light-sensitive material
US4737450A (en) Method for bleach-fixing of photographic elements
EP0446457B1 (fr) Révélateur photographique alcalin pour noir et blanc
US4391900A (en) Process for development-processing silver halide light-sensitive material
US4810622A (en) Method for processing silver halide photographic material with an alkaline black and white developer
US4717649A (en) Photographic bleach-fixing compositions
US5389502A (en) Hardening developer for silver halide photography and development method
EP0632323B1 (fr) Compositions de développement pour halogénure d'argent photographique et procédé pour former des images photographique d'argent
EP0810472B1 (fr) Développateur alcalin d'un matériau photographique à l'halogénure d'argent pour la photographie en noir et blanc
US3276875A (en) Developing composition with pyrrolidone anti-sludging agent
US5776666A (en) Triazolium thiolate baths for silver halide development acceleration
US5578434A (en) Photographic silver halide developer composition and process for forming photographic silver images
EP0753793B1 (fr) Composition de révélateur pour des matériaux photographiques à l'halogénure d'argent
US5686232A (en) Composition for developing an exposed photographic product having improved stability in air
EP0786698A1 (fr) Composition de révélateur organique-inorganique
EP0654148B1 (fr) Utilisation de cetogluconates en photographie
JPH07117710B2 (ja) 処理剤組成物
JPS58207045A (ja) ハロゲン化銀写真感光材料用現像剤
EP0736802A1 (fr) Développateur et méthode de développement de matériaux photographique à l'halogénure d'argent
JPH02118634A (ja) ハロゲン化銀感光材料用現像処理剤キット
JPH0318173B2 (fr)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19901217

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE CH DE FR GB LI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE CH DE FR GB LI

17Q First examination report despatched

Effective date: 19950316

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE FR GB LI

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: E. BLUM & CO. PATENTANWAELTE

REF Corresponds to:

Ref document number: 69029032

Country of ref document: DE

Date of ref document: 19961205

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19980109

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19980115

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981231

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981231

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981231

BERE Be: lapsed

Owner name: MINNESOTA MINING AND MFG CY

Effective date: 19981231

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20061106

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20061201

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20061229

Year of fee payment: 17

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20071217

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080701

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20081020

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20071217

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20071231