EP0738400B1 - Photographische entwicklerzusammensetzung ohne hydrochinon und verarbeitungsverfahren - Google Patents

Photographische entwicklerzusammensetzung ohne hydrochinon und verarbeitungsverfahren Download PDF

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Publication number
EP0738400B1
EP0738400B1 EP94919380A EP94919380A EP0738400B1 EP 0738400 B1 EP0738400 B1 EP 0738400B1 EP 94919380 A EP94919380 A EP 94919380A EP 94919380 A EP94919380 A EP 94919380A EP 0738400 B1 EP0738400 B1 EP 0738400B1
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Prior art keywords
amount
acid
mol
developer
ascorbic acid
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EP94919380A
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English (en)
French (fr)
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EP0738400A4 (de
EP0738400A1 (de
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Haixing Wan
Diane Zhang
David Carlson
Alan A. Bornstein
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Fuji Hunt Photographic Chemicals NV
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Fuji Hunt Photographic Chemicals NV
Fujifilm Hunt Chemicals USA Inc
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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
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • 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
    • G03C1/061—Hydrazine compounds
    • 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
    • G03C2200/00—Details
    • G03C2200/48—Polyoxyethylene
    • 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
    • G03C7/36—Couplers containing compounds with active methylene groups
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings

Definitions

  • This invention relates to a non-hydroquinone developer composition and its method of usage in development of photographic elements. More specifically, this invention relates to a non-hydroquinone developer composition which is particularly useful in the development of various types of photographic black-and-white photographic elements to assuredly achieve a lith quality development without the need for the presence of toxic hydroquinone. Even more particularly, the photographic developing composition of the present invention is advantageously used to develop internally boosted silver halide emulsions containing a hydrazine compound functioning as a nucleating agent.
  • the developer exhibits low capacity as a result of the fact that it contains hydroquinone as the sole developing agent and, further, aldehyde tends to react with the hydroquinone developer to cause undesirable changes in development activity. Further, the low sulfite ion concentration is inadequate to provide effective protection against aerial oxidation. As a consequence, the conventional "lith" developer solution is lacking in stability.
  • hydroquinone-based developing systems have allergenic effects. Therefore, the use of hydroquinone poses certain handling and disposal problems in view of applicable health, safety and environment guidelines and regulations.
  • WO 93/11456 describes a rapid access developer for hydrazine-containing films comprising at least one alkanolamine in an amount of 5-50 g/l; at least one ascorbic acid developing agent; and having a pH in the range of 10.7 to about 12.0.
  • the developer may further contain KOH and potassium carbonate.
  • alkanolamines possess the undesirable characteristic of toxicity, excessive volatility and unpleasant odor.
  • alkanolamines tend to adversely affect high contrast lith image performance.
  • U.S. Patent No. 5,196,298 which corresponds to European Patent Application No. 0 498 968 published August 19, 1992, proposes a photographic developing solution for immersion development having a pH of at least 12.0 and containing more than 0.4 mols/liter of a sugar derivative, or an alkali metal salt thereof, such as l-ascorbic acid and iso-ascorbic acid, which preferably contains no other developing agents and no sulfite ions.
  • the developer solution of U.S. Patent No. 5,196,298 is described as permitting the development of graphic arts photographic materials with lith quality while permitting the disposal of the depleted developer solutions in a more environmentally ready manner.
  • U.S. Patent No. 5,196,298 also states that the full benefits of that invention are achieved in a pH range of 12.3 to 13.5, which is a relatively high pH range, and which may not be acceptable to all users.
  • U.S. Patent No. 5,098,819 also discloses a non-hydroquinone and non-alkali metal hydroxide containing photographic developer composition.
  • the non-hydroquinone developer solution of this patent contains a developer selected from ascorbic acid and sugar-type derivatives thereof, together with a sulfite, an alkali metal carbonate and a 3-pyrazolidone developer compound, wherein the developer solution has a pH range of 9.75 to 10.6.
  • the U.S. Patent 5,098,819 describes the developer composition as being subject to degradation at pH's in excess of about 10.6.
  • 59-191035 published October 30, 1984 discloses a developer composition, which is especially adapted for processing a silver halide emulsion containing a black dye, wherein the developer is described as containing ascorbic acid, alkali metal carbonate, alkali metal sulfite and alkali hydroxide in a pH range of 10 to 14.
  • these two latter-mentioned publications do not describe lith developers in particular, nor do these publications describe testing data which shows lith quality development.
  • An object of the present invention is to provide a developer composition which does not require the presence of hydroquinone-type developer components and alkanolamines, and as a consequence, poses less of a threat to health and environment and can be more easily handled and disposed.
  • non-hydroquinone developer composition comprising the following:
  • the developer composition additionally contains one or more of the following additional components:
  • the restrainer is selected to be an alkali metal bromide
  • the organic anti-fogging agent is selected to be a combination of 0.01 to 0.1 g/l benzotriazole and 0.01 to 0.1 g/l phenyl mercaptotetrazole (PMT)
  • the sequestering or chelating agent is selected to be Na 2 EDTA.
  • the developer composition of the invention does not contain an alkanolamine.
  • Many alkanolamines possess the undesirable characteristics of toxicity, excessive volatility and unpleasant odor.
  • Many alkanolamines can form azeotropes with water that can complicate accurate replenishment of developer solutions, and such compounds are also quite costly.
  • alkanolamines tend to accelerate the process of chemical development at the expense of physical development. This phenomenon tends to produce an image which is more grainy than an image obtained without an alkanolamine, and is contrary to the goal of obtaining a very high contrast lith image.
  • the use of the developer composition of the present invention has been found to unexpectedly provide for the attainment of lith quality in an assured manner and therefore high dot quality without the need for the presence of hydroquinone or an alkanolamine.
  • Another embodiment of the present invention comprises developing an image-wise exposed silver halide photographic material containing a hydrazine compound as a nucleator with a developer comprising a developing agent selected from the group consisting of ascorbic acid and sugar-type derivatives thereof, or alkali salts and mixtures thereof, and substantially free from dihydroxybenzene with the term "substantially free from dihydroxybenzene” meaning the amount of the dihydroxybenzene is less than 5 x 10 4 mol/l and preferably is zero.
  • the other developer composition components described above can also be employed in combination in this method embodiment of the present invention.
  • Figure 1 shows D-LogE curves for a EK 2000 CGP internally boosted emulsion film as processed by the developer composition of the present invention and several representative prior art developer compositions.
  • Figure 2 shows D-LogE curves for a EK 2000 CLW internally boosted emulsion film as processed by the developer composition of the present invention and several representative prior art developer compositions.
  • Figure 3A shows D-LogE curves for a Fuji RO-100 conventional rapid access emulsion film developed by the developer composition of the present invention and the developer of European Patent No. 0 498 968 (U.S. Patent No. 5,196,298).
  • Figure 3B shows D-LogE curves for a Fuji RO-100 conventional rapid access emulsion film developed by the developer composition of the present invention and the developer of U.S. Patent No. 5,098,819.
  • Figure 3C shows D-LogE curves for a Fuji RO-100 conventional rapid access emulsion film developed by the developer composition of the present invention and the developer of Japanese Patent Application (OPI) No. 59-191035.
  • Figure 4A shows the D-LogE curve for different formulations of the developer composition of the present invention on an EK 2000 CGP internally boosted emulsion film.
  • Figure 4B shows the D-LogE curve for different formulations of the developer composition of the present invention on an EK 2000 CLW internally boosted emulsion film.
  • Figure 4C shows the D-LogE curve for different formulations of the developer composition of the present invention on an Fuji RO-100 rapid access emulsion film.
  • Figure 5A shows the effect of the sodium hydroxide level, i.e., the pH value, on D-LogE curves for an EK 200 CGP internally boosted emulsion films with an ascorbic acid-based developer formulation.
  • Figure 5B shows the effect of the sodium hydroxide level, i.e., the pH value, on D-LogE curves for EK 200 CLW internally boosted emulsion films with an ascorbic acid-based developer formulation.
  • Figure 5C shows the effect of the sodium hydroxide level, i.e., the pH value, on D-LogE curves for Fuji RO-100 rapid access emulsion films with an ascorbic acid-based developer formulation.
  • the ascorbic acid and sugar-type derivatives thereof useable as the developing agent also include stereoisomers and diastereoisomers of ascorbic acid and its sugar-type derivatives, their salts and mixtures thereof.
  • Suitable developers which fall within the scope of the above include, but are not limited to include, l-ascorbic acid, d-erythro-ascorbic acid (i.e., erythorbic or isoascorbic acid), d-gluco-ascorbic acid, 6-deoxy-l-ascorbic acid, l-rhamno-ascorbic acid, l-fucoascorbic acid, d-glucohepto-ascorbic acid, sorboascorbic acid, imino-l-ascorbic acid, ⁇ -lactoascorbic acid, maltoascorbic acid, l-araboascorbic acid, l-glucoascorbic acid, d-galacto
  • the ascorbic acids and ascorbic acid sugar derivatives used in this invention are generally used in amount ranging from 0.1 to 0.4 mol/l, or more, and preferably used in an amount ranging from 0.14 to 0.28 mol/l in the working developer solution. While the useful range of developer includes 0.1 to 0.4 mol/l, the useful amounts of developer can even exceed 0.4 mol/l in some circumstances, which generally will decrease the amount of auxiliary developer, such as phenidone that is needed.
  • Preferred ascorbic acid compounds for use in the present invention as the developing agent are alkali metal ascorbates and l-ascorbic acid.
  • the ascorbic acids and ascorbic acid sugar derivatives used in the present invention can be dissolved into the developing solution in the free acid form or, alternatively, they can be incorporated as an alkali salt, preferably the sodium or potassium salt thereof, or as a mixture of both free acid form and salt thereof.
  • an alkali salt preferably the sodium or potassium salt thereof, or as a mixture of both free acid form and salt thereof.
  • a lesser amount of alkali hydroxide is needed to establish a pH of 10.3 to 12.5, for example, an amount of about 3 to 15 g/l alkali hydroxide is generally used.
  • the free acid form of the sugar is used alone, 10 to 25 grams per liter of alkali metal hydroxide is usually employed to adjust the pH to 10.3 to 12.5.
  • Other examples of useable ascorbic acid and sugar-type derivatives useable as the developing agent for the developing solution of the present invention are described in U.S. Patent Nos. 5,098,819 and 5,196,298.
  • An auxiliary developing agent comprising a 3-pyrazolidone (or derivative thereof)(phenidone), an aminophenol compound or a mixture thereof is also included in the developer solution of the present invention in order to enhance the speed of the development of the developer composition.
  • 3-pyrazolidone developing agents are disclosed, for example, in U.S. Patent No. 5,098,819, with 1-phenyl-3-pyrazolidone being preferred.
  • Suitable aminophenols which can be used include p-methylamino-phenol (metol) and those disclosed in U.S. Patent 4,914,003.
  • the auxiliary developing agent is used in an effective amount to achieve high density and high contrast.
  • Such is generally used in an amount of from 0.001 to 0.12 mol/l, and preferably is used in an amount of from 0.001 to 0.006 mol/l for the 3-pyrazolidone or 0.001 to 0.02 mol/l for the p-aminophenol.
  • the developer composition of the present invention can be successfully employed without the need of any hydroquinone-type developer or an alkanolamine.
  • other important addenda to the developer composition of the present invention include an alkali metal sulfite, preferably sodium sulfite (Na 2 SO 3 ) used in an amount of up to 0.32 mol/l, preferably from 5 to 30 g/l (where Na 2 SO 3 is used), as a preservative and stabilizer against aerial oxidation.
  • alkali metal sulfite preferably sodium sulfite (Na 2 SO 3 ) used in an amount of up to 0.32 mol/l, preferably from 5 to 30 g/l (where Na 2 SO 3 is used
  • Other useable sulfites are disclosed in U.S. Patent No. 5,098,819.
  • the full benefits of this invention are obtained in a pH range of 10.3 to 12.5, more preferably from 10.5 or 10.8 to 11.5 or 12.2.
  • the alkalinity of the developer composition is maintained within the desired range by the presence of an alkali metal carbonate such as sodium or potassium carbonate in an amount of 0.1 to 0.4 mol/l or less, preferably from 0.14 to 0.28 mol/l.
  • the alkali metal carbonate is preferably used in conjunction with an alkali metal hydroxide in an amount of 3 to 25 g/l to adjust the pH range to the desired range.
  • the amount of alkali hydroxide added partly depends on whether the developer is used in a free acid from, where the amount of alkali hydroxide is generally used in an amount of 10 to 25 g/l, or if the developer is used in salt form, where the amount of alkali hydroxide is generally used in an amount of 3 to 15 g/l.
  • alkali metal carbonates give rise to less caustic compositions than alkali metal hydroxides.
  • alkali metal carbonates typically require greater amounts to be present to effect a pH adjustment in comparison to alkali hydroxides.
  • the alkalinity of the developer solution be established through a discretionary selection of amounts for each of alkali metal carbonate and alkali hydroxide, and with refinements made to the pH preferably being made by supplemental addition of alkali metal hydroxide.
  • the developer composition of the present invention also can contain a wide variety of other conventional additives and addenda, which serve other various desirable functions.
  • additional addenda include, but are not limited to, additional developing agents other than hydroquinone, antifogging agents, buffers, sequestering agents, swelling control agents, development accelerators.
  • the developer solution contains certain other addenda including each of a restrainer agent, an organic antifogging agent and a sequestering or chelating agent.
  • sodium or potassium bromides are preferably included as restrainers in an amount of 0.008 to 0.04 mol/l.
  • exemplary organic anti-fogging agents preferably include a combination of a benzotriazole and phenyl mercaptotetrazole each in an amount of 0.01 to 0.1 g/l, respectively.
  • Useful benzotriazoles are disclosed, for example, in U.S. Patent No. 4,975,354.
  • An exemplary mercaptotetrazole is 1-phenyl-5-mercaptotetrazole.
  • the present invention also encompasses the use of other antifogging agents, such as disclosed in U.S. Patent Nos. 5,098,819 and 5,196,298.
  • a small amount of a sequestering or chelating agent is generally used to sequester trace amounts of metal ions present in the components or water used in formulating the developer formulation.
  • exemplary sequestering agents useable in the present invention are disclosed by U.S. Patent No. 5,098,819, and are generally used in an amount of 0.5 to 3 g/l, preferably from 0.5 to 2.0 g/l.
  • the sequestering agent used in the present invention is Na 2 EDTA in the above amounts.
  • the developing solutions of the present invention can be employed to develop various types of photographic materials, especially black-and-white photographic elements including conventional rapid access films, such as Fuji RO-100 film by Fuji Photo Film Co., Ltd., as well as silver halide photographic materials containing a hydrazine compound as a nucleator, such as EK 2000 CGP and EK 2000 CLW film manufactured by Eastman Kodak Company.
  • the utility of the developing solution of the present invention is not limited thereto and is understood to extend to other black-and-white materials such as radiographic recording and duplicating materials, cinematographic recording and duplicating materials and microfilm.
  • the photographic elements which can be developed by the developer's solution of the present invention can take on conventional layering schemes such as disclosed in U.S. Patent No. 5,198,298.
  • films which can be used in the present invention is a silver halide photographic material containing a hydrazine compound as a nucleator.
  • Such photographic materials are shown in, for example, U.S. Patent 4,975,354, 4,988,604 and 4,994,365 with respect to the layer structure, the silver halide emulsion, the internal booster, and other components of the photographic material.
  • Non-limiting examples of hydrazine compounds are the following compounds:
  • hydrazine compounds which can be used in the photographic material, include those described in RESEARCH DISCLOSURE, Item 23516 (November, 1983, page 346) and the literature references referred to therein, as well as in U.S. Patents 4,080,207, 4,269,929, 4,276,364, 4,278,748, 4,385,108, 4,459,347, 4,560,638, 4,478,928, 4,737,452, 4,284,764, 4,686,167, 5,100,761, 5,006,445, 4,960,672, 4,971,890, 4,971,888, 4,950,578, 5,061,594, 5,017,456, 5,028,510, European Patent 217,310, European Patent 286,840 and British Patent 2,011,391.
  • the hydrazine compound may be introduced in any hydrophilic colloid layer of the photographic material, such as a silver halide emulsion layer, an inter layer, and a protective coating layer.
  • the amount of the hydrazine compound present in the photographic material is preferably from 1 x 10 -6 mol to 5 x 10 -2 mol, especially preferably from 1 x 10 -5 mol to 2 x 10 -2 mol, per mol of silver halide in the photographic light-sensitive element.
  • a photographic silver halide material to be developed by the developer composition of the present invention includes at least one emulsion layer or hydrophilic colloid layer comprising an amino compound in an amount effective to act as an incorporated booster, and at least one emulsion layer or hydrophilic colloid layer containing a nucleator compound comprising a hydrazine compound or a derivative thereof in an amount of from 1 x 10 -6 mol to 5 x 10 -2 mol per mol of silver halide.
  • the photographic material to be developed by the developing solutions of the present invention can be image-wise exposed by any convenient radiation source in accordance with this specific application.
  • an automatically operating apparatus is used provided with a system for automatic replenishment of the processing solutions.
  • the development step can be followed by a stop step, for example, using a stopping solution such as a 3% acetic acid solution used at approximately 90°F for 15 seconds, followed by a fixing bath, for example, using a commercially available fixer, such a F-O-G available from Fuji Hunt Photographic Chemicals, Inc., used at about 90°F for 30 seconds, followed by a washing or stabilization step.
  • a stop step for example, using a stopping solution such as a 3% acetic acid solution used at approximately 90°F for 15 seconds
  • a fixing bath for example, using a commercially available fixer, such a F-O-G available from Fuji Hunt Photographic Chemicals, Inc., used at about 90°F for 30 seconds, followed by a washing or stabilization step.
  • the photographic material is dried according to standard practices.
  • the developing conditions used were a temperature of 90° F and a developing time of 30 seconds for CGP and CLW films and 25 seconds for RO-100 film. Afterwards, a stop bath (3% acetic acid soln.) was used at 90° F for 15 seconds. Then a fix bath (commercially available F-O-G fixer with hardener from Fuji Hunt Photographic Chemicals, Inc.) was used at 90° F for 30 seconds.
  • Figure 1 shows D-LogE curves for a EK 2000 CGP internally boosted emulsion film as processed by the developer composition of the present invention and several representative prior art developer compositions.
  • Figure 2 shows D-LogE curves for a EK 2000 CLW internally boosted emulsion film as processed by the developer composition of the present invention and several representative prior art developer compositions.
  • Figure 3A shows D-LogE curves for a Fuji RO-100 rapid access emulsion film developed by the developer composition of the present invention and the developer of European Patent No. 0 498 968 (U.S. Patent No. 5,196,298).
  • Figure 3B shows D-LogE curves for a Fuji RO-100 rapid access emulsion film developed by the developer composition of the present invention and the developer of U.S. Patent No. 5,098,819.
  • Figure 3C shows D-LogE curves for a Fuji RO-100 rapid access emulsion film developed by the developer composition of the present invention and the developer of Japanese Patent Application (OPI) No. 59-191035.
  • Figure 4A shows the D-LogE curve for different formulations of the developer composition of the present invention on an EK 2000 CGP internally boosted emulsion film.
  • Figure 4B shows the D-LogE curve for different formulations of the developer composition of the present invention on an EK 2000 CLW internally boosted emulsion film.
  • Figure 4C shows the D-LogE curve for different formulations of the developer composition of the present invention on an Fuji RO-100 rapid access emulsion film.
  • Example 1 The effect of sodium hydroxide level, and, hence the pH value, was examined for the same three types of films used in Example 1 with the formulations used in Table 3-1 (all amounts are in g/l, unless indicated otherwise). The same developing conditions were used as in Example 1.
  • Figure 5A shows the effect of the sodium hydroxide level, i.e., the pH value, on D-LogE curves for an EK 2000 CGP internally boosted emulsion films with an ascorbic acid-based developer formulation.
  • Figure 5B shows the effect of the sodium hydroxide level, i.e., the pH value, on D-LogE curves for EK 2000 CLW internally boosted emulsion films with an ascorbic acid-based developer formulation.
  • Figure 5C shows the effect of the sodium hydroxide level, i.e., the pH value, on D-LogE curves for Fuji RO-100 rapid access emulsion films with an ascorbic acid-based developer formulation.
  • dot quality investigations also were made on the same developer formulations as solutions 1-7 and EK RA 2000 of Example 1 (Table 1-1), and on same three types of films used in Example 1.
  • dot quality is a standard methodology for evaluating the quality of lith developers. The better the lith quality, the better the dot quality. The sharper the dot, the lower the numerical rating assigned.

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Claims (13)

  1. Hydrochinonfreie, photographische Entwicklerzusammensetzung, umfassend:
    (a) einen Entwickler in einer Menge von 0,1 bis 0,4 Mol/Liter (mol/l), ausgewählt aus der Gruppe, bestehend aus Ascorbinsäure und Zuckertyp-Derivaten davon oder Alkalimetallsalzen und Gemischen davon,
    (b) ein Zusatzentwicklungmittel in einer Menge von 0,001 bis 0,12 mol/l, enthaltend eine 3-Pyrazolidon-Verbindung, ein Aminophenol oder ein Gemisch davon,
    (c) ein Alkalimetallsulfit in einer Menge von 0,32 mol/l oder weniger,
    (d) ein Alklaimetallcarbonat in einer Menge von 0,1 bis 0,4 mol/l,
    (e) ein Alkalimetallhydroxid in einer Menge von 10 bis 25 g/l, falls eine Ascorbinsäure oder ein Zuckertyp-Derivat davon in Form einer freien Säure vorhanden ist oder von 3 bis 15 g/l, falls eine Ascorbinsäure oder ein Zuckertyp-Derivat davon in Form eines Alkalimetallsalzes vorhanden ist, und
    (f) eine Entwicklerzusammensetzung mit einem pH-Wert von 10,3 bis 12,5 bei 25°C, wobei die Entwicklerzusammensetzung kein Alkanolamin enthält.
  2. Hydrochinonfreie, photographische Entwicklerzusammensetzung gemäß Anspruch 1, wobei der Entwickler ausgewählt ist aus der Gruppe, bestehend aus L-Ascorbinsäure, D-Erythroascorbinsäure, D-Glucoascorbinsäure, 6-Desoxy-L-ascorbinsäure, L-Rhamnoascorbinsäure, L-Fucoascorbinsäure, D-Glucoheptoascorbinsäure, Sorboascorbinsäure, Imino-L-ascorbinsäure, ω-Lactoascorbinsäure, Maltoascorbinsäure, L-Araboascorbinsäure, L-Glucoascorbinsäure, D-Galactoascorbinsöäure, L-Guloascorbinsäure und L-Alloascorbinsäure.
  3. Hydrochinonfreie, photographische Entwicklerzusammensetzung gemäß Anspruch 1, wobei der Entwickler ein Alkalimetallsalz der Ascorbinsäure umfasst.
  4. Hydrochinonfreie, photographische Entwicklerzusammensetzung gemäß irgendeinem der Ansprüche 1 bis 3, wobei die Entwicklerzusammensetzung zusätzlich eine oder mehrere von folgenden umfasst:
    (g) einem Verzögerer, vorhanden in einer Menge von 0,008 bis 0,04 mol/l, um die Entwicklung des nicht belichteten Silberhalogenids zu verlangsamen,
    (h) einem organischen Antischleiermittel in einer Menge von 0,02 bis 2 g/l, und
    (i) einem Maskierungs- oder Chelatisierungsmittel in einer Menge von 0,5 bis 3 g/l, wobei der Verzögerer Natriumbromid, das organische Antischleiermittel ein Gemisch von Benzotriazol und 1-Phenyl-5-mercaptotetrazol und das Maskierungsmittel Na2EDTA umfasst.
  5. Verfahren zum Entwickeln eines bildartig belichteten, Schwarzweiß-Photomaterials, welches das Entwickeln des Photomaterials mit einer hydrochinonfreien Entwicklerzusammensetzung einschließt, umfassend:
    (a) einen Entwickler in einer Menge von 0,1 bis 0,4 mol/Liter (mol/l), ausgewählt aus der Gruppe, bestehend aus Ascorbinsäure und Zuckertyp-Derivaten davon oder Alkalimetallsalzen und Gemischen davon,
    (b) ein Zusatzentwicklungmittel in einer Menge von 0,001 bis 0,12 mol/l, enthaltend eine 3-Pyrazolidon-Verbindung, ein Aminophenol oder ein Gemisch davon
    (c) ein Alkalimetallsulfit in einer Menge von 0,32 mol/l oder weniger,
    (d) ein Alklaimetallcarbonat in einer Menge von 0,1 bis 0,4 mol/l,
    (e) ein Alkalimetallhydroxid in einer Menge von 10 bis 25 g/l, falls eine Ascorbinsäure oder ein Zuckertyp-Derivat davon in Form einer freien Säure vorhanden ist oder von 3 bis 15 g/l, falls eine Ascorbinsäure oder ein Zuckertyp-Derivat davon in Form eines Alkalimetallsalzes vorhanden ist, und
    (f) eine Entwicklerzusammensetzung mit einem pH-Wert von 10,3 bis 12,5 bei 25°C, wobei die Entwicklerzusammensetzung kein Alkanolamin enthält.
  6. Verfahren gemäß Anspruch 5, bei dem der Entwickler ausgewählt ist aus der Gruppe, bestehend aus L-Ascorbinsäure, D-Erythroascorbinsäure, D-Glucoascorbinsäure, 6-Desoxy-L-ascorbinsäure, L-Rhamno-ascorbinsäure, L-Fucoascorbinsäure, D-Glucoheptoascorbinsäure, Sorboascorbinsäure, Imino-L-ascorbinsäure, ω-Lactoascorbinsäure, Maltoascorbinsäure, L-Araboascorbinsäure, L-Glucoascorbinsäure, D-Galactoascorbinsöäure, L-Guloascorbinsäure und L-Alloascorbinsäure.
  7. Verfahren gemäß Anspruch 5, bei dem der Entwickler ein Alkalimetallsalz der Ascorbinsäure umfasst.
  8. Verfahren gemäß Anspruch 5, bei dem der Entwickler zusätzlich wenigstens einen von einem Verzögerer in einer Menge von 0,008 bis 0,04 mol/l, um die Entwicklung des nicht belichteten Silberhalogenids zu verlangsamen,
    einem organischen Antischleiermittel in einer Menge von 0,02 bis 2 g/l, und
    einem Maskierungsmittel in einer Menge von 0,5 bis 3 g/l enthält,
    wobei der Verzögerer ein Alkalimetallbromid, das organische Antischleiermittel ein Gemisch von Benzotriazol und Phenylmercaptotetrazol und das Maskierungsmittel Na2EDTA umfasst.
  9. Verfahren gemäß irgendeinem der Ansprüche 5 bis 7, bei dem der Entwickler in einer Menge von 0,14 bis 0,28 mol/l und das Alkalimetallcarbonat in einer Menge von 0,14 bis 0,28 mol/l vorliegt, wobei die Entwicklerzusammensetzung zusätzlich umfasst:
    (g) einen Verzögerer in einer Menge von 0,008 bis 0,04 mol/l,
    (h) ein organisches Antischleiermittel in einer Menge von 0,02 bis 2 g/l, und
    (i) ein Maskierungs- oder Chelatisierungsmittel in einer Menge von 0,5 bis 3 g/l, wobei der Verzögerer Natriumbromid, das organische Beschlagverhinderungsmittel ein Gemisch von Benzotriazol und 1-Phenyl-5mercaptotetrazol und das Maskierungsmittel Na2EDTA umfasst.
  10. Verfahren zum Erhalten eines kontrastreichen Bildes gemäß irgendeinem der Ansprüche 5 bis 7, bei dem das photographische Material ein Silberhalogenid-Photomaterial ist, das eine Hydrazin-Verbindung enthält, wobei die Entwicklerzusammensetzung im Wesentlichen frei von 1,2 Dihydroxybenzol ist.
  11. Verfahren gemäß Anspruch 10, bei dem die Entwicklerzusammensetzung zusätzlich wenigstens eine einschließt aus
    einem Verzögerer in einer Menge von 0,008 bis 0,04 mol/l, um die Entwicklung des nicht belichteten Silberhalogenids zu verlangsamen,
    einem organischen Antischleiermittel in einer Menge von 0,02 bis 2 g/l und einem Maskierungsmittel in einer Menge von 0,5 bis 3 g/l,
    wobei der Verzögerer Natriumbromid, das organische Antischleiermittel ein Gemisch von Benzotriazol in einer Menge von 0,01 bis 0,1 g/l und 1-Phenyl-5-mercaptotetrazol in einer Menge von 0,01 bis 0,1 g/l und das Maskierungsmittel Na2EDTA umfasst.
  12. Das Verfahren gemäß Anspruch 10, bei dem das Silberhalogenid-Photomaterial wenigstens eine Emulsionschicht oder hydrophile Kolloidschicht, umfassend eine Amino-Verbindung in einer effektiven Menge, um als eingebauter Verstärker zu wirken, enthält und wenigstens eine Emulsionsschicht oder hydrophile Kolloidschicht, die eine Keimbildner-Verbindung enthält, welche eine Hydrazin-Verbindung oder ein Derivat davon in einer Menge von 1•10-6 mol bis 5•10-2 mol pro mol Silberhalogenid umfasst.
  13. Verfahren gemäß Anspruch 9, bei dem das photographische Material ein Silberhalogenid-Photomaterial ist, enthaltend eine Silberhalogenidemulsion mit einer Hydrazin-Verbindung als Keimbildner, und bei dem der Verzögerer in einer Menge von 0,0084 bis 0,042 mol/l vorliegt.
EP94919380A 1993-06-18 1994-06-10 Photographische entwicklerzusammensetzung ohne hydrochinon und verarbeitungsverfahren Expired - Lifetime EP0738400B1 (de)

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US7802493A 1993-06-18 1993-06-18
US78024 1993-06-18
PCT/US1994/006353 WO1995000881A1 (en) 1993-06-18 1994-06-10 Non-hydroquinone photographic developer composition and processing method

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US5942379A (en) * 1995-08-10 1999-08-24 Eastman Kodak Company 3-pyrazolidone compounds and photographic developer solutions containing same
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US5702875A (en) * 1996-06-28 1997-12-30 Eastman Kodak Company Weakly alkaline ascorbic acid developing composition, processing kit and method using same
US5866309A (en) * 1997-10-22 1999-02-02 Fitterman; Alan S. Method for processing roomlight handleable photographic elements
US5932398A (en) * 1997-11-14 1999-08-03 Eastman Kodak Company Kit for roomlight processing of black-and-white photographic elements
US5871890A (en) * 1997-11-14 1999-02-16 Eastman Kodak Company Method for processing roomlight handleable radiographic films using two-stage development
ES2224757B1 (es) * 1998-10-13 2005-12-16 Luis Casademunt Garre Revelador fotografico para avance de la sensibilidad efectiva en peliculas con emulsion de blanco y negro.
US6277290B1 (en) * 1999-12-17 2001-08-21 Metafix Inc. Process for recovering silver from photographic solutions
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CN103343068A (zh) * 2013-06-18 2013-10-09 厦门市豪尔新材料有限公司 剥胶剂
CN104765244A (zh) * 2015-04-30 2015-07-08 石家庄太行科工有限公司 一种环保型显影液及其制备方法和应用

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AU689168B2 (en) 1998-03-26
SG34338A1 (en) 2000-12-19
WO1995000881A1 (en) 1995-01-05
JPH09500221A (ja) 1997-01-07
USH2048H1 (en) 2002-09-03
AU1092295A (en) 1995-01-17
DE69426780T2 (de) 2001-10-04
MY111751A (en) 2000-12-30
AU689168C (en) 2001-11-22
EP0738400A4 (de) 1996-06-18
ATE199461T1 (de) 2001-03-15
EP0738400A1 (de) 1996-10-23
CN1053970C (zh) 2000-06-28
CN1129989A (zh) 1996-08-28
DE69426780D1 (de) 2001-04-05

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