EP0118071B1 - Révélateur photographique - Google Patents

Révélateur photographique Download PDF

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Publication number
EP0118071B1
EP0118071B1 EP84101714A EP84101714A EP0118071B1 EP 0118071 B1 EP0118071 B1 EP 0118071B1 EP 84101714 A EP84101714 A EP 84101714A EP 84101714 A EP84101714 A EP 84101714A EP 0118071 B1 EP0118071 B1 EP 0118071B1
Authority
EP
European Patent Office
Prior art keywords
developer
color
polymaleic anhydride
compounds
developer composition
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
Application number
EP84101714A
Other languages
German (de)
English (en)
Other versions
EP0118071A2 (fr
EP0118071A3 (en
Inventor
Helmut Häseler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert AG
Original Assignee
Agfa Gevaert AG
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 Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0118071A2 publication Critical patent/EP0118071A2/fr
Publication of EP0118071A3 publication Critical patent/EP0118071A3/de
Application granted granted Critical
Publication of EP0118071B1 publication Critical patent/EP0118071B1/fr
Expired legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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 invention relates to a photographic developer composition for producing photographic images, which has improved limescale protection.
  • photographic developers are usually added further compounds to improve the properties of the developer mixture, e.g. B. so-called sequestering agents or limescale protection agents, in particular to prevent the precipitation of calcium compounds.
  • compounds are usually used which increase the oxidation resistance in the developer composition, e.g. B. hydroxylamine.
  • limescale protection agents are e.g. B. polyphosphates and amino group-containing carboxylic acids.
  • the effectiveness of these compounds depends to a large extent on the composition of the developer.
  • photographic color developers which contain a p-phenylenediamine as the developer substance and hydroxylamine to improve the resistance to oxidation, it is further aggravated that many of the compounds used as anti-limescale cause the decomposition of hydroxylamine.
  • organic compounds with at least one phosphono group and at least one carboxy group in the molecule are said to complex heavy metal and calcium ions.
  • such compounds can represent a wastewater pollution due to their phosphorus content.
  • Aminopolycarboxylic acids e.g. As is known from US Pat. No. 3,462,269, the activity of a color developer can change in such a way that changes in the development of the individual layers of a recording material which are difficult to predict occur.
  • the applicability of these compounds is further limited by the fact that they reduce the stability of color photographic developers. This is probably due to an accelerated decomposition of the substances added to improve the oxidation stability, e.g. B. of hydroxylamine.
  • the use of aminopolycarboxylic acids in the substoichiometric range, based on Ca ions leads to the formation of relatively hard precipitates which are extremely disruptive in the development of photographic recording materials.
  • Aminopolyphosphonic acids e.g. B. are known from US-PS 3 201 246, also change the activity of a color developer.
  • copolymers of maleic anhydride are said to be brittle as dispersants for poorly soluble developer components.
  • a limescale protection effect of these copolymers is not apparent from US Pat. No. 3,785,824; rather, a completely different compound is used as a sequestering agent in Example 1 (column 4, line 29).
  • the object of the invention is to provide improved limescale protection in photographic developer compositions.
  • the limescale protection should not affect the sensitometric properties.
  • the resistance of any additional antioxidants added should not be impaired.
  • the developer composition for the development of silver halide-containing recording materials which contains at least one complexing agent for binding undesirable metal ions.
  • the developer composition contains hydrolyzed polymaleic anhydride as complexing agent.
  • hydrolyzed polymaleic anhydride is known per se. It can be obtained by hydrolysis of polymerized maleic anhydride, e.g. B. by heating with water.
  • the polymaleic anhydride which can be used as the starting material can be e.g. B. according to GB-PS 1 024725.
  • the product formed in the hydrolysis of polymaleic anhydride contains a number of carboxylic acid groups and possibly a small number of remaining anhydride groups and is usually referred to in DE-AS 2159 172 as hydrolyzed polymaleic anhydride. It is believed that a certain decarboxylation of the polymer can occur during the polymerization or the subsequent hydrolysis, so that the acid value of the hydrolysed Polymaleic anhydride can be lower than the theoretical value.
  • Hydrolysed polymaleic anhydride which is particularly suitable for the present invention, is obtainable according to Example 1 of DE-AS 2159 172 and US Pat. No. 3,810,834.
  • a particularly suitable hydrolyzed polymaleic anhydride has an average molecular weight of 800 to 1,000. It is soluble in water in all proportions, has a viscosity at 22 ° C of 50 to 100 cP, a boiling point of 100 to 101 ° C and a freezing point between - 5 and -12 ° C.
  • the hydrolyzed polymaleic anhydride can be used in any amount in a photographic developer.
  • the amount used is between 0.01 to 50 g, preferably 0.05 to 20 g, in particular 0.5 to 2.5 g, per 1 of the color developer.
  • the compounds to be used according to the invention have neither nitrogen nor phosphorus, they represent only a low level of wastewater pollution.
  • the developer compositions according to the invention are primarily color developers. These preferably contain p-phenylenediamine derivatives, e.g. B.: N, N-dimethyl-p-phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline, 2-amino-5-diethylamino-toluene, N-butyl-N- ⁇ -sulfobutyl -p-phenylenediamine, 2-amino-5- (N-ethyl-N-ß-methanesulfonamidoethylamino) -toluoi, N-ethyl-N-ß-hydroxyethyl-p-phenylenediamine, N, N-bis- (ß- hydroxyethyl) -p-phenylenediamine, 2-amino-5- (N-ethyl-N- ⁇ -hydroxyethylamino) tolu
  • hydrolyzed polymaleic anhydride can also be used in black and white developers, e.g. B. dihydroxybenzenes, 3-pyrazolidones, aminophenols, 1-phenyl-3-hydrazolines, ascorbic acid or other customary developer substances.
  • compounds for oxidation protection can additionally be contained in the developer composition according to the invention, such as, for. B. hydroxylamine, ascorbic acid, certain sugars and glucosamine.
  • organic phosphonic acids e.g. organic phosphonic acids, phosphonocarboxylic acids, aminopolycarboxylic acids and aminopolyphosphonic acids.
  • the developer compositions of the invention are thus useful for both negative and reverse processing. They are particularly suitable for rapid processing at higher temperatures. They can still be used in developers intended for reinforcement processes. In the case of amplification processes, for example, the decomposition of hydrogen peroxide on metal nuclei can be used.
  • the developer compositions according to the invention are suitable for processing conventional photographic recording materials. If color materials are involved, they can contain the couplers necessary for producing a color image in the recording material. However, the couplers can also be present in the developer composition.
  • the red-sensitive silver halide emulsion layers are each assigned at least one non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or a-naphthol type.
  • the green-sensitive silver halide emulsion layers are generally assigned at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone and indazolone types usually being used.
  • the blue-sensitive silver halide emulsion layers are usually assigned at least one non-diffusing color coupler for producing the yellow partial color image, generally a color coupler with an open-chain ⁇ -diketomethylene or ⁇ -diketomethine grouping.
  • the color couplers can be standard 4-equivalent couplers as well as 2-equivalent couplers.
  • the 2-equivalent couplers include the known white couplers, which, however, do not give rise to a dye when reacting with color developer oxidation products, as well as DIR couplers, which are couplers that contain a detachable residue in the coupling point, which acts as a diffusing development inhibitor in Freedom can be set.
  • the silver halide emulsions used in the materials can contain chloride, bromide and iodide or mixtures thereof as the halide.
  • bromide and bromide iodide emulsions are used, which can be ripened and optically sensitized in the usual way.
  • the recording materials can be stabilized.
  • Particularly suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are e.g. B. in the article by Birr, Z.
  • Suitable stabilizers are u. a. heterocyclic mercapto compounds, e.g. B. phenyl mercaptotetrazole, quaternary benzothiazole derivatives and benzotriazole.
  • the following developer a) is produced by adding the constituents in the order given: with water to 1 liter.
  • Developer b) This contains 1 g of diethylenetriaminepentaacetic acid instead of trisodium nitrilotriacetic acid.
  • Developer c) This is a developer composition according to the invention which, instead of nitrilotriacetic acid, contains hydrolyzed polymaleic anhydride in an amount of 1.5 ml of a 50% strength aqueous solution.
  • Developer a The calcium contained in the developer is present in a compact, hard-crystalline form at the bottom of the vessel.
  • the precipitated calcium compounds are in a fluffy, voluminous form and do not form any hard deposits on the bottom of the vessel.
  • a developer is produced a) by adding the individual components in the following order: fill up to 1 liter with water.
  • a developer b) according to the invention is prepared which, instead of the 1-hydroxyethane-1,1-diphosphonic acid, contains polymaleic anhydride hydrolyzed according to the invention in an amount of 2 ml of a 50% aqueous solution.
  • a commercially available light-sensitive color photographic recording material which contains a blue-sensitive yellow layer, a green-sensitive purple layer and a red-sensitive blue-green layer on a polyethylene-coated paper support. In any case, this material is exposed in the same way and subjected to the following processing:
  • the developer contains 1.5 g of diethylenetriaminepentaacetic acid.
  • the developer contains 3 ml of 40% pentasodium amino trimethylphosphonate solution.
  • pH 10.2 (as developer 1).
  • the developer contains 1.5 g of nitrilotriacetic acid trisodium salt.
  • pH 10.2 (as developer 1).
  • the stop bath used contains 2% acetic acid and the bleach-fix bath has the following composition:
  • the optical reflection densities of the materials processed in this way were measured with a densitometer through red, green and blue filters. The results are shown in the table below.
  • the density specified in «Measuring field 1 and « Measuring field 2 is obtained with the same exposure intensity. The difference in the densities thus obtained is called the «relative contrast.
  • the results obtained with developer 1 are taken as a standard, since this developer contains no complexing agent. The percentage deviations from this standard when using the individual complexing agents are entered in percent in the columns labeled A.
  • developers 3, 4 and 5 result in considerable sensitometric deviations. Only developer 2 with the complexing agent according to the invention showed no, or negligible, sensitometric deviations.
  • This example examines the durability of hydroxylamine in photographic developers using various complexing agents.
  • the following developers are produced for this:
  • the developer is produced in the same way as described for developer 2. However, 4 ml of 40% pentasodium amino trimethylphosphonate solution is used as a complexing agent.
  • hydrolyzed polymaleic anhydride is added in an amount of 3 ml of a 50% solution as a complexing agent instead of the ethylenediaminetetraacetic acid.
  • the remaining components were then dissolved as in developer 2.
  • the content of hydroxylammonium sulfate per liter was 2.6 g in developers 1 to 5 immediately after the solutions had been prepared.
  • the developer 1 without complexing agent is unusable despite good hydroxylamine resistance due to the precipitation of calcium compounds.
  • the developer 5 according to the invention with the hydrolyzed polymaleic anhydride as complexing agent practically does not impair the resistance of the hydroxylamine at all.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (6)

1. Composition de révélateur pour le développement de matériaux de prise de vues contenant des halogénures d'argent, renfermant au moins un agent complexant pour la fixation des ions métalliques, caractérisée en ce qu'elle contient comme agent complexant un anhyride polymaléique hyrolysé.
2. Composition de révélateur selon la revendication 1, caractérisée en ce que l'anhyride polymaléique hydrolysé présente un poids moléculaire moyen compris entre 800 et 1 000.
3. Composition de révélateur selon la revendication 1, caractérisée en ce qu'elle contient l'anhydride polymaléique hydrolysé en quantité de 0,01 à 50 g/I de révélateur.
4. Composition de révélateur selon la revendication 1, caractérisée en ce qu'elle contient comme substance développatrice une p-phénylènediamine.
5. Composition de révélateur selon la revendication 1, caractérisée en ce qu'elle contient un agent anti-oxydant.
6. Composition de révélateur selon la revendication 5, caractérisée en ce qu'elle contient comme agent anti-oxydant de l'hydroxylamine.
EP84101714A 1983-03-03 1984-02-20 Révélateur photographique Expired EP0118071B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19833307507 DE3307507A1 (de) 1983-03-03 1983-03-03 Fotografische entwicklerzusammensetzung
DE3307507 1983-03-03

Publications (3)

Publication Number Publication Date
EP0118071A2 EP0118071A2 (fr) 1984-09-12
EP0118071A3 EP0118071A3 (en) 1986-10-15
EP0118071B1 true EP0118071B1 (fr) 1988-06-15

Family

ID=6192402

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84101714A Expired EP0118071B1 (fr) 1983-03-03 1984-02-20 Révélateur photographique

Country Status (4)

Country Link
US (1) US4615971A (fr)
EP (1) EP0118071B1 (fr)
JP (1) JPS59165057A (fr)
DE (2) DE3307507A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0323405A3 (en) * 1987-12-28 1990-06-13 Ciba-Geigy Ag Photographic developing composition
US4927746A (en) * 1988-06-03 1990-05-22 Eastman Kodak Company Photographic stabilizing bath containing polyarcylic acid
US4923782A (en) * 1988-06-03 1990-05-08 Eastman Kodak Company Photographic stabilizing bath containing hydrolyzed polymaleic anhydride
US5004669A (en) * 1988-10-31 1991-04-02 Konica Corporation Light-sensitive silver halide photographic material
JP2640143B2 (ja) * 1989-07-21 1997-08-13 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
US6645709B1 (en) * 2002-08-12 2003-11-11 Eastman Kodak Company Photographic color developing composition containing calcium ion sequestering agent combination and method of use

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2159172A1 (de) * 1970-11-30 1972-06-08 Ciba Geigy Ag Verfahren zur Wasseraufbereitung

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2015403A1 (de) * 1970-04-01 1971-10-21 Agfa-Gevaert Ag, 5090 Leverkusen Photographische Farbentwickler
US3785824A (en) * 1971-09-24 1974-01-15 Minnesota Mining & Mfg Photographic aqueous dispersion concentrates
JPS5439735B2 (fr) * 1972-06-30 1979-11-29
JPS5351742A (en) * 1976-10-21 1978-05-11 Konishiroku Photo Ind Co Ltd Developing liquid for silver halide color photographic photosensitive material
US4374733A (en) * 1981-04-01 1983-02-22 Betz Laboratories, Inc. Method for treating aqueous mediums

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2159172A1 (de) * 1970-11-30 1972-06-08 Ciba Geigy Ag Verfahren zur Wasseraufbereitung

Also Published As

Publication number Publication date
EP0118071A2 (fr) 1984-09-12
EP0118071A3 (en) 1986-10-15
DE3307507A1 (de) 1984-09-06
DE3472174D1 (en) 1988-07-21
JPS59165057A (ja) 1984-09-18
US4615971A (en) 1986-10-07

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