EP0267264B1 - Kontrastreiche entwicklung von photographischen elementen - Google Patents

Kontrastreiche entwicklung von photographischen elementen Download PDF

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Publication number
EP0267264B1
EP0267264B1 EP19870903549 EP87903549A EP0267264B1 EP 0267264 B1 EP0267264 B1 EP 0267264B1 EP 19870903549 EP19870903549 EP 19870903549 EP 87903549 A EP87903549 A EP 87903549A EP 0267264 B1 EP0267264 B1 EP 0267264B1
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developing solution
aqueous alkaline
phenyl
developing
developing agent
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French (fr)
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EP0267264A1 (de
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Ronald J. Nothnagle
James H. Barrows
Paul A. Zielinkski
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • G03C5/305—Additives other than developers

Definitions

  • the invention relates in general to photography and in particular to the black-and-white development of photographic elements. More specifically, this invention relates to the development of high contrast photographic elements, such as lithographic films used in the field of graphic arts.
  • lithographic films are ordinarily carried out using special developers which are known in the art as “lith” developers.
  • high contrast is achieved using the "lith effect” (also referred to as infectious development) as described by J. A. C. Yule in the Journal of the Franklin Institute, Vol. 239, 221-230, (1945).
  • This type of development is believed to proceed autocatalytically.
  • a low, but critical, concentration of free sulfite ion is maintained by use of an aldehyde bisulfite adduct, such as sodium formaldehyde bisulfite, which, in effect, acts as a sulfite ion buffer.
  • the low sulfite ion concentration is necessary to avoid interference with the accumulation of developing agent oxidation products, since such interference can result in prevention of infectious development.
  • the developer typically contains only a single type of developing agent, namely, a developing agent of the dihydroxybenzene type, such as hydroquinone.
  • U.S. patent 4,269,929 describes the use of a very wide variety of amino compounds as contrast-promoting agents.
  • inorganic amines such as the hydroxylamines
  • organic amines including aliphatic amines, aromatic amines, cyclic amines, mixed aliphatic-aromatic amines, and heterocyclic amines.
  • Primary, secondary and tertiary amines, as well as quaternary ammonium compounds, are included within the broad scope of the disclosure.
  • U.S. patent 4,269,929 represents a very important advance in the art, its commercial utilization has been hindered by the disadvantageous characteristics exhibited by many amino compounds.
  • some amines suffer from the problem of toxicity, some from the problem of excessive volatality, some are characterized by highly unpleasant odors, some tend to form azeotropes with water, some exhibit an inadequate degree of solubility in an aqueous alkaline photographic developing solution, and some are costly yet must be used at a relatively high concentration such that they constituted a substantial portion of the total cost of the developing solution.
  • many amines exhibit a degree of activity as contrast-promoters in the method and composition of U.S. patent 4,269,929 that is less than is desired for commercial operation.
  • the present invention provides a method for high contrast development of a photographic element comprising at least one silver halide emulsion layer, which method comprises contacting said element in the presence of a hydrazine compound with an aqueous alkaline developing solution which has a pH of above 10 and below 12 and contains a dihydroxybenzene developing agent, an auxiliary super-additive developing agent, and a sulfite preservative, characterized in that said developing solution also contains a contrast-promoting amount of an hydroxyalkylated piperidine compound.
  • the present invention also provides development solutions for use in high contrast development of photographic elements.
  • Photographic elements which can be processed in the novel high contrast developing solutions of this invention are not limited to “lith” films.
  • “lith” films contain high chloride emulsions (at least about 60 percent by weight silver chloride based on total silver halide), most usually in the form of silver chlorobromides or silver chlorobromoiodides. Such films give excellent results when used in the novel high contrast developing solutions of this invention.
  • the novel high contrast developing solutions of this invention can also be usefully employed with other types of silver halide photographic elements, for example with elements utilizing silver bromide or silver bromoiodide emulsions.
  • the hydrazine compound can be incorporated in the photographic element or in the developing solution, the essential requirement being that it be present during development of the exposed element. Incorporation of a hydrazine compound in both the photographic element and in the developing solution is, of course, a further alternative that can be utilized where it is desired to do so.
  • contrast or "gamma" of a photographic element refers to the rate of change of density with exposure and is measured by the slope of the straight line portion of the characteristic curve.
  • Photographic elements processed in the novel developing solutions of this invention typically exhibit very high contrast, by which is meant a gamma of greater than 10.
  • a hydrazine compound is intended to include hydrazine and hydrazine derivatives, including those which are suited for incorporation in developing solutions and those which are suited for incorporation in photographic elements.
  • Hydrazine (H 2 N-NH 2 ) is an effective contrast-promoting agent which can be incorporated in the developing solutions of this invention.
  • any of a wide variety of water-soluble hydrazine derivatives can be added to the developing solution.
  • Preferred hydrazine derivatives for use in the developing solutions of this invention include organic hydrazine compounds of the formula: where R' is an organic radical and each of R 2 , R 3 and R 4 is a hydrogen atom or an organic radical.
  • Organic radicals represented by R 1 , R 2 , R 3 and R 4 include hydrocarbyl groups such as an alkyl group, an aryl group, an aralkyl group, an alkaryl group, and an alicyclic group, as well as hydrocarbyl groups substituted with substituents such as alkoxy groups, carboxy groups, sulfonamido groups, and halogen atoms.
  • Particularly preferred hydrazine derivatives for incorporation in the developing solutions of this invention include alkylsulfonamido aryl hydrazines such as p-(methylsulfonamido)phenylhydrazine and alkylsulfonamidoalkyl aryl hydrazines such as p-(methylsulfonamidomethyl)phenylhydrazine.
  • the hydrazine compound be incorporated in the photographic element.
  • it can be incorporated in a silver halide emulsion used in forming the photographic element.
  • the hydrazine compound can be present in a hydrophilic colloid layer of the photographic element, preferably a hydrophilic colloid layer which is coated to be contiguously adjacent to the emulsion layer in which the effects of the hydrazine compound are desired. It can, of course, be present in the photographic element distributed between or among emulsion and hydrophilic colloid layers, such as undercoating layers, interlayers, and overcoating layers.
  • Photographic elements which are particularly preferred for use in the method of this invention include elements containing a hydrazine compound of the formula: wherein R' is a phenyl nucleus having a Hammett sigma value-derived electron withdrawing characteristic of less than +0.30.
  • R' can take the form of a phenyl nucleus which is either electron donating (electropositive) or electron withdrawing (electronegative); however, phenyl nuclei which are highly electron withdrawing produce inferior nucleating agents.
  • the electron withdrawing or electron donating characteristics of specific phenyl nucleus can be assessed by reference to Hammett sigma values.
  • the phenyl nucleus can be assigned a Hammett sigma value-derived electron withdrawing characteristic which is the algebraic sum of the Hammett sigma values of its substituents (i.e., those of the substituents, if any, to the phenyl group).
  • the Hammett sigma values of any substituents to the phenyl ring of the phenyl nucleus can be determined algebraically simply by determining from the literature the known Hammett sigma values for each substituent and obtaining the algebraic sun thereof. Electron donating substituents are assigned negative sigma values.
  • R' can be a phenyl group which is unsubstituted.
  • the hydrogens attached to the phenyl ring each have a Hammett sigma value of 0 by definition.
  • the phenyl nuclei can include halogen ring substituents.
  • ortho- or para-chloro or fluoro substituted phenyl groups are specifically contemplated, although the chloro and fluoro groups are each mildly electron withdrawing.
  • Preferred phenyl group substituents are those which are not electron withdrawing.
  • the phenyl groups can be substituted with straight or branched chain alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, n-octryl, tert-octyl, n-decyl, n-dodecyl and similar groups).
  • the phenyl groups can be substituted with alkoxy groups wherein the alkyl moieties thereof can be chosen from among the alkyl groups described above.
  • the phenyl groups can also be substituted with acylamino groups.
  • Illustrative acylamino groups include acetylamino, propanoylamino, butanoylamino, octanoylamino, benzoylamino, and similar groups.
  • the alkyl, alkoxy and/or acylamino groups are in turn substituted with a conventional photographic ballast, such as the ballasting moieties of incorporated couplers and other immobile photographic emulsion addenda.
  • the ballast groups typically contain at least eight carbon atoms and can be selected from both aliphatic and aromatic relatively unreactive groups, such as alkyl, alkoxy, phenyl, alkylphenyl, phenoxy, alkylphenoxy and similar groups.
  • the alkyl and alkoxy groups, including ballasting groups, if any, preferably contain from 1 to 20 carbon atoms, and the acylamino groups, including ballasting groups, if any, preferably contain from 2 to 21 carbon atoms. Generally, up to about 30 or more carbon atoms in these groups are contemplated in heir ballasted form. Methoxyphenyl, tolyl (e.g., p-tolyl and m-tolyl) and ballasted butyramidophenyl nuclei are specifically preferred.
  • hydrazine compounds are the following: 1-Formyl-2-(4-[2-(2,4-di-tert-pentylphenoxy)butyramido]phenyl)hydrazine
  • Preferred photographic elements for use in the method of this invention also include those in which the hydrazide comprises an adsorption promoting moiety.
  • Hydrazides of this type contain an unsubstituted or mono-substituted divalent hydrazo moiety and an acyl moiety.
  • the adsorption promoting moiety can be chosen from among those known to promote adsorption of photographic addenda to silver halide grain surfaces. Typically, such moieties contain a sulfur or nitrogen atom capable of complexing with silver or otherwise exhibiting an affinity for the silver halide grain surface. Examples of preferred absorption promoting moieties include thioureas, heterocyclic thioamides and triazoles.
  • Exemplary hydrazides containing an adsorption promoting moiety include:
  • Hydrazine compounds incorporated in the developing solution in the practice of this invention are effective at very low levels of concentration. For example, hydrazine gives effective results in the developing solution in an amount of only 0.1 grams per liter. Hydrazine compounds incorporated in the photographic element are typically employed in a concentration of from about 10- 4 to about 10- 1 mole per mole of silver, more preferably in an amount of from about 5 x 10- 4 to about 5 x 10- 2 mole per mole of silver, and most preferably in an amount of from about 8 x 10- 4 to about 5 x 10- 3 mole per mole of silver.
  • the hydrazides containing an adsorption promoting moiety can be used at a level as low as about 5 x10 -6 mole per mole of silver.
  • dihydroxybenzene developing agents employed in the aqueous alkaline developing solutions of this invention are well known and widely used in photographic processing.
  • the preferred developing agent of this class is hydroquinone.
  • Other useful dihydroxybenzene developing agents include:
  • auxiliary super-additive developing agents employed in the aqueous alkaline developing solutions of this invention are also well known and widely used in photographic processing.
  • “super-additivity” refers to a synergistic effect whereby the combined activity of a mixture of two developing agents is greater than the sum of the two activities when each agent is used alone in the same developing solution (Note especially the paragraph entitled "Superadditivity” on Page 29 of Mason).
  • the preferred auxiliary super-additive developing agents are the 3-pyrazolidone developing agents.
  • Particualrly preferred developing agents of this class are those represented by the formula: in which R' is aryl (including substituted aryl) and R 2 , R 3 , and R 4 are hydrogen or alkyl (including substituted alkyl). Included within the definition of R 1 are phenyl and phenyl substituted with groups such as methyl, chloro, amino, methylamino, acetylamino, methoxy and methylsulfonamidoethyl.
  • R 2 , R 3 and R 4 are unsubstituted alkyl and alkyl substituted with groups such as hydroxy, carboxy, or sulfo.
  • the most commonly used developing agents of this class are 1-phenyl-3-pyrazolidone,1-phenyl-4,4-dimethyl-3-pyrazolidone,1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone.
  • Other useful 3-pyrazolidone developing agents include:
  • aminophenols More preferred but also useful auxiliary super-additive developing agents for use in the aqueous alkaline developing solutions of this invention are the aminophenols.
  • useful aminophenols include:
  • auxiliary super-additive developing agent can be incorporated in the developing solutions of this invention, if desired.
  • the developing solution can contain hydroquinone, 1-phenyl-3-pyrazolidone, and p-methylaminophenol sulfate.
  • More than one dihydroxybenzene developing agent can, of course, also be utilized, if desired.
  • the aqueous alkaline photographic developing compositions of this invention contain a sulfite preservative at a level sufficient to protect the developing agents against aerial oxidation and thereby promote good stability characteristics.
  • Useful sulfite perservatives include sulfites, bisulfites, metabisulfites, and carbonyl bisulfite adducts.
  • Typical examples of sulfite preservatives include:
  • an hydroxyalkylated piperidine compound is incorporated in the aqueous alkaline developing solution in a contrast-promoting amount; the term "an hydroxyalkylated piperidine compound” being used herein to mean a compound comprising at least one piperidine ring and at least one hydroxylalkyl group.
  • an hydroxyalkylated piperidine compound permits high contrast development in the presence of a hydrazine compound to be accomplished at low ph levels as compared to the pH level needed to achieve the same contrast without the use of an hydroxyalkylated piperidine compound.
  • hydroxyalkylated piperidine compound also permits high contrast development in the presence of a hydrazine compound to be carried out at lower pH levels than does the use of many of the other amino compounds.
  • the advantages of being able to carry out development at low pH levels will be readily apparent to those skilled in the art of photographic processing. For example, with the use of a low pH level, the developing solution is much less hazardous and its effective life greatly enhanced.
  • the aqueous alkaline developing solutions of this invention can vary widely in regard to the concentration of the various ingredients included therein.
  • the dihydroxybenzene developing agent is used in an amount of from about 0.045 to about 0.65 moles per liter, more preferably in an amount of about 0.09 to about 0.36 moles per liter;
  • the auxiliary super-additive developing agent is used in an amount of from about 0.0005 to about 0.01 moles per liter, more preferably in an amount of from about 0.001 to about 0.005 moles per liter;
  • the sulfite preservative is used in an amount of from about 0.04 to about 0.80 moles per liter, more preferably in an amount of from about 0.12 to about 0.60 moles per liter;
  • the hydroxyalkylated piperidine compound is used in an amount of from about 0.001 to about 0.15 moles per liter, more preferably in an amount of from about 0.002 to about 0.1 moles per liter.
  • discrimination a term which is used herein to describe the ratio of the extent of shoulder development to “pepper fog” level. Good discrimination, i.e., full shoulder development with low pepper fog, is necessary to obtain good halftone dot quality.
  • pepper fog is commonly utilized in the photographic art, and refers to fog of a type characterized by numerous fine black specks).
  • hydroxyalkylated piperidine compounds meet all the criteria necessary to provide optimum performance in the invention of U.S. patent 4,269,929.
  • the hydroxyalkylated piperidine compounds are highly active, have an adequate degree of solubility, exhibit very low volatility, have an azeotropic characteristics, are non-toxic, exhibit no odor, and provide very low pepper fog, excellent discrimination and excellent halftone dot quality.
  • Preferred hydroxyalkylated piperidine compounds for use in this invention include compounds of the formula: where each n is independently an integer with a value of from 1 to 4, and compounds of the formula: where R, and R 2 are independently selected from the group consisting of hydrogen, alkyl groups of 1 to 6 carbon atoms, and radicals of the formula: where X is 0 to 3, y is 0 to 3, and Z is 1 to 3, with the proviso that at least one of R 1 and R 2 is a radical of the above formula.
  • the compound 1,3-di(N-2-hydroxyethyl)-4-piperidyl)propane which is a well known compound that is commercially available, is illustrative of compounds of formula I above. It has the formula:
  • An alternative name for this compound is 4,4'-(1,3-propanediyl)-bis-1,1'-piperidineethanol.
  • hydroxyalkylated piperidine compounds of Formula II above include: 1-methyl-2-piperidinemethanol 1-methyl-3-piperidinemethanol 1-piperidineethanol 3-piperidino-1,2-propanediol
  • the very high degree of activity as a contrast-promoting agent exhibited by the hydroxyalkylated piperidine compounds is of particular benefit in permitting the use of lower pH levels than is feasible with many other amino compounds, with resulting improvement in the effective life of the develoDina solution. that is, the length of time that it can be used or stored and still provide acceptable development characteristics.
  • the hydroxyalkylated piperidine compounds can be used at very low concentration levels - such as levels of a few grams per liter and, in some instances, as low as one gram per liter or less - and still provide very high contrast. This is important . for reasons of economy, since the cost of the amino compound can be a substantial portion of the cost of the entire developing solution, and use of very low concentrations of the amino compound provides very significant cost savings. Certain of the amino compounds employed in the working examples of U.S patent 4,269,929 also provided very high contrast when used at very low concentration levels. For example, as shown in Table II of U.S.
  • the aqueous alkaline developing solution of this invention have a pH of about 10 and below 12.
  • the preferred pH range for the aqueous alkaline developing solutions of this invention is from 10.3 to 11.8.
  • a particular preferred pH range is from 11.2 to 11.6.
  • alkaline agents whose function is to control pH, such as carbonates or phosphates, can be included in the developing solution, if necessary, but adequate control of pH can also be provided by amino compounds. In some instances, it will be useful to utilize two different amino compounds, one to promote contrast and one to control pH.
  • a particularly useful developing solution is one which is free of pH buffers such as carbonates or phosphates, which contains 2-methylaminoethanol in an amount sufficient to provide the desired pH, and which contains a contrast-promoting amount of an hydroxyalkylated piperidine compound.
  • This developing solution is particularly useful in combination with a hardening fix, since it avoids the problems of precipitate formation that can occur when a developing solution containing a phosphate buffer is used in combination with a hardening fix.
  • the developing solutions of this invention can utilize much higher levels of sulfite ion, and thereby achieve the advantage of increased stability, since the higher level of sulfite ion provides increased protection against aerial oxidation.
  • organic antifoggants In carrying out the method of this invention, it is preferred to employ one or more organic antifoggants to minimize fog formation.
  • the organic antifoggants can be incorporated in the photographic element or they can be added to the developing solution, the essential requirement being that they be present during the developing process. Particularly advantageous results are achieved with the use of benzotriazole antifoggants.
  • a further preferred class of organic antifoggants are the mercapto azole antifoggant.
  • Inorganic antifoggants, or restrainers, such as alkali metal bromides, can be utilized in conjunction with the use of an organic antifoggant if desired.
  • benzotriazole anti-foggant for use in the developing solutions of this invention are benzotriazole, halo-substituted benzotriazoles such as 4-chlorobenzotriazoles; 4-bromobenzotriazole and 5-chlorobenzotriazole, and alkyl-substituted benzetriazoles such as 5-methylbenzotriazole.
  • Preferred mercapto azole antifoggants are those represented by the formula: wherein Z represents the atoms necessary to complete a 5 or 6 member heterocyclic ring, such as pyrimidine, triazine, tetrazole, triazole, imidazole, diazole, oxadiazole orthiadiazole ring; and SX represents a mercapto function, n being a whole number, typically a number from 1 to about 3, any free bonds being satisfied by hydrogen atoms.
  • X is a cation which includes hydrogen, an alkali metal, e.g., sodium or potassium, ammonium or an organic amine residue of such amines as triethyl amine, triethanol amine, morpholine and the like.
  • Mercapto tetrazole antifoggants are especially suitable in the practice of this ivention and include those of the formula: wherein R is an aliphatic or aromatic radical containing up to about 30 carbon atoms and SX is a mercapto function.
  • mercapto azole antifoggants include:
  • Photographic elements processed in the aqueous alkaline developing solutions of this invention comprise one or more layers formed from a negative-working silver halide emulsion comprised of a binder and radiation-sensitive silver halide grains capable of forming a surface latent image.
  • the useful silver halide emulsions include the high chloride emulsions conventionally employed in forming "lith" photographic elements as well as silver bromide and silver bromoiodide emulsion, which are recognized in the art to be capable of attaining higher photographic speeds.
  • the iodide content of the silver halide emulsions is less than about 10 mole percent silver iodide, based on total silver halide.
  • the silver halide grains of the emulsions are capable of forming a surface latent image, as opposed to being of the internal latent image-forming type.
  • Surface latent image silver halide grains are employed in the overwhelming majority of negative-working silver halide emulsions, whereas internal latent image-forming silver halide grains, though capable of forming a negative image when developed in an internal developer, are usually employed with surface developers to form direct-positive images.
  • the distinction between surface latent image and internal latent image silver halide grains is generally well recognized in the art. Generally, some additional ingredient or step is required in preparation to form silver halide grains capable of preferentially forming an internal latent image as compared to a surface latent image.
  • the silver halide emulsions can be spectrally sensitized with dyes from a variety of classes, including the polymethine dye class, which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra- and poly-nuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyryls and streptocyanines.
  • the polymethine dye class which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra- and poly-nuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyryls and streptocyanines.
  • the developing solutions of this invention can optionally contain any of a wide variety of addenda known to be useful in photographic developing compositions.
  • they can contain solvents, buffers, sequestering agents, development accelerators, agents to reduce swelling of the emulsion layers, and the like.
  • the time and temperature employed for development can be varied widely.
  • the development temperature will be in the range of from about 20°C (68°F) to about 50°C (122°F), more preferably in the range of from about 25°C (77°F) to about 40°C (104°F), while the development time will be in the range of from about 10 seconds to about 150 seconds, more preferably in the range of from about 20 seconds to about 120 seconds.
  • Developing solutions were prepared as in Example 1, except that the amino compound was 3- - piperidino-1,2-propanediol and similar results were obtained. With this amino compound, the optimum concentration in the developing solution was about 15 grams per liter.

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Claims (35)

1. Verfahren zur kontrastreichen Entwicklung eines photographischen Elementes mit mindestens einer Silberhalogenidemulsionsschicht, bei dem man das Element in Gegenwart einer Hydrazinverbinung mit einer wäßrigen alkalischen Entwicklungslösung in Kontakt bringt, die einen pH-Wert von über 10 unter 12 hat und eine Dihydroxybenzol-Entwicklerverbindung, eine Hilfsentwicklerverbindung mit super-additivem Effekt sowie ein Sulfit-Präservierungsmittel enthält, dadurch gekennzeichnet, daß die Entwicklungslösung ferner eine den Kontrast steigernde Menge einer hydroxyalkylierten Piperidinverbindung enthält.
2. Verfahren nach Anspruch 1, in dem die den Kontrast steigernde hydroalkyliete Piperidinverbindung der folgenden Formel:
Figure imgb0027
in der n jeweils unabhängig voneinader eine Zahl mit einem Wert von 1 bis 4 ist oder der Formel:
Figure imgb0028
entspricht, in der R, und R2 unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Wasserstoff, Alkylgruppen mit 1 bis 6 Kohlenstoffatomen und Resten der Formel:
Figure imgb0029
in der x gleich 0 bis 3, y gleich 0 bis 3 und z gleich 1 bis 3 ist, wobei gilt, daß mindestens einer der Reste R1 und R2 ein Rest der obigen Formel ist.
3. Verfahren nach Anspruch 1 oder 2, in dem die hydroxyalkylierte Piperidinverbindung ausgewählt ist aus der Gruppe von Verbindungen bestehend aus: 1,3-Di(N-2-hydroxyethyl-4-piperidyl)propan, 1-Methyl-2-piperdinmethanol, 1-Methyl-3-piperidinmethanol, 1-Piperidinethanol und 3-Piperidino-1,2-propandiol.
4. Verfahren nach Anspruch 1, in dem die Silberhalogenidemulsionsschicht die Hydrazinverbindung enthält.
5. Verfahren nach Anspruch 1, in dem die Entwicklungslösung die Hydrazinverbindung enthält.
6. Verfahren nach Anspruch 1, in dem die Entwicklungslösung einen pH-Wert im Bereich von 10,3 bis 11,8 aufweist.
7. Verfahren nach Anspruch 1, in dem die Entwicklungslösung einen pH-Wert von 11,2 bis 11,6 aufweist.
8. Verfahren nach Anspruch 1, in dem die Dihydroxybenzol-Entwicklerverbindung Hydrochinon ist.
9. Verfahren nach Anspruch 1, in dem die Hilfsentwicklerverbindung mit dem super-additiven Effekt eine 3-Pyrazolidon-Entwicklerverbindung ist.
10. Verfahren nach Anspruch 9, in dem die Hilfsentwicklerverbindung mit dem super-additiven Effekt l-Phenyi-3-pyrazoiidon, 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidon- oder 1-Phenyl-4,4-dimethyl-3-pyrazolidon ist.
11. Verfahren nach Anspruch 1, in dem die Hilfsentwicklerverbindung mit dem super-additiven Effekt eine Aminophenol-Entwicklerverbindung ist.
12. Verfahren nach Anspruch 11, in dem die Hilfsentwicklerverbindung mit dem super-additiven Effekt p-Methylaminophenolsulfat ist.
13. Verfahren nach Anspruch 1, in dem das Sulfit-Präservierungsmittel Natriumsulfit ist.
14. Verfahren nach Anspruch 1, in dem die Entwicklungslösung zusätzlich ein Benzotriazol-Antischleiermittel enthält.
15. Verfahren nach Anspruch 14, in dem die Entwicklungslösung zusätzlich 5-Methylbenzotriazol enthält.
16. Verfahren nach Anspruch 14, in dem die Entwicklungslösung zusätzlich eine Kombination aus Benzotriazol, 5 Methylbenzotriazol und 1-Phenyl-5-mercaptotetrazol enthält.
17. Verfahren nach Anspruch 4, in dem die Silberhalogenidemulsionsschicht 1-Formyl-2-(4-[2-(2-,4-di- t-pentylphenoxy)butyramido]phenylhydrazid enthält und die Entwicklungslösung einen pH-Wert im Bereich von 11,2 bis 11,6 hat und enthält Hydrochinon, 1-Phenyl-4,4-dimethyl-3-pyrazolidon, Natriumsulfit und eine den Kontrast steigernde Menge von 3-Piperidino-1,2-propandiol.
18. Verfahren nach Anspruch 17, in dem die Entwicklungslösung etwa fünfzehn Gramm 3-Piperidino-1,2-propandiol pro Liter Lösung enthält.
19. Wäßrige alkalische photographische Entwicklungslösung zur Verwendung bei der kontrastreichen Entwicklung photographischer Elemente in Gegenwart einer Hydrazinverbindung mit einem pH-Wert von über 10 und unter 12 und einem Gehalt an einer Dihydroxybenzol-Entwicklerverbindung, einer Hilfsentwicklerverbindung mit einem super-additiven Effekt sowie einem Sulfit-Präservierungsmittel, dadurch gekennzeichnet, daß die Entwicklungslösung weiterhin eine den Kontrast steigernde Menge einer hydroxyalkylierten Piperidinverbindung enthält.
20. Wäßrige alkalische Entwicklungslösung nach Anspruch 19, in der die den Kontrast steigernde hydroxyalkylierte Piperidinverbindung der folgenden Formel:
Figure imgb0030
in der n jewils unabhängig voneinander eine Zahl mit einem Wert von 1 bis 4 ist oder der Formel:
Figure imgb0031
entspricht, in der R, und R2 unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Wasserstoff, Alkylgruppen mit 1 bis 6 Kohlenstoffatom und Resten der Formel:
Figure imgb0032
in der x gleich 0 bis 3, y gleich 0 bis 3 und z gleich 1 bis 3 ist, wobei gilt, daß mindestens einer der Reste R1 und R2 ein Rest der obligen Formel ist.
21. Wäßrige alkalische Entwicklungslösung nach Anspruch 19, mit einem pH-Wert im Bereich von 10,3 bis 11,8.
22. Wäßrige alkalische Entwicklungslösung nach Anspruch 19, mit einem pH-Wert im Bereich von 11,2 bis 11,6.
23. Wäßrige alkalische Entwicklungslösung nach Anspruch 19, in dem die Dihydroxybenzol-Entwicklerverbindung Hydrochinon ist.
24. Wäßrige alkalische Entwicklungslösung nach Anspruch 19, in der die Hilfsentwicklerverbindung mit dem super-additiven Effekt eine 3-Pyrazolidon-Entwicklerbindung ist.
25. Wäßrige alkalische Entwicklungslösung nach Anspruch 24, in der die Hilfsentwicklerverbindung mit dem super-additiven Effekt 1-Phenyl-3-pyrazolidon, 1-Phenyl-4-methyl-4-hydroxy-methyl-3-pyrazolidon- oder 1-Phenyl-4,4-dimethyl-3-pyrazolidon ist.
26. Wäßrige alkalische Entwicklungslösung nach Anspruch 19, in der die Hilfsentwicklerverbindung mit dem super-additiven Effekt eine Aminophenol-Entwicklerverbindung ist.
27. Wäßrige alkalische Entwicklungslösung nach Anspruch 26, in der die Hilfsentwicklerverbindung mit dem super-additiven Effekt p-Methylaminophenolsulfat ist.
28. Wäßrige alkalische Entwicklungslösung nach Anspruch 19, in der das Sulfit-Präservierungsmittel Natriumsulfit ist.
29. Wäßrige alkalische Entwicklungslösung nach Anspruch 19, die zusätzlich 2-Methylaminoethanol enthält.
30. Wäßrige alkalische Entwicklungslösung nach Anspruch 19, die zusätzlich ein Benzotriazol-Antischleiermittel enthält.
31. Wäßrige alkalische Entwicklungslösung nach Anspruch 30, die zusätzlich 5-Methylbenzotriazol enthält.
32. Wäßrige alkalische Entwicklungslösung nach Anspruch 30, die zusätzlich eine Kombination aus Benzotriazol, 5-Methylbenzotriazol und 1-Phenyl-5-Mercapt-tetrazol enthält.
33. Wäßrige alkalische Entwicklungslösung nach Anspruch 19, mit einem pH-Wert im Bereich von 10,3 bis 11,8 und mit einem Gehalt an Hydrochinon, 1-Phenyl-4,4-dimethyl-3-pyrazolidon, Natriumsulfit und 3-Piperidino-1,2-propandiol.
34. Wäßrige alkalische Entwicklungslösung nach Anspruch 19, enthaltend die Hydrazinverbindung, eine Dihydroxybenzol-Entwicklerverbindung, eine Hilfsentwicklerverbindung mit einem super-additiven Effekt, ein Sulfit-Präservierungsmittel und eine den Kontrast steigernde Menge von 3-Piperidino-1,2-propandiol.
35. Wäßrige alkalische Entwicklungslösung nach Anspruch 34, mit einem pH-Wert im Bereich von 11,2 bis 11,6.
EP19870903549 1986-05-14 1987-05-04 Kontrastreiche entwicklung von photographischen elementen Expired - Lifetime EP0267264B1 (de)

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