US2688548A - Photographic developer composition - Google Patents

Photographic developer composition Download PDF

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US2688548A
US2688548A US372166A US37216653A US2688548A US 2688548 A US2688548 A US 2688548A US 372166 A US372166 A US 372166A US 37216653 A US37216653 A US 37216653A US 2688548 A US2688548 A US 2688548A
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pyrazolidone
acid
imino
compounds
developer
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George A Reynolds
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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
    • 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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • 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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets

Definitions

  • imino-sorboascorbic acid imino-w-lactoascorbic acid, imino-maltoascorbic acid, imino-l-araboascorbic acid, imino-d-glucoascorbic acid, imino-d-galactoascorbic acid, imino-l-guloascorbic acid, and imino-l-alloascorbic acid.
  • the above compounds difier principally in the structure of the terminal group R-CH2-(CHOH)n iand in some cases the compounds are stereoisomers.
  • the compounds are described in particular by Pigman and Wolfrom, Advances in Carbohydrate Chemistry, Academic Press, New York, 1946, pp. 80-82.
  • the above iminoascorbic acid analogs are named to denote the particular sugar from which they can be synthesized. It will be observed that the compounds are non-aromatic and contain the characteristic mononuclear heterocyclic ene-diol group.
  • the compounds are particularly distinguished from aromatic silver halide developing agents such as catechol or pyro gallol which show serious disadvantages such as strong tendency to form colored oxidation products in the development reaction or on contact with the oxygen in the air which products discolor solutions and stain photographic materials.
  • 3-pyrazolidone compounds such as 1-phenyl-3-pyrazolidone
  • 3-pyrazolidone compounds are highly unstable in alkaline developer compositions free of a preservative and tend to darken and lose development activity quickly particularly through aerial oxidation.
  • the 3-pyrazolidone compounds when development is carried out with the 3-pyrazolidone compounds in the presence of the enediol compounds, the latter function as preservatives and the developer is highly resistant to discoloration and loss of activity.
  • Another advantageous characteristic of the ene-diol-pyrazolidone developer compositions is that the developers show little tendency for the formation of silver sludge or for the formation of dichroic stain on silver images.
  • a further advantage is that since the ene-diol compounds are very effective preservatives for the pyrazolidone developing agents and are highly soluble in water, it
  • a further characteristic of the ene-diolpyrazolidone developer compositions of the invention resides in the fact that the compositions behave as strong surface latent image developers as opposed to internal latent image developers, as long as they are free of silver halide solvents such as sodium sulfite. That is, developer compositions containing 3-pyrazolidone compounds have been described in the literature but invariably they have been compounded so as to con tain a silver halide solvent such as sodium sulfite as a preservative.
  • the 3-pyrazolidone developers free of preservative are very unstable.
  • the ene-diol compounds are incorporated into the 3-pyrazolidone developer compositions, the ene-diol compounds supply the required preservative effect and the surface latent image developer characteristics are maintained.
  • the 3-pyrazolidone developer compositions of the invention containing the above ene-diol compounds can be readily converted to internal latent image developer compositions by merely adding a silver halide solvent such as sodium thiosulfate thereto.
  • the resultant internal latent image developer composition by virtue of the presence of one of the mentioned ene-diol compounds, likewise possesses excellent keeping properties even in the absence of the usual sulfite preservative.
  • the 3-pyrazolidone silver halide developing agents employed in the developer compositions together with ascorbic acid and its analogs have the general formula in which the R groups each represent various substituents such as hydrogen, alkyl or aryl groups, for example, R1 can be hydrogen or a group such as alkyl preferably containing from 1 to 4 carbon atoms, or an aryl group of the benzene or naphthalene series substituted or not, and R2, R3, R4 and R5 can be hydrogen atoms,
  • 1-phenyl-4,4-dimethyl-3-pyrazo1idone 15. 1 m aminophenyl 4 methyl 4 propyl- S-pyrazolidone 16. 1 o chlorophenyl 4 methyl 4 ethyl- S-pyrazolidone 17. 1 m acetamidophenyl 4,4 diethyl 3- pyrazolidone 18. 1 (p 3 hydroxyethylphenyl) 4,4 dimethyl-3-pyrazolidone 19. 1 p hydroxyphenyl 4,4 dimethyl 3- pyrazolidone 2'0. 1 p methoxyphenyl 4,4 diethyl 3- pyrazolidone 21.
  • the 4,4-dialkyl-3-pyrazolidone compounds 13 to 23 and 26 above are particularly efiicacious for use in the developer compositions of my invention inasmuch as they are more active developing agents than are compounds 1 to 12 which contain a single substituent or only hydrogen atoms in the 4-position of the pyrazolidone nucleus.
  • the 4,4-dialkyl-3-pyrazolidone compounds are described and claimed in the Allen et al. U. S. patent application Serial No. 372,148 filed concurrently herewith.
  • w-hydroxyalkyl-3-pyrazolidones for example, compounds iminoreductone derivative such as p-aminobenzoic acid reductone, mand p-aminosalicylic acid reductone and sulfanilic acid reductone are similar in structure to the imino ascorbic acid compounds and their use in developer compositions is disclosed and claimed in the Henn and Reynolds U. S. patent application Serial No. 372,168 filed concurrently herewith.
  • Example 1 The striking superadditivity obtained by combining the pyrazolidones and ene-diols, is shown in the following table. It is seen that the individual agents develop only weakly, but that when combined, they develop vigorously, producing images of high density.
  • the formulas compare the activity of the enediol ascorbic acid alone at an 0.02 molar concentration (3.5 grams per liter), of the pyrazolidone by itself, at 0.0025 molar concentration (0.4 to 0.5 gram per liter), and combinations of the agents in these concentrations.
  • the activity was tested with a fine grain positive film, given a step wedge exposure and developed for a series of times at 68 F. and with high agitation.
  • the ene-diol compounds imino-d-glucoascorbic acid above obtained from d-glucose is representative of a number of ene-diol compounds containing the iminoascorbic acid group derived from sugars.
  • the compound is of particular value in my invention since its development rate is markedly accelerated by the 3-pyrazolidone silver halide developing agents, particularly l-phenyl-3-pyrazolidone.
  • the other ene-diol compounds containing the imino group can be prepared by the methods of the reference immediately above from, for example, erythrose, galla-ctose, sorbose, mannose, maltose, and lactose and are likewise useful in the 3-pyrazolidone developer compositions where the latter compounds appreciably accelerate the development rate of the ene-diol compounds.
  • Example 2 The following developer compositions are particularly suitable as negative developers for color films:
  • the developers of this example can be used in any of the well-known processes of color development Where a black-and-white developer is required.
  • the developers are especially useful in 7 mixed grain color processes employing films such as disclosed in Mannes et a1.
  • developer compositions containing or free of silver halide solvents, are prepared from mixtures of at least one of the indicated 3-pyrazolidone compounds and at least one of the iminoascorbic acid compounds.
  • the enediol-pyrazolidone developer composition of the above example exhibits internal latent image development characteristics particularly by virtue of the presence of the silver halide solvent.
  • developer compositions in addition to that exemplified above, are those containing imino-d-glucoascorbic acid and either l-phenyl-B-pyrazolidone or a l-tolyl-3-pyrazolidone such as l-p-tolyl-3-pyrazolidone or l-ptolyl-4A-dimethyl-3-p-yrazolidone or a l-(p-flhydroxyalkylphenyl) 4,4 dialkyl 3 pyrazolidone such as 1-(p-c-hydroxyethylphenyl)- 4,4-dimethyl-3pyrazolidone, or a 1-(p-B-w-hY- droxyalkylphenyl) -3-pyrazolidone' such as 1- (pfl-hydroxyethylphenyl) -3-pyrazolidone.
  • l-phenyl-B-pyrazolidone or a l-tolyl-3-pyrazolidone such as l-p-to
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and a compound having the general structure prising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and a compound having the struc- 4.
  • a photographic developer composition comprising an aqueous alkaline solution containin a mixture of a 3-pyrazolidone silver halide developing agent and a compound having the structure 5.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and a compound having the structure 6.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of a B-pyrazolidone silver halide developing agent and a compound having the structure 7.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and imino-d-glucoascorbic acid.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 1-tolyl-3-pyrazolidone and iminod-glucoascorbic acid.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-p-tolyl-4,4-dimethyl-3-pyrazolidone and imino-d-glucoascorbic acid.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-phenyl-4A-dimethyl-3-pyrazolidone and. imino-d-glucoascorbic acid.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-(p-/3-hydroxyethy1phenyl-3-pyrazolidone and imino-d-glucoascorbic acid.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-(p-B-hydroxyethylphenyl)-4,4-dimethyl 3 pyrazolidone and imino d glucoascorbic acid.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-phenyl-3-pyrazolidone and iminod-glucoascorbic acid.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-p-tolyl-3-pyrazolidone and iminod-glucoascorbic acid.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and a compound of the class consisting of imino-l-ascorbic acid, imino-d-ascorbic acid, imino-l-erythroascorbic acid, imino-l-glucoascorbic acid, imino-d-glucoascorbic acid, iminod gelactoascorbic acid, imino l guloascorbic acid, imino-l-alloascorbic acid, imino-d-glucoheptoascorbic acid, imino 1 rhamnoascorbic acid, imino-l-fucoascorbic acid, imino-l-araboascorbic acid, imino-sorboascorbic acid, iminoisoascorbic acid, imino-fi-desoxy-l-ascorbie acid,

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Description

Patented Sept. 7, 1954 PHOTOGRAPHIC DEVELOPER COMPOSITION George A. Reynolds, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application August 3, 1953, Serial No. 372,166
19 Claims. 1
R-CHg(CHOH)n-1-CHO=C =NH OH OH wherein R represents a hydroxyl group when n represents a positive integer from 1 to 4 and R. represents a hydrogen atom when n represents a positive integer from 2 to 4.
The following compounds are representative of compounds having the above general formula with which my invention is concerned.
CHzOH imino-l-erythoascorbic acid HN=C noc': 1 ll H 0 OJ H9; H0 (3H JHz O H imino-l-ascorbic acid C=NH O i OH O H La O OH C H2OH imino-d-glucoascorbic acid HN=C HO (J HO ('3 0 EU H O H imino-G-desoxy-l-ascorbic acid HN=C HO H HO C 0 Hal HO 43H H O OH imino-l-rhamnoascorbic acid HN=C H O 0 Hot 0 H O C H imino-l-fucoascorbic acid HO [I H0 ((Ej HO JH H O H In) OH imino-d-glucoheptoascorbic acid Other compounds contemplated by the invention which have the above general structure are imino-d-ascorbic acid, imino-l-ascorbic acid, imino-isoascorbic acid and other iminoascorbic acid analogs, e. g., imino-sorboascorbic acid, imino-w-lactoascorbic acid, imino-maltoascorbic acid, imino-l-araboascorbic acid, imino-d-glucoascorbic acid, imino-d-galactoascorbic acid, imino-l-guloascorbic acid, and imino-l-alloascorbic acid.
As will be apparent, the above compounds difier principally in the structure of the terminal group R-CH2-(CHOH)n iand in some cases the compounds are stereoisomers. The compounds are described in particular by Pigman and Wolfrom, Advances in Carbohydrate Chemistry, Academic Press, New York, 1946, pp. 80-82. Accordingly, the above iminoascorbic acid analogs are named to denote the particular sugar from which they can be synthesized. It will be observed that the compounds are non-aromatic and contain the characteristic mononuclear heterocyclic ene-diol group. The compounds are particularly distinguished from aromatic silver halide developing agents such as catechol or pyro gallol which show serious disadvantages such as strong tendency to form colored oxidation products in the development reaction or on contact with the oxygen in the air which products discolor solutions and stain photographic materials.
I have discovered that the developing rate of developer solutions containing the above enediol compounds can be markedly accelerated by the addition to the ene-diol silver halide developing compositions of 3-pyrazolidone compounds which themselves are only moderately active developing agents for silver halide. The activity of the resulting developer solution containing both the ene-diol and the pyrazolidone is very much greater than would be expected from summing up the separate activities. An added feature of the ene-diol-pyrazolidone developer compositions resides in the stability of the developing solution. That is, 3-pyrazolidone compounds such as 1-phenyl-3-pyrazolidone, are highly unstable in alkaline developer compositions free of a preservative and tend to darken and lose development activity quickly particularly through aerial oxidation. On the other hand, when development is carried out with the 3-pyrazolidone compounds in the presence of the enediol compounds, the latter function as preservatives and the developer is highly resistant to discoloration and loss of activity. Another advantageous characteristic of the ene-diol-pyrazolidone developer compositions is that the developers show little tendency for the formation of silver sludge or for the formation of dichroic stain on silver images. A further advantage is that since the ene-diol compounds are very effective preservatives for the pyrazolidone developing agents and are highly soluble in water, it
is possible to prepare concentrated develop-er or groups such as alkyl preferably of 1 to 4 carcompositions more readily than in the case where a less soluble preservative such as sodium sulfite is used. A further characteristic of the ene-diolpyrazolidone developer compositions of the invention resides in the fact that the compositions behave as strong surface latent image developers as opposed to internal latent image developers, as long as they are free of silver halide solvents such as sodium sulfite. That is, developer compositions containing 3-pyrazolidone compounds have been described in the literature but invariably they have been compounded so as to con tain a silver halide solvent such as sodium sulfite as a preservative. In order to convert such a developer composition to a surface latent image developer, I have found it to be necessary to dispense with the silver halide solvent in the developer composition. However, as mentioned, the 3-pyrazolidone developers free of preservative are very unstable. When, according to my invention, the ene-diol compounds are incorporated into the 3-pyrazolidone developer compositions, the ene-diol compounds supply the required preservative effect and the surface latent image developer characteristics are maintained. Therefore, the fortuitous choice of 3-pyrazolidone compounds to accelerate the development rate of the ene-diol compounds has resulted in the latter compounds exerting a complementary preservative effect as well as providing a stable 3-pyrazolidone developer system which has surface latent image development characteristics and shows no tendency for physical development. For these reasons the developers of the invention are very useful in color development processes where a black-and-white developer is required.
An additional unexpected feature of the developers containing the 3-pyrazolidone and ascorbic acid compounds resides in the fact that similar developer compositions can be prepared, in which the pyrazolidone is replaced by a conventional developing agent, for example, containing a mixture of N-methyl-p-aminophenol and ascorbic acid, which compositions do not exhibit the mentioned development acceleration effect to any great extent.
The 3-pyrazolidone developer compositions of the invention containing the above ene-diol compounds can be readily converted to internal latent image developer compositions by merely adding a silver halide solvent such as sodium thiosulfate thereto. The resultant internal latent image developer composition, by virtue of the presence of one of the mentioned ene-diol compounds, likewise possesses excellent keeping properties even in the absence of the usual sulfite preservative.
The 3-pyrazolidone silver halide developing agents employed in the developer compositions together with ascorbic acid and its analogs, have the general formula in which the R groups each represent various substituents such as hydrogen, alkyl or aryl groups, for example, R1 can be hydrogen or a group such as alkyl preferably containing from 1 to 4 carbon atoms, or an aryl group of the benzene or naphthalene series substituted or not, and R2, R3, R4 and R5 can be hydrogen atoms,
bon atoms or aryl such as phenyl.
The following compounds are representative of 3-pyrazolid0ne silver halide developing agents which are useful in the developer compositions of the invention:
cocoacncnyswrog- 14. 1-phenyl-4,4-dimethyl-3-pyrazo1idone 15. 1 m aminophenyl 4 methyl 4 propyl- S-pyrazolidone 16. 1 o chlorophenyl 4 methyl 4 ethyl- S-pyrazolidone 17. 1 m acetamidophenyl 4,4 diethyl 3- pyrazolidone 18. 1 (p 3 hydroxyethylphenyl) 4,4 dimethyl-3-pyrazolidone 19. 1 p hydroxyphenyl 4,4 dimethyl 3- pyrazolidone 2'0. 1 p methoxyphenyl 4,4 diethyl 3- pyrazolidone 21. 1-p-tolyl-4,4-dimethyl-3-pyrazolidone 22. 1 (7 hydroxy 2 naphthyl) 4 methyl- 4-n-propy1-3-pyrazolidone 23. 1-p-diphenyl-4,4-dimethyl-3pyrazolidone 24. 1- (p-p-hydroxyethylphenyl) -3-pyrazolidone 25. 1-o-tolyl-3-pyrazolidone 26. 1o-tolyl-4,4-dimethyl-3-pyrazolidone The 4,4-dialkyl-3-pyrazolidone compounds 13 to 23 and 26 above are particularly efiicacious for use in the developer compositions of my invention inasmuch as they are more active developing agents than are compounds 1 to 12 which contain a single substituent or only hydrogen atoms in the 4-position of the pyrazolidone nucleus. The 4,4-dialkyl-3-pyrazolidone compounds are described and claimed in the Allen et al. U. S. patent application Serial No. 372,148 filed concurrently herewith. The w-hydroxyalkyl-3-pyrazolidones, for example, compounds iminoreductone derivative such as p-aminobenzoic acid reductone, mand p-aminosalicylic acid reductone and sulfanilic acid reductone are similar in structure to the imino ascorbic acid compounds and their use in developer compositions is disclosed and claimed in the Henn and Reynolds U. S. patent application Serial No. 372,168 filed concurrently herewith.
Example 1 The striking superadditivity obtained by combining the pyrazolidones and ene-diols, is shown in the following table. It is seen that the individual agents develop only weakly, but that when combined, they develop vigorously, producing images of high density.
These formulas all contained 25 grams of sodium sulfite and 25 grams of monohydrated sodium carbonate per liter, in addition to the indicated developing agents. In each case the pH of the formula was adjusted to 10.0 with acetic acid, to bring all solutions under parallel conditions.
The formulas compare the activity of the enediol ascorbic acid alone at an 0.02 molar concentration (3.5 grams per liter), of the pyrazolidone by itself, at 0.0025 molar concentration (0.4 to 0.5 gram per liter), and combinations of the agents in these concentrations. The activity was tested with a fine grain positive film, given a step wedge exposure and developed for a series of times at 68 F. and with high agitation.
18 and 24 above, are also especially useful in concentrated formulas, in replenishers and in the presence of high salt concentrations where their increased solubility enables obtaining and holding adequate amounts of the pyrazolidone compound in solution. The compounds are described and claimed in the Allent et a1. U. S. patent application Serial No. 372,148 filed concurrently herewith and the Reynolds and Tinker U. S. patent application Serial No. 372,167 filed concurrently.
The ene-diol compounds imino-d-glucoascorbic acid above obtained from d-glucose (J. Chem. Soc. 1934, p. 1194) is representative of a number of ene-diol compounds containing the iminoascorbic acid group derived from sugars. The compound is of particular value in my invention since its development rate is markedly accelerated by the 3-pyrazolidone silver halide developing agents, particularly l-phenyl-3-pyrazolidone. The other ene-diol compounds containing the imino group can be prepared by the methods of the reference immediately above from, for example, erythrose, galla-ctose, sorbose, mannose, maltose, and lactose and are likewise useful in the 3-pyrazolidone developer compositions where the latter compounds appreciably accelerate the development rate of the ene-diol compounds.
As will be apparent above, the
Example 2 The following developer compositions are particularly suitable as negative developers for color films:
(1) Without sulfite: Grams/liter Sodium hexametaphosphate 0.5 Potassium bromide 1.0 Sodium carbonate monohydrate 25.0 Potassium iodide 0.002 l-phenyl-3-pyrazolidone 1.0 Imino-d-glucoascorbic acid 12.5 1-phenyl-5-mercapto tetrazole 0.01 Water to make 1.0 liter (2) With sulfite: Grams/liter Sodium hexametaphosphate 0.5 Sodium sulfite 40.0 Sodium carbonate monohydrate 25.0 Potassium bromide 1.0 Potassium iodide 0.002 l-phenyl-3-pyrazolidone 1.0 Imino-d-glucoascorbic acid 12. 1-phenyl-5-mercapto tetrazole 0.01
Water to make 1.0 liter The developers of this example can be used in any of the well-known processes of color development Where a black-and-white developer is required. The developers are especially useful in 7 mixed grain color processes employing films such as disclosed in Mannes et a1. U. S. Patent 2,388,856 or in the Carroll et a1. U. S. Patent 2,614,925, October 21, 1952, wherein, for example, is shown a two-layer film, one layer containing blue-sensitive silver halide, the other containin a mixture of green and red-sensitive silver halide grains. When the developers immediately above are used in the color process of the patents as the negative developer for such a film it is observed, particularly with the Formula 1 free of sulfite, that physical development effects are minimized with the result that clean highlights free of stain are obtained and the color developed images have increased saturation because of decreased physical development in the negative developer of the invention.
Results similar to those of the above examples are obtained when developer compositions, containing or free of silver halide solvents, are prepared from mixtures of at least one of the indicated 3-pyrazolidone compounds and at least one of the iminoascorbic acid compounds. The enediol-pyrazolidone developer composition of the above example exhibits internal latent image development characteristics particularly by virtue of the presence of the silver halide solvent. Particularly valuable developer compositions in addition to that exemplified above, are those containing imino-d-glucoascorbic acid and either l-phenyl-B-pyrazolidone or a l-tolyl-3-pyrazolidone such as l-p-tolyl-3-pyrazolidone or l-ptolyl-4A-dimethyl-3-p-yrazolidone or a l-(p-flhydroxyalkylphenyl) 4,4 dialkyl 3 pyrazolidone such as 1-(p-c-hydroxyethylphenyl)- 4,4-dimethyl-3pyrazolidone, or a 1-(p-B-w-hY- droxyalkylphenyl) -3-pyrazolidone' such as 1- (pfl-hydroxyethylphenyl) -3-pyrazolidone.
It will be understood that my invention as specified by the claims hereinafter, includes the mentioned developer compositions in either the liquid form exemplified above, or in the dry powder form as packaged developer formulas suitable for dissolving in water to form a liquid developer. Such dry compositions include the mentioned 3-pyrazolidone compounds, the ene-diol compound, and alkaline material such as sodium carbonate, caustic alkali or sodium metaborate.
What I claim is:
1. A photographic developer composition comprising an alkaline material, a 3-pyrazolidone silver halide developing agent and a compound havin the general structure RCH2(OHOH),.-1CHC:CC=NH wherein R represents a hydroxyl group when n represents a positive integer from 1 to 4 and R represents a hydrogen atom when n represents a positive integer from 2 to 4.
2. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and a compound having the general structure prising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and a compound having the struc- 4. A photographic developer composition comprising an aqueous alkaline solution containin a mixture of a 3-pyrazolidone silver halide developing agent and a compound having the structure 5. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and a compound having the structure 6. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of a B-pyrazolidone silver halide developing agent and a compound having the structure 7. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and imino-d-glucoascorbic acid.
8. The developer composition of claim 2 wherein the designated 3-pyrazolidone is 1-phenyl3- pyrazolidone.
9. The developer composition of claim 2 wherein the designated B-pyrazolidone is a 4,4-dialkyl- 3-pyrazolidone.
10. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 1-tolyl-3-pyrazolidone and iminod-glucoascorbic acid.
11. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-p-tolyl-4,4-dimethyl-3-pyrazolidone and imino-d-glucoascorbic acid.
12. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-phenyl-4A-dimethyl-3-pyrazolidone and. imino-d-glucoascorbic acid.
13. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-(p-/3-hydroxyethy1phenyl-3-pyrazolidone and imino-d-glucoascorbic acid.
14. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-(p-B-hydroxyethylphenyl)-4,4-dimethyl 3 pyrazolidone and imino d glucoascorbic acid.
15. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-phenyl-3-pyrazolidone and iminod-glucoascorbic acid.
16. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-p-tolyl-3-pyrazolidone and iminod-glucoascorbic acid.
17. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and a compound of the class consisting of imino-l-ascorbic acid, imino-d-ascorbic acid, imino-l-erythroascorbic acid, imino-l-glucoascorbic acid, imino-d-glucoascorbic acid, iminod gelactoascorbic acid, imino l guloascorbic acid, imino-l-alloascorbic acid, imino-d-glucoheptoascorbic acid, imino 1 rhamnoascorbic acid, imino-l-fucoascorbic acid, imino-l-araboascorbic acid, imino-sorboascorbic acid, iminoisoascorbic acid, imino-fi-desoxy-l-ascorbie acid,
10 imino-w-lactoascorbic acid and imino-maltoascorbic acid.
18. The developer composition designated in claim 1 which has been adapted to the development of the internal latent image of exposed silver halide by the addition of a silver halide solvent.
19. The developer composition designated in claim 1 which is free of a silver halide solvent.
No references cited.

Claims (1)

1. A PHOTOGRAPHIC DEVELOPER COMPOSITION COMPRISING AN ALKALINE MATERIAL, A 3-PYRAZOLIDONE SILVER HALIDE DEVELOPING AGENT AND A COMPOUND HAVING THE GENERAL STRUCTURE
US372166A 1953-08-03 1953-08-03 Photographic developer composition Expired - Lifetime US2688548A (en)

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US371948A US2751297A (en) 1953-08-03 1953-08-03 Photographic emulsion layer containing a 3-pyrazolidone
US372168A US2691589A (en) 1953-08-03 1953-08-03 Photographic developer compositions
US372166A US2688548A (en) 1953-08-03 1953-08-03 Photographic developer composition

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US2875048A (en) * 1957-09-30 1959-02-24 Eastman Kodak Co Combined photographic developing and stabilizing solution
US3330661A (en) * 1962-11-13 1967-07-11 Eastman Kodak Co Photographic development precursors
US3649280A (en) * 1968-11-29 1972-03-14 Eastman Kodak Co Photographic elements and compositions
US3942985A (en) * 1973-08-24 1976-03-09 Minnesota Mining And Manufacturing Company High contrast, rapid access, air stable, regenerable iron chelate developer solutions
US4038080A (en) * 1972-09-21 1977-07-26 Minnesota Mining And Manufacturing Company Fix and bleach-fix bath desilvering
EP0508691A1 (en) * 1991-04-10 1992-10-14 Audenried W. Knapp Gluconic-acid based developer composition
US5236816A (en) * 1992-04-10 1993-08-17 Eastman Kodak Company Photographic developing solution and use thereof in the high contrast development of nucleated photographic elements
US5264323A (en) * 1992-04-10 1993-11-23 Eastman Kodak Company Photographic developing solution and use thereof in the high contrast development of nucleated photographic elements
US5273865A (en) * 1990-04-24 1993-12-28 Minnesota Mining And Manufacturing Company Photographic color developing composition and method for processing a silver halide color photographic element
US5384232A (en) * 1991-12-02 1995-01-24 E. I. Du Pont De Nemours And Company Process for rapid access development of silver halide films using pyridinium as development accelerators
US5384233A (en) * 1992-06-15 1995-01-24 Konica Corporation Chemicals kit including a container formed of multilayer film, for processing photographic light-sensitive materials
US5399457A (en) * 1993-10-15 1995-03-21 Minnesota Mining And Manufacturing Company Process for reducing sludge in diffusion transfer printing plates
US5503965A (en) * 1993-09-27 1996-04-02 Fuji Photo Film Co., Ltd. Process for development of black-and-white- silver halide photographic material
EP0774687A1 (en) * 1995-10-30 1997-05-21 Konica Corporation Solid processing composition and method for processing silver halide photographic light-sensitive material
US5648205A (en) * 1994-10-13 1997-07-15 Fuji Photo Film Co., Ltd. Processing method for silver halide photographic material
EP0785467A1 (en) * 1996-01-16 1997-07-23 Konica Corporation Solid processing composition for silver halide photographic light sensitive material
US5766830A (en) * 1994-09-09 1998-06-16 Konica Corporation Photographic processing method for processing a silver halide photographic light-sensitive material
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US5798204A (en) * 1994-07-26 1998-08-25 Fuji Photo Film Co., Ltd. Development processing method of ultrahigh-contrast black-and-white silver halide photographic material
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Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2875048A (en) * 1957-09-30 1959-02-24 Eastman Kodak Co Combined photographic developing and stabilizing solution
US3330661A (en) * 1962-11-13 1967-07-11 Eastman Kodak Co Photographic development precursors
US3649280A (en) * 1968-11-29 1972-03-14 Eastman Kodak Co Photographic elements and compositions
US4038080A (en) * 1972-09-21 1977-07-26 Minnesota Mining And Manufacturing Company Fix and bleach-fix bath desilvering
US3942985A (en) * 1973-08-24 1976-03-09 Minnesota Mining And Manufacturing Company High contrast, rapid access, air stable, regenerable iron chelate developer solutions
US5273865A (en) * 1990-04-24 1993-12-28 Minnesota Mining And Manufacturing Company Photographic color developing composition and method for processing a silver halide color photographic element
EP0508691A1 (en) * 1991-04-10 1992-10-14 Audenried W. Knapp Gluconic-acid based developer composition
US5384232A (en) * 1991-12-02 1995-01-24 E. I. Du Pont De Nemours And Company Process for rapid access development of silver halide films using pyridinium as development accelerators
US5236816A (en) * 1992-04-10 1993-08-17 Eastman Kodak Company Photographic developing solution and use thereof in the high contrast development of nucleated photographic elements
US5264323A (en) * 1992-04-10 1993-11-23 Eastman Kodak Company Photographic developing solution and use thereof in the high contrast development of nucleated photographic elements
US5384233A (en) * 1992-06-15 1995-01-24 Konica Corporation Chemicals kit including a container formed of multilayer film, for processing photographic light-sensitive materials
US5503965A (en) * 1993-09-27 1996-04-02 Fuji Photo Film Co., Ltd. Process for development of black-and-white- silver halide photographic material
EP0649062A2 (en) * 1993-10-15 1995-04-19 Minnesota Mining And Manufacturing Company Process for reducing sludge in diffusion transfer printing plates
EP0649062A3 (en) * 1993-10-15 1995-08-16 Minnesota Mining & Mfg Process for reducing sludge in diffusion transfer printing plates.
US5399457A (en) * 1993-10-15 1995-03-21 Minnesota Mining And Manufacturing Company Process for reducing sludge in diffusion transfer printing plates
US5824458A (en) * 1994-02-28 1998-10-20 Fuji Photo Film Co., Ltd. Developer and fixing solution for silver halide photographic material and processing method using the same
US5798204A (en) * 1994-07-26 1998-08-25 Fuji Photo Film Co., Ltd. Development processing method of ultrahigh-contrast black-and-white silver halide photographic material
US5766830A (en) * 1994-09-09 1998-06-16 Konica Corporation Photographic processing method for processing a silver halide photographic light-sensitive material
US5648205A (en) * 1994-10-13 1997-07-15 Fuji Photo Film Co., Ltd. Processing method for silver halide photographic material
EP0774687A1 (en) * 1995-10-30 1997-05-21 Konica Corporation Solid processing composition and method for processing silver halide photographic light-sensitive material
US5851742A (en) * 1995-10-30 1998-12-22 Konica Corporation Solid processing composition and method for processing silver halide photographic light-sensitive material
EP0785467A1 (en) * 1996-01-16 1997-07-23 Konica Corporation Solid processing composition for silver halide photographic light sensitive material
US5834171A (en) * 1996-01-16 1998-11-10 Konica Corporation Solid processing composition for silver halide photographic light sensitive material
EP0848287A1 (en) 1996-12-11 1998-06-17 Imation Corp. Photographic silver halide developer composition and process for forming photographic silver images
US5998110A (en) * 1996-12-11 1999-12-07 Ferrania S.P.A. Photographic silver halide developer composition and process for forming photographic silver images

Also Published As

Publication number Publication date
US2751297A (en) 1956-06-19
GB767704A (en) 1957-02-06
BE530883A (en) 1957-10-25
FR1106813A (en) 1955-12-23
FR1109575A (en) 1956-01-31
BE530887A (en) 1957-10-25
FR1106144A (en) 1955-12-12
GB767699A (en) 1957-02-06
US2691589A (en) 1954-10-12

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