US3617273A - Competing color developer process and composition - Google Patents

Competing color developer process and composition Download PDF

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US3617273A
US3617273A US835224A US3617273DA US3617273A US 3617273 A US3617273 A US 3617273A US 835224 A US835224 A US 835224A US 3617273D A US3617273D A US 3617273DA US 3617273 A US3617273 A US 3617273A
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hydroxyanilinomethyl
color
developing agent
pyridine
competing
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Atsuaki Arai
Mitsugu Tanaka
Haruhiko Iwano
Isao Shimamura
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
    • 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
    • G03C5/3021—Developers with oxydisable hydroxyl or amine groups linked to an aromatic ring

Definitions

  • X is hydrogen, alkyl, hydroxylalkyl, phenyl or halogen
  • Y is a substituted or unsubstituted N, S or 0 containing heterocyclic ring, and process for the use thereof.
  • the present invention relates to developer compositions for color photography, and more particularly, to a color-forming developer composition containing a novel water soluble competing developing agent.
  • reversal color photographic light-sensitive elements which are to be developed in a coupler-containing developer are, after exposure, subjected to black and white development, and then, after being subject to a reversal exposure, processed in a color developer which contains couplers.
  • This type of element usually has multiple emulsion layers which include three selective light-sensitive emulsion layers.
  • a sup port carries the following layers: 1) a lowermost red-sensitive emulsion layer, 2) a green-sensitive emulsion layer, 3) a yellow filter layer, 4) a blue-sensitive emulsion layer, and 5) an upper protective layer (formed on the support in the order given).
  • the color-forming developer used for developing such reversal color photographic Iigh'tsensitive elements usually comprises: 1) an alkaline aqueous solution containing a pphenylenediamine-type developing agent which has at least one primary amino group, 2) a color-forming coupler, and 3) additives, such as an alkali metal sulfite, e.g. sodium sultite, an alkali metal sulfite, e.g. sodium sultite, an alkali metal sulfite, e.g. sodium sultite, an alkali metal sulfite, e.g. sodium sultite, an alkali metal sulfite, e.g. sodium sultite, an alkali metal sulfite, e.g. sodium sultite, an alkali metal sulfite, e.g. sodium sultite, an alkali metal sulfite
  • I alkali metal bromide e.g. sodium bromide, an alkali metal iodide, etc.
  • color-forming developer compositions contain a phenolic or naphtholic coupler as a cyan dyeformer, a pyrazolone coupler as a magenta dye-former, and an open-chain ketomethylene coupler as a yellow dye-former.
  • a competing developing agent When subjecting a reversal color photographic element to cyan development using a color-forming developer containing a color former or coupler, to suppress the formation of cyan fogs in the green-sensitive and the blue-sensitive emulsion layers, a competing developing agent is incorporated into the cyan developer.
  • N-benzyl-p-aminophenol is widely used as one such "competing developing agent.” It is generally known that the competing developing agent will reduce an oxidized color developing agent to the state of the original developing agent, and will reduce an exposed silver halide into metallic silver. The competing developing agent will thus contribute to suppressing cyan contamination in the blue-sensitive emulsion layer and, in particular, in the green-sensitive emulsion layer, thus yielding a correct red reproduction of the subject photographed. This is due to the fact that the competing developing agent and the color developing agent will both compete for reaction with the exposed silver halide.
  • a competing developing agent to be employed in photographic processing must be capable of increasing the red contrast by removing cyan contamination, and also must be capable of increasing the sensitivity of the red-sensitive emulsion layer. Furthermore, the competing developing agent must not reduce the maximum density of the red-sensitive emulsion layer, must not reduce the high degree of clarity of the cyan color developing agent, and must not reduce the photographic properties of the emulsion without also reducing the stability of the cyan developer.
  • Another object is to provide a color developer composition containing a novel competing developing agent which will yield a high purity red reproduction, and which will also increase the sensitivity of a red-sensitive emulsion layer.
  • a still further object is to provide a competing developing agent which will not reduce the maximum density of a red-sensitive emulsion layer, will not reduce the clarity of a cyan color developing agent and which will not reduce the photographic properties of the emulsion, such as reversal sensitivity, red purity, and the red filter density-blue filter density ratio, without reducing the stability of the cyan developer.
  • the water-soluble competing developing agents of the present inventign include those represented by the formula:
  • X represents a hydrogen atom, an alkyl group having from one to four carbon atoms such as methyl, ethyl, propyl,
  • Y represents a heterocyclic ring having at least one N, S or 0 atom, such as pyrrole, pyrazole, imidazole, pyridine, pyrimidine, indole, thiophene, furan, oxazole, etc.
  • the heterocyclic ring may be substituted by an alkyl group having from one to four carbon atoms or a benzyl group.
  • the color developer composition of the present invention comprises, therefore, (A) a primary aromatic amino developing agent, (8) a color-forming coupler, (C) an alkali, and (D) a water-soluble competing developing agent having the formula (I).
  • the competing developing agents of this invention are used to advantage in color developer solutions for processing color photographic elements in instances where it is desirable to control color'contrast, fog, etc.
  • the competing developing agents of the present invention are unexpectedly better than some known competing developing agents and are valuable for use in color photographic processing.
  • a cyan color developer which contains a p-phenylenediamine type color developing agent
  • the cyan .developer used in this invention exhibits an excellent cyan fog preventing property and an excellent red reproduction of the original.
  • the color developer containing the competing developing agent of this invention shows better stability or gives less degradation of its properties and provides images having good photographic characteristics when the developer is stored or repeatedly used for a long period of time.
  • the concentration of the competing developing agents of this invention will vary, depending upon the type and concentration of the color developing agent and coupler used in the color developer, and will also vary with the pH of the color developer. However, in general, a concentration of 0.0l-5.0 g./liter of developer is preferably employed. Further, it has been found that the most effective concentration utilized is about 0. l-l .0 g./liter.
  • the competing developing agents of this invention are commonly used in the form of salts, such as the hydrochloride, which are more stable than the free amine.
  • the competing developing agents of this invention can be effectively used in any cyan color developer, magenta color developer, or yellow color developer, but it is most effectively used in a cyan color developer.
  • the color developing agent used in the color developer composition of this invention is generally a p-phenylenediamine derivative, such as: N,N-diethyl-p-phenylenediamine sulfite; N,N-diethyl-3-methyl-p-phenylenediamine hydrochloride; 4-amino-3-methyl-N-ethyl-N-methanesulfonamido ethylaniline sulfate; 4-amino-3-methyl-N-ethyl-N- hydroxyethyl-aniline sulfate; N-ethyl-N-hydroxyethyl-p-phenylenediamine sulfate, etc.
  • the p-aminophenols and their substituted materials may also be used.
  • color formers used in this invention there are: 2,4-dichloro-l-naphthol; 2,4-dich1oro-5 tolylsulfonamido-l-naphthol; l-oxy-2-benzylnaphthamide; 2,6-dibromo-l,S-dihydroxynaphthalene; benzoylacetanilide; O-benzoyl-4-(p-toluenesulfonamido)acetanilide; 1-phenyl-3- (m-nitrobenzoyl-amino)--pyrazolone; and cyanoacetyl coumaron.
  • other color formers which are conventionally utilized, may be employed in this invention.
  • the free amines were converted to the salts such as the sulfate or the hydrochloride by the known procedure in the art.
  • a multilayer color photographic film was formed of the following layers (in the order given) on a photographic film support: (1) a red-sensitive gelatino silver iodo-bromide emulsion layer, (2) a green-sensitive gelatino silver iodobromide emulsion layer, (3) a blue-absorbing yellow filter layer comprising colloidal silver, and (4) a blue-sensitive gelatino silver iodobromide emulsion layer.
  • This film was exposed by means of a sensitometer, and subjected to the following processes:
  • compositions of the processing baths used in the above processes are as follows:
  • Magenta Color Developer Sodium sulfite 5.0 g. 2-Amino-5-N.N-diethylaminotoluene hydrochloride 2.0 g. Potassium bromide 0.8 g. l-phenyl-3'(m-nitrobenzoylamino)-5- pyrozolone l.4 g. Sodium hydroxide 2.0 g. n-Butylamine 5.0 ml. Water to make I000 ml.
  • the competing developing agents shown inthe following table were (individually) added to the cyan color developer, and the effect of the competing developing agents on the photographic properties of the film was measured.
  • the photographic properties of the processed film are shown in the following table, with each of the three competing developing agents, in which: (I) the reversal sensitivity is shown by the inverse logarithm of the amount of exposure at which the coupling density obtained corresponds to L0; (2) the purity of the red color reproduction is shown by the ratio of the red filter density to the green filter density (D,/D,,) of a portion of the film exposed to red light (called red patch); and (3) the ratio of the red filter density to the blue filter density (D /D of said portion is also shown.
  • the ratio D,/D,, or D,/D is a value which illustrates the color purity of a reproduced color when a red object is reproduced in a color photograph, and the smaller that this value is, the better the reproduction.
  • EXAMPLE ll Using the same basic procedures as in example l. a cyan color development was carried out. After being washed with water for eight minutes after the cyan development, the cyandeveloped color film was subjected to bleaching, washing and fixing. as in example 1. to provide cyan-colored images. in this case, the photographic properties of the color photographs which were improved by the competing developing agent of this invention were measured. The results thereof are shown in the following table.
  • the reversal sensitivity (A) relates to the red-sensitive emulsion layer
  • the cyan contamination density (B) is shown by the sum of the cyan coupling density in the portion of the green-sensitive emulsion layer exposed to red light and the cyan coupling density in the portion of the blue-sensitive emulsion layer exposed to red light.
  • These two light sensitive emulsion layers are ones which will not be developed to any extent in a cyan color development, and, hence, cyan coupling these portions causes undesirable developing fogs in the green-sensitive emulsion layer to be magenta coupled and undesirable fogs in the blue-sensitive emulsion layer to be yellow coupled.
  • the cyan coupling causes color turbidity, which results in a degrading of the quality of the color photographic image.
  • Cyan Color Developer The photographic properties obtained by adding the competing developing agent of this invention to the cyan developer were compared with those obtained by adding.
  • a conventional competing developing agent N- benzyl-p-aminophenol hydrochloride.
  • the amount and the type of competing developing agent used are shown below:
  • the competing developing agent of this invention illustrated an excellent effect during this experiment, when compared with the known competing developing agent.
  • a color developer composition comprising (1) a primary aromatic amino developing agent, (2) a color-forming coupler, (3) an alkali, and (4alkali a water-soluble competing developing agent having the formula:
  • X represents a member selected from the class consisting of a hydrogen atom, an alkyl group having from one to four carbon atoms, a hydroxyalkyl group having from one to four carbon atoms, a phenyl group and a halogen atom
  • Y represents a substituted or unsubstituted heterocyclic ring having at least one N, S or O atom, said heterocyclic ring, when substituted, being substituted with a member selected from the class consisting of an alkyl group having from one to four carbon atoms, and a benzyl group.
  • composition of claim 1 wherein said composition additionally contains a member selected from the class consisting of an alkali metal bromide, an alkali metal sulfite, and alkali metal iodide.
  • coupler is selected from the class consisting of phenolic couplers, naphtholic couplers, pyrazolone couplers, coumarone couplers and the open-chain ketomethylene couplers.
  • HOG-NH-GH -Y wherein X represents a member selected from the class consisting of a hydrogen atom, an alkyl group having from one to four carbon atoms, a hydroxyalkyl group having from one to four carbon atoms, a phenyl group and a halogen atom and Y represents a substituted or unsubstituted heterocyclic ring having at least one N, S or O atom, said heterocyclic ring, when substituted, being substituted with a member selected from the class consisting of an alkyl group having from one to four carbon atoms and a benzyl group.
  • one of said baths is a yellow developer, and contains B-(p-hydroxyanilinomethyl)pyridine as the competing develo inga ent.
  • one of said baths is a magenta developer
  • conwater-soluble competing developing agent is selected from the class consisting of B-(p-hydroxyanilinomethyl)-pyridine a-(phydroxyanilinomethyl)pyridine, y-(p-hydroxyanilinomethyl)pyridine, a-(p-hydroxyanilinomethyl)furan, B-(3-methyl-4-hydroxyanilinomethyl)pyridine, [3-(3-phenyl-4 -hydroxyanilinomethyl)furan, a-(p-hydroxyanilinomethyl) thiophene, 2-(p-hydroxyanilinomethyl)-5-methylthiophene, l-benzyl-3-(p-hydroxyanilinomethyl)indole, a-(3chloro-4- hydroxyanilinomethyl)furan and a-(3-methyl-4-hydroxyanilinomethyl)furan said competing developing agent being present in an amount of 0.01 to 5.0 g./liter of the
  • a composition for preparing a color developer solution comprising (1) a primary aromatic amino developing agent, and (2) a water-soluble competing developing agent having the formula:
  • X represents a member selected from the class consisting of a hydrogen atom, an alkyl group having from one to four carbon atoms, a hydroxyalkyl group having from one to four carbon atoms, a phenyl group and a halogen atom
  • Y represents a substituted or unsubstituted heterocyclic ring having at least one N, S or O atom, said heterocyclic ring, when substituted, being substituted with a member selected from the class consisting of an alkyl group having from one to four carbon atoms and a benzyl group.
  • composition of claim 10 wherein said competing developing agent is selected from the class consisting of B-(phydroxyanilinomethyl)pyridine, a-(p-hydroxyanilinomethyl)pyridine, -y-(p-hydroxyanilinomethyl)pyridine, a-(p-hydroxyanilinomethyl)furan, B-(3-methyl-4-hydroxyanilinomethyl)pyridine, B-(3-phenyl-4 -hydroxyanilinomethyl)furan, a-(phydroxyanilinomethyl)thiophene, 2-(p-hydroxyanilinomethyl)-5- methylthiophene, l-benzyl-3-(p-hydroxyanilinomethyl)indole, a-(3-chloro-4-hydroxyanilinomethyl)furan and a-(3- methyl-4-hydroxyanilinomethyl)furan.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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Abstract

A novel competing color-developing agent having the formula:

WHEREIN X is hydrogen, alkyl, hydroxylalkyl, phenyl or halogen, and Y is a substituted or unsubstituted N, S or O containing heterocyclic ring, and process for the use thereof.

Description

United States Patent Inventors Atsuaki Aral;
Mltsugu Tanaka; l-laruhlko lwano; lsao Shimamura, all of Kanagawa, Japan Appl. No. 835,224 Filed June 20, 1969 Patented Nov. 2, 1971 Assignee Fuji Photo Film Co., Ltd.
Kanagawa, Japan Priority June 20, 1968 Japan 43/4284 1 COMPETING COLOR DEVELOPER PROCESS AND COMPOSITION 11 Claims, No Drawings US. Cl 96/22, 96/55, 96/59 Int. Cl E03c 7/16,
E03c 7/00. 1503c 5/50 501 Field of Search 96/22, 55, 66, 59
[ 56] References Cited UNITED STATES PATENTS 3,141,771 7/l964 Bard et al. 96/22 3,300,305 1/1967 Pesch et al 96/22 Primary Examiner- Norm an G. Torchin Assistant Examiner-Mary F. Kelley AttorneySughrue, Rothwell, Mion, Zinn & Macpeak ABSTRACT: A novel competing color-developing agent having the formula:
wherein X is hydrogen, alkyl, hydroxylalkyl, phenyl or halogen, and Y is a substituted or unsubstituted N, S or 0 containing heterocyclic ring, and process for the use thereof.
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to developer compositions for color photography, and more particularly, to a color-forming developer composition containing a novel water soluble competing developing agent.
2. Summary of the Prior Art In general, reversal color photographic light-sensitive elements which are to be developed in a coupler-containing developer are, after exposure, subjected to black and white development, and then, after being subject to a reversal exposure, processed in a color developer which contains couplers. This type of element usually has multiple emulsion layers which include three selective light-sensitive emulsion layers. For example, in one such color photographic element, a sup port carries the following layers: 1) a lowermost red-sensitive emulsion layer, 2) a green-sensitive emulsion layer, 3) a yellow filter layer, 4) a blue-sensitive emulsion layer, and 5) an upper protective layer (formed on the support in the order given).
The color-forming developer used for developing such reversal color photographic Iigh'tsensitive elements usually comprises: 1) an alkaline aqueous solution containing a pphenylenediamine-type developing agent which has at least one primary amino group, 2) a color-forming coupler, and 3) additives, such as an alkali metal sulfite, e.g. sodium sultite, an
I alkali metal bromide, e.g. sodium bromide, an alkali metal iodide, etc. Usually, such color-forming developer compositions contain a phenolic or naphtholic coupler as a cyan dyeformer, a pyrazolone coupler as a magenta dye-former, and an open-chain ketomethylene coupler as a yellow dye-former.
When subjecting a reversal color photographic element to cyan development using a color-forming developer containing a color former or coupler, to suppress the formation of cyan fogs in the green-sensitive and the blue-sensitive emulsion layers, a competing developing agent is incorporated into the cyan developer. N-benzyl-p-aminophenol is widely used as one such "competing developing agent." It is generally known that the competing developing agent will reduce an oxidized color developing agent to the state of the original developing agent, and will reduce an exposed silver halide into metallic silver. The competing developing agent will thus contribute to suppressing cyan contamination in the blue-sensitive emulsion layer and, in particular, in the green-sensitive emulsion layer, thus yielding a correct red reproduction of the subject photographed. This is due to the fact that the competing developing agent and the color developing agent will both compete for reaction with the exposed silver halide.
A competing developing agent to be employed in photographic processing, must be capable of increasing the red contrast by removing cyan contamination, and also must be capable of increasing the sensitivity of the red-sensitive emulsion layer. Furthermore, the competing developing agent must not reduce the maximum density of the red-sensitive emulsion layer, must not reduce the high degree of clarity of the cyan color developing agent, and must not reduce the photographic properties of the emulsion without also reducing the stability of the cyan developer.
However, to date, when a cohventional color developer containing a competing developing agent for use in color reversal processing has been employed, the red contrast and the fog prevention have been insufficient. In particular, sensitivity has been greatly reduced as time passes, and there has been a marked increase in fog formation, thus yielding unsatisfactory results. Cyan contamination in the green-sensitive emulsion layer becomes greatly increased with the use of a conventional developer and it becomes necessary to increase the amount of developer needed, which greatly lowers the utility of the color developing process and leads to increased expense.
SUMMARY OF THE INVENTION It is an object of the present invention to provide a developer composition which contains a novel competing 5 developing agent which will suppress the formation of fogs in photographic emulsion layers, and most especially will suppress the formation of cyan fogs in green-sensitive and bluesensitive emulsion layers.
Another object is to provide a color developer composition containing a novel competing developing agent which will yield a high purity red reproduction, and which will also increase the sensitivity of a red-sensitive emulsion layer.
A still further object is to provide a competing developing agent which will not reduce the maximum density of a red-sensitive emulsion layer, will not reduce the clarity of a cyan color developing agent and which will not reduce the photographic properties of the emulsion, such as reversal sensitivity, red purity, and the red filter density-blue filter density ratio, without reducing the stability of the cyan developer.
The aforesaid objects of the present invention are accomplished by using certain substituted p-aminophenols as competin'g developing agents in color developer solutions.
DESCRIPTION OF THE INVENTION The water-soluble competing developing agents of the present inventign include those represented by the formula:
wherein X represents a hydrogen atom, an alkyl group having from one to four carbon atoms such as methyl, ethyl, propyl,
butyl, a hydroxyalkyl group having from one to four carbon atoms such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, a phenyl group, or a halogen atom, and Y represents a heterocyclic ring having at least one N, S or 0 atom, such as pyrrole, pyrazole, imidazole, pyridine, pyrimidine, indole, thiophene, furan, oxazole, etc. The heterocyclic ring may be substituted by an alkyl group having from one to four carbon atoms or a benzyl group.
The color developer composition of the present invention comprises, therefore, (A) a primary aromatic amino developing agent, (8) a color-forming coupler, (C) an alkali, and (D) a water-soluble competing developing agent having the formula (I).
The competing developing agents of this invention are used to advantage in color developer solutions for processing color photographic elements in instances where it is desirable to control color'contrast, fog, etc. The competing developing agents of the present invention are unexpectedly better than some known competing developing agents and are valuable for use in color photographic processing. In particular, when the competing developing agents of the present invention are used in conjunction with a cyan color developer which contains a p-phenylenediamine type color developing agent, a
phenol or naphtholic cyan color-forming coupler, and an alkali, excellent results are obtained, as compared with the use of known competing developing agents in cyan color developers having the same composition. That is, the cyan .developer used in this invention exhibits an excellent cyan fog preventing property and an excellent red reproduction of the original. Furthermore, the color developer containing the competing developing agent of this invention shows better stability or gives less degradation of its properties and provides images having good photographic characteristics when the developer is stored or repeatedly used for a long period of time.
The following typical examples will serve to illustrate our competing developing agents but it is to be understood that our invention is not limited to these examples.
Compound 1 Compound 2 Compound 3 y-(p-hydroxyanilinomethyllpyridine Compound 4 B-l p-hydroxyanilinomethyl)pyridine a-( p-hydroxyanilinomethg'llpyridine u-( p-hydroxyanilinomethyl )luran Compound 5 B-(J -methyl-4- hydroxyanilinornethyl)pyridine Compound 6 fl-(3-phenyl-4- hydroxyanilinomethyl)furun Compound 7 a-(p-hydroxyanilinomethyl)thiophene Compound 8 2-(p-hydroxyanilinomethyl)-5- methylthiophene Compound 9 l -benzyl-3-(phydroxyanilinomethyl)indole Com ound l a-(3-chloro-4- hydroxyanilinomethyl)fursn Compound ll a-(J-methyl-A- hydroxyanilinomethyl )furan It is advantageous to include a compound, such as hydroxylamine sulfate. hydroxylamine hydrochloride, etc. in the aqueous solution of the color developer composition in order to extend the useful life of the developer especially during storage.
The concentration of the competing developing agents of this invention will vary, depending upon the type and concentration of the color developing agent and coupler used in the color developer, and will also vary with the pH of the color developer. However, in general, a concentration of 0.0l-5.0 g./liter of developer is preferably employed. Further, it has been found that the most effective concentration utilized is about 0. l-l .0 g./liter.
The competing developing agents of this invention are commonly used in the form of salts, such as the hydrochloride, which are more stable than the free amine.
The competing developing agents of this invention can be effectively used in any cyan color developer, magenta color developer, or yellow color developer, but it is most effectively used in a cyan color developer.
The color developing agent used in the color developer composition of this invention is generally a p-phenylenediamine derivative, such as: N,N-diethyl-p-phenylenediamine sulfite; N,N-diethyl-3-methyl-p-phenylenediamine hydrochloride; 4-amino-3-methyl-N-ethyl-N-methanesulfonamido ethylaniline sulfate; 4-amino-3-methyl-N-ethyl-N- hydroxyethyl-aniline sulfate; N-ethyl-N-hydroxyethyl-p-phenylenediamine sulfate, etc. The p-aminophenols and their substituted materials may also be used.
Moreover, illustrative of the color formers used in this invention, there are: 2,4-dichloro-l-naphthol; 2,4-dich1oro-5 tolylsulfonamido-l-naphthol; l-oxy-2-benzylnaphthamide; 2,6-dibromo-l,S-dihydroxynaphthalene; benzoylacetanilide; O-benzoyl-4-(p-toluenesulfonamido)acetanilide; 1-phenyl-3- (m-nitrobenzoyl-amino)--pyrazolone; and cyanoacetyl coumaron. However, other color formers, which are conventionally utilized, may be employed in this invention.
The preparation of the novel competing developing agents used in this invention may be illustrated by the examples shown below.
1. Preparation of fi-(p-hydroxyanilinomethyl) pyridine (Compound I). A mixture of 32.7 g. of p-aminophenol and 32.1 g. of nicotinic aldehyde was refluxed for 30 minutes in 500 ml. of ethanol. 50 g. of the Schiff base obtained was dissolved in 300 ml. of methanol, and, while stirring. l2.0 g. of sodium borohydride was added to this solution over a minute period at room temperature. The reaction mixture was poured into I000 ml. of ice water containing l7 ml. of acetic acid and the crystals that formed were separated, and recrystallized from benzene to yield 35 g. of colorless crystals ofCompound I having a melting pointof l35.5-l36.5C. The sulfate of Compound 1 crystallizes as colorless needles having a melting point of 228-240 C. (decomposes).
2. Preparation of a-(p-hydroxyanilinomethyl) pyridine (Compound 2). A Schiff base prepared by the reaction of2 l .9 g. of p-aminophenol with 21.5 g. of picolinic aldehyde in 400 ml. of ethanol was reduced with sodium borohydride as in the preparation of Compound l. The amine compound thus obtained was recrystallized from benzene to yield 25.5 g. of colorless plates of Compound 2 having a melting point of l54.5-l 56.5 C.
3. Preparation of 'y-(p-hydroxyanilinomethyl) pyridine (Compound 3). The amine was prepared by the same method as in the preparation of Compound l using I l g. of paminophenol and 10.8 g. of isonicotinic aldehyde as starting materials and was recrystallized from ethanol to yield 13 g. of colorless needles of Compound 3 having a melting point of 167-169 C.
Compounds 4 to ll were prepared in a manner similar to that of above examples. The properties of these compounds are as follows:
a-(p-hydroxyanilinomethyl)furan hydrochloride (Compound 4): Colorless needles recrystallized from diluted hydrochloric acid, m.p. l 30l40 C. (decomposed).
,B-(3-methyl-4-hydroxyanilinomethyl)pyridine (Compound 5): Colorless columns (recrystallized from benzene), m.p. l25.5-l27bL C.
[3-(3-phenyl-4-hydroxyanilinomethyl)furan (Compound 6): Colorless flakes (recrystallized from petroleum benzin), m.p. 101-102 C.
a-(p-hydroxyanilinomethyl)thiophene hydrochloride (Compound 7): Colorless needles (recrystallized from diluted hydrochloric acid), m.p. ISO-158 C. (decomposed).
2-(p-hydroxyanilinomethyl)-5-methylthiophene (Compound 8): Colorless needles (recrystallized from benzene), m.p. l30.5l32 C.
l-benzyl-3-(p-hydroxyanilinomethyl) indole (Compound 9): Colorless needles (recrystallized from ethanol), m.p. 132.5-134bL C.
a-(3-chloro-4-hydroxyanilinomethyl)furan (Compound 10): Colorless crystals (recrystallized from petroleum benzine), m.p. 79.580.5 C.
a-(3-methyl-4-hydroxyanilinomethyl)furan (Compound 11): Colorless recrystals (recrystallized from benzene), m.p. 103.5-104bL C.
The reduction of Schiff bases in the preparation of Compounds 1 to ll was carried out by using sodium borohydride in the above examples, but other known reductants such as, sodium hydroxide-zinc, hydrochloric acid-iron, etc. may be effectively used.
In the above examples, the free amines were converted to the salts such as the sulfate or the hydrochloride by the known procedure in the art.
The following examples show that a color developer containing the competing developing agent of this invention is quite superior to color developers which contain conventional competing developing agents.
EXAMPLE I A multilayer color photographic film was formed of the following layers (in the order given) on a photographic film support: (1) a red-sensitive gelatino silver iodo-bromide emulsion layer, (2) a green-sensitive gelatino silver iodobromide emulsion layer, (3) a blue-absorbing yellow filter layer comprising colloidal silver, and (4) a blue-sensitive gelatino silver iodobromide emulsion layer. This film was exposed by means of a sensitometer, and subjected to the following processes:
Second black and white development The compositions of the processing baths used in the above processes are as follows:
Black and White Developer N-methyl-p-aminophenol sulfate 2.0 g. Sodium sulfite 9.0 g. Hydroquinone 8.0 g. Sodium carbonate (monohydrate) 52.5 g. Potassium bromide 5.0 g. Potassium thiocyanate 1.0 g. Water to make I000 ml.
Cyan Color Developer 2-Amino-5-N.N-diethylamino toluene hydrochloride 0.6 g. Sodium carbonate (monohydrate) 15.0 5. Potassium bromide 0.5 g. Sodium Sulfite 5.0 g. Potassium iodide (0.l2.p aq. soln.) 5 ml. l,5 -dihydroxy-2.G-dibrornonapbthalene 1.2 g. Sodium hydroxide 2.0 g. Water to make I000 ml.
Yellow Color Developer Sodium sulfite 5.0 g. N.N-diethyl-p-phenylenediamine sulfite 2.5 g. Potassium bromide l.0 g. Potassium iodide (0.l% aq. soln.) 5.0 ml. m-henzoyM-tp-toluenesull'onamido) acetunilide 1.2 g. Sodium hydroxide 2.5 g. Water to make I000 ml.
Magenta Color Developer Sodium sulfite 5.0 g. 2-Amino-5-N.N-diethylaminotoluene hydrochloride 2.0 g. Potassium bromide 0.8 g. l-phenyl-3'(m-nitrobenzoylamino)-5- pyrozolone l.4 g. Sodium hydroxide 2.0 g. n-Butylamine 5.0 ml. Water to make I000 ml.
Bleaching Solution Potassium forrlcynnide 100.0 g. Potassium bromide 10.0 g. Borax 20.0 g. Boric acid l.0 g. Water to make I000 ml.
Fixing Solution Sodium thiosullute l50.0 g.
Sodium sulfite Water to make g. I000 ml.
in the aforesaid reversal color developing process, the competing developing agents shown inthe following table were (individually) added to the cyan color developer, and the effect of the competing developing agents on the photographic properties of the film was measured.
Exp. No. Competing Developing Agent Amount 1 N-benzyl-p-aminophenol hydrochloride 0.85 2 B-(p-hydroxyanilinomethyl) pyridine sulfate 0.85 3 a-(p-hydroxyanilinomethyl) furan hydrochloride 0.85
' mmoles/l000 ml. of developer The photographic properties of the processed film are shown in the following table, with each of the three competing developing agents, in which: (I) the reversal sensitivity is shown by the inverse logarithm of the amount of exposure at which the coupling density obtained corresponds to L0; (2) the purity of the red color reproduction is shown by the ratio of the red filter density to the green filter density (D,/D,,) of a portion of the film exposed to red light (called red patch); and (3) the ratio of the red filter density to the blue filter density (D /D of said portion is also shown. The ratio D,/D,, or D,/D is a value which illustrates the color purity of a reproduced color when a red object is reproduced in a color photograph, and the smaller that this value is, the better the reproduction.
Exp. No. Reversal Sensitivity Purity of red color reproduced Cyan Yellow Magenta DJD, 0,10,, l [.13 L27 L20 0.33 0.27 2 L15 1128 1.23 0 28 0.23 3 l.l6 1.28 L25 0.29 0.24
Exp. No. Reversal Sensitivity Purity of red color reproduced Cyan Yellow Magenta D,/D, D,/D, l 0.68 1.07 0.92 0.30 0.34 2 0.80 L13 0.98 0.33 0.26 3 0.76 [.10 0.96 0.35
These results show that by the addition of the competing developing agent of this invention, the cyan color developer will exhibit a more constant effect, even when it is degradated by air oxidation, when compared with a conventional competing developing agent. This particular advantage of the com peting developing agent of this invention was not anticipated, and it shows even more clearly the excellent usefulness of the competing developing agent of the present invention.
EXAMPLE ll Using the same basic procedures as in example l. a cyan color development was carried out. After being washed with water for eight minutes after the cyan development, the cyandeveloped color film was subjected to bleaching, washing and fixing. as in example 1. to provide cyan-colored images. in this case, the photographic properties of the color photographs which were improved by the competing developing agent of this invention were measured. The results thereof are shown in the following table. In the table, the reversal sensitivity (A) relates to the red-sensitive emulsion layer, and the cyan contamination density (B) is shown by the sum of the cyan coupling density in the portion of the green-sensitive emulsion layer exposed to red light and the cyan coupling density in the portion of the blue-sensitive emulsion layer exposed to red light. These two light sensitive emulsion layers are ones which will not be developed to any extent in a cyan color development, and, hence, cyan coupling these portions causes undesirable developing fogs in the green-sensitive emulsion layer to be magenta coupled and undesirable fogs in the blue-sensitive emulsion layer to be yellow coupled. in other words, the cyan coupling causes color turbidity, which results in a degrading of the quality of the color photographic image.
Exp. N o. Competing developing agent Amount (A)" (B) 1 N-benzyl-p-aminophenol 0.85 1. 27 0.38
hydrochloride.
2 B-(p-hydroxyaniliuomethyl) 0.85 1.36 0.33
pyridine sulfate.
3 a-(p-hydroxyanilomethyl) 0.85 1.33 0.32
furan hydrochloride.
'M.mol per 1000 ml. of developer. Reversal sensitivity. Cyan contemp ation color density.
The results show that the competing developing agent of this invention has an excellent effect when compared with a conventional competing developing agent, N-benzyl-paminophenol hydrochloride.
EXAMPLE 111 Exp. No. Competing Developing Agent (A)' (13)" l N-benzyl-p-aminophenol hydrochloride 1.05 0.63 2 [Hp-hydroxyanilinornethyl) pyridine sulfate 1.12 0.56 3 u(p-hydroxyanilinomethyl) furan hydrochloride 1.09 0.60
' revc rsal sensitivity cyan contamination color density The cyan developer containing the competing developing agent of this invention again gave excellent results in comparison to the cyan developer containing the known competing developing agent.
EXAMPLE IV The same basic procedure as was used in example 1 was repeated while conducting the cyan development for six minutes at 24 C.. using the following cyan developer:
Cyan Color Developer The photographic properties obtained by adding the competing developing agent of this invention to the cyan developer were compared with those obtained by adding. thereto, a conventional competing developing agent (N- benzyl-p-aminophenol hydrochloride). The amount and the type of competing developing agent used are shown below:
Exp. No. Competing Developing Agent Amount I N-benzyl-p-aminophenol hydro chloride 0.85 2 B-(p-hydroxyunilinomethyl) pyridine sulfate 0.85 3 a-(p-hydroxyanilinomethyl) furan hydrochloride 0.85
' mmoles/IOOO ml. ofdeveloper The results obtained are shown in the following table:
Exp. No. Reversal Sensitivity Purity of red color reproduced Cyan Yellow Magenta D,/D, D,/D, l 1.20 1.31 1.26 0.25 0.23 2 1.26 1.38 1.31 0.22 0.21 3 1.27 1.36 1.33 0.21 0.20
After allowing the three kinds of cyan developers to oxidize in air for seven days, the same procedure used above was repeated, again using the cyan developers. The effect of the degraded cyan developers on the photographic properties was then determined, the results ofwhich are shown in the following table: Exp. No. Reversal Sensitivity Purity of red color produced Cyan Yellow Magenta D,/D, D,ID,, l 0.97 1.08 1.10 0.35 0.33 2 1.07 1.16 0.31 0.31 3 1.01 1.12 1.11 0.33 0.32
it can be seen that the competing developing agent of this invention illustrated an excellent effect during this experiment, when compared with the known competing developing agent.
EXAMPLE V The same basic procedure used in example 1 was repeated while incorporating a competing developing agent (including a known competing developing agent) in each of the cyan color developers. The types and amounts utilized are shown in the following table:
Exp. No. Competing developing agent Amount 1 N-benzyl-p-aminophenol hydrochloride 0.85 2 B-( 3-methyl-4-hydroxyanilinomethyl1 pyridine sulfate 0.85 3 B-i3-phenyl-4-hydroxyanilinomethyl) furan 0.85 4 a-(p-hydroxyanilinomethyli thiophenc hydrochloride 0.85
mrnolcs 1000 m1. ofdcveloper The multilayer color photographic films thus prepared were processed as in example 1, using the aforesaid cyan developers, the results of this processing being as follows:
These results show that the competing developing agent of this invention will give a high reversal sensitivity and a high red color reproduction purity in the red-sensitive emulsion layer in comparison with the conventional competing developing agent.
What is claimed is:
l. A color developer composition comprising (1) a primary aromatic amino developing agent, (2) a color-forming coupler, (3) an alkali, and (4alkali a water-soluble competing developing agent having the formula:
wherein X represents a member selected from the class consisting of a hydrogen atom, an alkyl group having from one to four carbon atoms, a hydroxyalkyl group having from one to four carbon atoms, a phenyl group and a halogen atom, and Y represents a substituted or unsubstituted heterocyclic ring having at least one N, S or O atom, said heterocyclic ring, when substituted, being substituted with a member selected from the class consisting of an alkyl group having from one to four carbon atoms, and a benzyl group.
2. The color developer composition of claim 1, wherein said composition additionally contains a member selected from the class consisting of an alkali metal bromide, an alkali metal sulfite, and alkali metal iodide.
3. The color developer composition of claim 1, wherein said coupler is selected from the class consisting of phenolic couplers, naphtholic couplers, pyrazolone couplers, coumarone couplers and the open-chain ketomethylene couplers.
4. The color developer composition of claim 1, wherein said primary aromatic amino developing agent is selected from the class consisting of a 4-aminophenol and a p-phenylenediamine.
5. The color developer composition of claim 1, wherein said of color development baths each containing a color developing agent, after exposure to light through an original image, the improvement which comprises the use, in at least one of said color developing baths, of a watersoluble competing developing agent having the formula:
HOG-NH-GH -Y wherein X represents a member selected from the class consisting ofa hydrogen atom, an alkyl group having from one to four carbon atoms, a hydroxyalkyl group having from one to four carbon atoms, a phenyl group and a halogen atom and Y represents a substituted or unsubstituted heterocyclic ring having at least one N, S or O atom, said heterocyclic ring, when substituted, being substituted with a member selected from the class consisting of an alkyl group having from one to four carbon atoms and a benzyl group.
7. The color reversal development process of claim 6, wherein one of said baths is a cyan developer, and contains [3- (p-hydroxyanilinomethyl) pyridine as the competing develop ing agent.
8. The color reversal development process of claim 6, wherein one of said baths is a yellow developer, and contains B-(p-hydroxyanilinomethyl)pyridine as the competing develo inga ent.
e co or reversal development process of claim 6,
wherein one of said baths is a magenta developer, and conwater-soluble competing developing agent is selected from the class consisting of B-(p-hydroxyanilinomethyl)-pyridine a-(phydroxyanilinomethyl)pyridine, y-(p-hydroxyanilinomethyl)pyridine, a-(p-hydroxyanilinomethyl)furan, B-(3-methyl-4-hydroxyanilinomethyl)pyridine, [3-(3-phenyl-4 -hydroxyanilinomethyl)furan, a-(p-hydroxyanilinomethyl) thiophene, 2-(p-hydroxyanilinomethyl)-5-methylthiophene, l-benzyl-3-(p-hydroxyanilinomethyl)indole, a-(3chloro-4- hydroxyanilinomethyl)furan and a-(3-methyl-4-hydroxyanilinomethyl)furan said competing developing agent being present in an amount of 0.01 to 5.0 g./liter of the developer composition.
6. ha process for the color reversal development of a multilayer, multicolor photographic element, utilizing a plurality tains ,B-(p-hydroxyanilinomethyl)pyridine as a competing developing agent.
10. A composition for preparing a color developer solution comprising (1) a primary aromatic amino developing agent, and (2) a water-soluble competing developing agent having the formula:
noQ-nmom-y wherein X represents a member selected from the class consisting of a hydrogen atom, an alkyl group having from one to four carbon atoms, a hydroxyalkyl group having from one to four carbon atoms, a phenyl group and a halogen atom, and Y represents a substituted or unsubstituted heterocyclic ring having at least one N, S or O atom, said heterocyclic ring, when substituted, being substituted with a member selected from the class consisting of an alkyl group having from one to four carbon atoms and a benzyl group.
11. The composition of claim 10 wherein said competing developing agent is selected from the class consisting of B-(phydroxyanilinomethyl)pyridine, a-(p-hydroxyanilinomethyl)pyridine, -y-(p-hydroxyanilinomethyl)pyridine, a-(p-hydroxyanilinomethyl)furan, B-(3-methyl-4-hydroxyanilinomethyl)pyridine, B-(3-phenyl-4 -hydroxyanilinomethyl)furan, a-(phydroxyanilinomethyl)thiophene, 2-(p-hydroxyanilinomethyl)-5- methylthiophene, l-benzyl-3-(p-hydroxyanilinomethyl)indole, a-(3-chloro-4-hydroxyanilinomethyl)furan and a-(3- methyl-4-hydroxyanilinomethyl)furan.
10K k 8 i

Claims (10)

  1. 2. The color developer composition of claim 1, wherein said composition additionally contains a member selected from the class consisting of an alkali metal bromide, an alkali metal sulfite, and alkali metal iodide.
  2. 3. The color developer composition of claim 1, wherein said coupler is selected from the class consisting of phenolic couplers, naphtholic couplers, pyrazolone couplers, coumarone couplers and the open-chain ketomethylene couplers.
  3. 4. The color developer composition of claim 1, wherein said primary aromatic amino developing agent is selected from the class consisting of a 4-aminophenol and a p-phenylenediamine.
  4. 5. The color developer composition of claim 1, wherein said water-soluble competing developing agent is selected from the class consisting of Beta -(p-hydroxyanilinomethyl)-pyridine Alpha -(p-hydroxyanilinomethyl)pyridine, gamma -(p-hydroxyanilinomethyl)pyridine, Alpha -(p-hydroxyanilinomethyl)furan, Beta -(3-methyl-4-hydroxyanilinomethyl)pyridine, Beta -(3-phenyl-4-hydroxyanilinomethyl)furan, Alpha -(p-hydroxyanilinomethyl) thiophene, 2-(p-hydroxyanilinomethyl)-5-methylthiophene, 1-benzyl-3-(p-hydroxyanilinomethyl)indole, Alpha -(3chloro-4-hydroxyanilinomethyl)furan and Alpha -(3-methyl-4-hydroxyanilinomethyl)furan said competing developing agent being present in an amount of 0.01 to 5.0 g./liter of the developer composition.
  5. 6. In a process for the color reversal development of a multilayer, multicolor photographic element, utilizing a plurality of color development baths each containing a color developing agent, after exposure to light through an original image, the improvement which comprises the use, in at least one of said color developing baths, of a water-soluble competing developing agent having the formula:
  6. 7. The color reversal development process of claim 6, wherein one of said baths is a cyan developer, and contains Beta -(p-hydroxyanilinomethyl) pyridine as the competing developing agent.
  7. 8. The color reversal development process of claim 6, wherein one of said baths is a yellow developer, and contains Beta -(p-hydroxyanilinomethyl)pyridine as the competing developing agent.
  8. 9. The color reversal development process of claim 6, wherein one of said baths is a magenta developer, and contains Beta -(p-hydroxyanilinomethyl)pyridine as a competing developing agent.
  9. 10. A composition for preparing a color developer solution comprising (1) a primary aromatic amino developing agent, and (2) a water-soluble competinG developing agent having the formula:
  10. 11. The composition of claim 10 wherein said competing developing agent is selected from the class consisting of Beta -(p-hydroxyanilinomethyl)pyridine, Alpha -(p-hydroxyanilinomethyl)pyridine, gamma -(p-hydroxyanilinomethyl)pyridine, Alpha -(p-hydroxyanilinomethyl)furan, Beta -(3-methyl-4-hydroxyanilinomethyl)pyridine, Beta -(3-phenyl-4-hydroxyanilinomethyl)furan, Alpha -(p-hydroxyanilinomethyl)thiophene, 2-(p-hydroxyanilinomethyl)-5-methylthiophene, 1-benzyl-3-(p-hydroxyanilinomethyl)indole, Alpha -(3-chloro-4-hydroxyanilinomethyl)furan and Alpha -(3-methyl-4-hydroxyanilinomethyl)furan.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4161406A (en) * 1977-12-07 1979-07-17 Philip A. Hunt Chemical Corp. Solution and method for processing high speed video news film
US4543322A (en) * 1983-03-31 1985-09-24 Fuji Photo Film Co., Ltd. Process for the processing of color photographic silver halide light-sensitive material
US5695914A (en) * 1995-09-15 1997-12-09 Eastman Kodak Company Process of forming a dye image
EP2518063A1 (en) * 2006-12-21 2012-10-31 Sloan-Kettering Institute For Cancer Research Pyridazinones and furan-containing compounds
US20210340138A1 (en) * 2014-02-20 2021-11-04 Novita Pharmaceuticals, Inc. Compounds and methods for inhibiting fascin
US11866440B2 (en) 2012-08-22 2024-01-09 Cornell University Methods for inhibiting fascin

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US3141771A (en) * 1961-02-01 1964-07-21 Eastman Kodak Co Aldehyde scavengers for photographic silver halide developers
US3300305A (en) * 1962-10-25 1967-01-24 Eastman Kodak Co Color developers containing competing developing agents

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3141771A (en) * 1961-02-01 1964-07-21 Eastman Kodak Co Aldehyde scavengers for photographic silver halide developers
US3300305A (en) * 1962-10-25 1967-01-24 Eastman Kodak Co Color developers containing competing developing agents

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4161406A (en) * 1977-12-07 1979-07-17 Philip A. Hunt Chemical Corp. Solution and method for processing high speed video news film
US4543322A (en) * 1983-03-31 1985-09-24 Fuji Photo Film Co., Ltd. Process for the processing of color photographic silver halide light-sensitive material
US5695914A (en) * 1995-09-15 1997-12-09 Eastman Kodak Company Process of forming a dye image
EP2518063A1 (en) * 2006-12-21 2012-10-31 Sloan-Kettering Institute For Cancer Research Pyridazinones and furan-containing compounds
US11866440B2 (en) 2012-08-22 2024-01-09 Cornell University Methods for inhibiting fascin
US20210340138A1 (en) * 2014-02-20 2021-11-04 Novita Pharmaceuticals, Inc. Compounds and methods for inhibiting fascin
US11858929B2 (en) * 2014-02-20 2024-01-02 Cornell University Compounds and methods for inhibiting fascin

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