US2860976A - Antifoggants for photographic developers - Google Patents

Antifoggants for photographic developers Download PDF

Info

Publication number
US2860976A
US2860976A US602067A US60206756A US2860976A US 2860976 A US2860976 A US 2860976A US 602067 A US602067 A US 602067A US 60206756 A US60206756 A US 60206756A US 2860976 A US2860976 A US 2860976A
Authority
US
United States
Prior art keywords
photographic
silver halide
developer
color
development
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US602067A
Other languages
English (en)
Inventor
Catherine M Spath
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BE559754D priority Critical patent/BE559754A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US602067A priority patent/US2860976A/en
Priority to GB24078/57A priority patent/GB873198A/en
Priority to FR1192199D priority patent/FR1192199A/fr
Application granted granted Critical
Publication of US2860976A publication Critical patent/US2860976A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers

Definitions

  • This invention relates to photographic developers, and more particularly, a method of inhibiting or preventing fog during development.
  • the unwanted density occurring as a result of the action of the black-and-white developer is particularly apparent in those portions of the emulsion layers intended to record the cyan image, i. e., where no red area, or a reduced amount of red, is present in the original subject.
  • a similar effect occurs in the emulsion layers intended to record the magenta and yellow images.
  • Silver halide emulsions which have been subjected to a first development for producing a black-and-white image, followed at some later stage by color development for producing a cyan image, and'which contain a fog-inhibiting agent in the first developer as outlined below, have improved contrast and color density.
  • an object of my invention to provide improved developers in photographic processes. Another object is to provide a method of inhibiting the fog resulting from the action of certain black-and-white developers. Still another object is to improve the accuracy of rendition of color images, particularly in the cyan layer of multilayer photographic elements which have been differentially sensitized to record specific regions of the spectrum. Other objects will become apparent from a consideration of the following description and examples.
  • I provide improved photographic developers containing 4-carboxythiazolidines, or water-soluble salts thereof, in addition to the usual alkaline agent and black-and-white developing agent.
  • R7o OH H s wherein R represents a hydrogen atom, an alkyl group (e. g., methyl, ethyl, etc.), especially a lower alkyl group,
  • tassium, lithium, etc. an ammonium ion, or an organic ammonium ion, such as pyridinium (R is hydrogen), tr1- ethyl ammonium (R is hydrogen-, etc.
  • car boxyl as used herein is intended to define the COOH group as well as water-soluble derivatives thereof.
  • the compounds of Formula I can be added to the strongly alkaline developing agents in the form of their esters which are easily hydrolyzed, such as methyl or ethyl esters, to give the desired water-soluble alkali metal salts.
  • the 4-carboxythiazolidines useful in practicing my invention are added to the developers commonly employed in the photographic art for producing black-and-white images.
  • Such developers include the compounds known as polyhydroxybenzenes (e. g., hydroquinone, catechol, pyrogallol, etc.), and N-substituted aminophenols (e. g., N-methylaminophenols, N-ethylaminophenols, 'etc.) or mixtures of such developers.
  • Prominent among such developing agents for the rapid development of photographicimages are those comprising hydroquinone and Elon (p- N-methylaminophenol). While such developing agentsof the emulsion where no exposure took place.
  • the additives of my invention eliminate or materially reduce delayers.
  • the 4-carboxythiazolidines employed in the developers of my nvention can be utilized in various concentrations. depending on the particular emulsions employed and the concentrationof silver halide in the emulsions and concentration of developing agents in the. developers. In general, not less than 10 mg. per liter of developer of 4- carboxythiazolidine should be employed.
  • the most advantageous concentration of 4-carboxvthiazolidine compound can be determined by developing a series of test strips of silver halide emulsions wherein the concentration of the 4-carboxythiazolidine compounds is varied, aswvell as the-concentrationofi-developing a ent (if desired); The usual addenda can be employed. in thedevelopersa such: as-stronglvalkaline agents (e. g.. sodium carbonate, potassiumcarbonate, sodium hydroxide, ctc.),
  • as-stronglvalkaline agents e. g.. sodium carbonate, potassiumcarbonate, sodium hydroxide, ctc.
  • Myinvention is primarily directed to the development of the ordinarily employed gelatino-siliver-halide developmg-out emulsions-e. g., gelatino-silver-chloride, -chlorobromide. -chloroiodide, -chlorobromiodide. -bromide and -bromiodide. developing-out emulsions. While the results in the following examples were obtained using gelatinosilver-bromiodide emulsions, excellent results have also been obtained usingother silver halide emulsions. These emulsions can be coated'in the usual manner on any suitable support, e.
  • Photographic silver halide emulsions useful in my invention can also contain such addenda as chemical sensitlzers, e. g., sulfur sensitizers (e. g., allyl thiocarbamide, thiourea, allyl isothiocyanate, cystine, etc).
  • chemical sensitlzers e. g., sulfur sensitizers (e. g., allyl thiocarbamide, thiourea, allyl isothiocyanate, cystine, etc).
  • gold compounds e. g., potassium chloroaurate, auric trichloride, etc.
  • various azaindene compounds such as those disclosed in U. S.
  • Patent 2,716.062 condensation products of alkylene oxides, such' as those shown in U. S. Patent 2,400,532, as well as the additives mentioned in Jones et al. U.. S. application Serial No. 575,160, filed March 30, 1956. i
  • COUPLER (1) 1- hydroxy 2 [-2',4'-di-tert.amylphenoxy)-nbutylJ-naphthamide (U. S. Patent 2,474,293) (2) 1-hydroxy-4phenylazo-4-(p-tert.-butylphenoxy)-2- naphthanilide (U. S. Patent 2,521,908) (3) 2- 2,4-di-tert.amylphenoxyacetamino -4,6-dichloro- S-methyl phenol (U. S.
  • Patent 2,725,291) (4) 2-(a-di-tert.amylphenoxy-n-butyrylamino)- 4,6 dichloro-t-methyl phenol (5) 6- ⁇ a- ⁇ 4-[a-(2,4-di-tert.amylphenoxy)butyrarnido] phenoxy ⁇ acetamido ⁇ -2,4-dichloro-3-methyl phenol (6) 2- [3'-(2",4"-diamylphenoxy) -acetamido] -benzamido-4-chloro-5-methylphenol (7) 1-(2,4',6"- trichlorophenyl)-3-[3"-(2',4"'-di-tert.- amylphenoxyacetamido) -benzamidoJ-5-pyrazolone (U. S. Patent 2,600,788) (8) 1-(2',4',6 trichloropl1enyl) 3-[3"-(2",4"
  • Couplers which are primarily useful in color developers have previously been described in a number of patents and technical articles. Spence and'Carroll U. S. Patent 2,640,776, issued June 2, 1953, enumerates a number of couplersuseful in color developers which have been found particularly useful in my invention. Typical of such coupers for producing cyan images are:
  • the oleyl ether of a polyethylene glycol having a molecular weight greater than 300 was added to a second portion of this emulsion at a concentration of 5 grams'of the oleyl ether per mole of silver halide, and the emulsion was coated on a cellulose acetate support (identified as coating 2 below).
  • coating 2 a cellulose acetate support
  • One strip of each coating was exposed for second to a SOD-watt, 3000 K. light source on an Eastman type lb sensitometer.
  • the exposed coatings were then developed for three minutes in developer A having the following composition:
  • the coatings were washed in the usual manner and dried.
  • the coatings were washed for ten minutes and treated for two minutes in a silver bleach bath having the following composition:
  • Potassium ferricyanide g a 100 Potassium. bromide g Borax g 7.5 Boric acid g 5.0
  • Example 1 Example 1
  • 4-carboxy-2-(m-nitrophenyl)thiazolidine was added to one of the black-and-white developers in the amount of 0.03 g. per liter of developer in place of the corresponding chloro compound employed in Example 1.
  • the .developer containing no thiazolidine com-- pound is identified as A below, while the developer containing said compound is identified as B below.
  • the color-forming developers useful in my invention have been previously described in the prior art, and my in vention is not to be restricted to the use of any particular color-forming developer.
  • the most useful of such colorforming developers are the phenylenediamines and substituted derivatives thereof.
  • Typical of such color-forming developers are the sulfonamido substituted p-phenylenediamines disclosed in Weissberger et a1.
  • U. S. Patent 2,548,574, issued April 10, 1951 the substituted p-phenylenediamines disclosed in Weissberger et al.
  • U. S. Patents 2,552,240-2 issued May 8, 1951
  • the substituted pphenylenediamines disclosed in Weissberger et al. U. S. Patent 2,566,271, issued August 28, 1951 and the substituted pphenylenediamines disclosed in Weissberger et al. U. S. Patent 2,566,271, issued August 28, 1951.
  • alkylene oxide polymers the alkylene oxides generally containing from 2 to 4 carbon atoms.
  • alkylene oxide polymers include polyalkylene glycols and conden sation products of alkylene oxides with organic compounds 7 containing an active hydrogen. atom, such as alcohols, amines, mercaptans, acids, amides, etc. Generally, such alkylene oxide.
  • polymers have a molecular weight of at. least 300,. asfsliown in U. S.-application Serial No. 50,495 mentioned above. It is to be further understoodlilattheemulsions. employedin my invention need notbe chemically sensitized, although particularly usefulresults have been obtainedwith emulsions which havebeenchemically' sensitized with such alkylene oxide polymers.
  • a photographic developer having. a reduced tendency to fog photographic silver halide emulsions comprising an alkaline solution of (1).a silver halide developing agent selected from the group consisting of .polyhydroxybenzenes, N-monoalk-ylaminophenols, and mixtures of said polyhydroxybenzenes and N-monoallgylaminophenols and at least mg. per liter of solution of (2) a compound selected from. the group consisting of (18) those represented by the following general formula:
  • R represents a member selected from the group consisting of a hydrogen atom, a lower alkyl group containing from 1 to 2 carbon atoms and a monocyclic aryl group of the benzene series, and (B) a water-soluble salt of said compound.
  • a photographic developer having a reduced tendency to fog photographic silver halide emulsions comprising an alkaline solution of hydroquinone and N-methyl-p-aminophenol, and at least 10 mg. per liter of solution of a watersoluble salt of a compound selected from those repre: sented by the following general formula:
  • R represents a monocyclic aryl group of the benzene series.
  • A-photographic developer having a reduced tendency A-photographic developer having a reduced tendency:
  • fog photographic silver halide emulsions comprising an alkaline aqueous solution of hydroquinone, N-methyl-paminophenol and at least-1'0 mg. per liter of solution, of a water soluble salt of 4-carboxy-2-(p-chlorophenyl)- thiazolidine.
  • a photographic developer having a reduced tendency to fog photographic silver halide emulsions comprising an alkaline aqueous solution of hydroquinone, N-methyl-paminophehol and at least 10 mg. per liter of solution of a water soluble salt of 4-car boxy-2-(m-nitrophenyl)thiazolidine.
  • R represents a member selected from the group consisting of a hydrogen atom, a lower alkyl group containing from 1 to 2 carbon atoms and a monocyclic aryl group of the benzene series, and (2) a water-soluble salt of said compound.
  • R represents a member'selected from the group consistingof a hydrogen atom, a lower alkyl group containing from 1 to 2 carbon atoms and a monocyclic aryl group of the benzene series.
  • a multilayer photographic element containing a plurality of differentially sensitized photographic silver halide emulsion layers is given a first exposure, followed by development in a photographic developer for producing a black-and-white negative image and a second exposure followed by at least one additional development in a photographic developer for producing a colored image, said colored image bearing a complementary relationship to the region of the spectrum to which the photographic silver halide emulsion has been difierentially sensitized
  • the step of developing said first exposed silver halide emulsion layers in a black-and-white developer having a reduced tendency to fog said silver halide emulsions comprising an alkaline solution of a photographic silver halide developer selected from the group consisting of hydroquinone, N-methyl-p-aminophenol and mixtures of hydroquinone and N-methyl-p-aminophenol, an alkali metal sulfite and at least mg. per liter of solution of a water-soluble
  • R-C H2 wherein R represents a monocyclic aryl group of the benzene series.
  • a multilayer photographic element containing a plurality of differentially sensitized photographic silver halide emulsion layers is given a first exposure, followed by development in a photographic developer for producing a black-and-white negative image and a second exposure followed by at least one additional development in a photographic developer for producing a colored image, said colored image bearing a complementary relationship to the region of the spectrum to which the photographic silver halide emulsion has been differentially sensitized, the step of developing said first exposed silver halide emulsion layers in a black-and-white photographic developer having a reduced tendency to fog said photographic silver halide emulsions comprising an aqueous solution of (1) a photographic silver halide developer selected from the group consisting of hydroquinone, N- methyl-p-aminophenol, and mixtures of hydroquinone and N-methyl-p-aminophenol, (2) sodium carbonate, (3) an alkali metal sulfite, and (4) a compound
  • R represents a monocyclic aryl group of the benzene series.
  • R represents a member selected from the group consisting of a hydrogen atom, a lower alkyl group containing from 1 to 2 carbon atoms and a monocyclic aryl group of the benzene series.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US602067A 1956-08-03 1956-08-03 Antifoggants for photographic developers Expired - Lifetime US2860976A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE559754D BE559754A (enrdf_load_stackoverflow) 1956-08-03
US602067A US2860976A (en) 1956-08-03 1956-08-03 Antifoggants for photographic developers
GB24078/57A GB873198A (en) 1956-08-03 1957-07-30 Improvements in photographic developers and in reversal processes of colour photography
FR1192199D FR1192199A (fr) 1956-08-03 1957-08-02 Nouveau révélateur photographique et ses applications, notamment à la photographie en couleurs

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US602067A US2860976A (en) 1956-08-03 1956-08-03 Antifoggants for photographic developers

Publications (1)

Publication Number Publication Date
US2860976A true US2860976A (en) 1958-11-18

Family

ID=24409835

Family Applications (1)

Application Number Title Priority Date Filing Date
US602067A Expired - Lifetime US2860976A (en) 1956-08-03 1956-08-03 Antifoggants for photographic developers

Country Status (4)

Country Link
US (1) US2860976A (enrdf_load_stackoverflow)
BE (1) BE559754A (enrdf_load_stackoverflow)
FR (1) FR1192199A (enrdf_load_stackoverflow)
GB (1) GB873198A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3473924A (en) * 1967-12-11 1969-10-21 Polaroid Corp Novel photographic products and processes
DE2112728A1 (de) * 1970-03-20 1971-09-30 Eastman Kodak Co Photographisches Aufzeichnungsmaterial
US4396711A (en) * 1982-03-29 1983-08-02 E. I. Du Pont De Nemours And Company Speed-increasing adjuvants for silver halide emulsions
US4481359A (en) * 1982-01-04 1984-11-06 E. I. Du Pont De Nemours And Company Silver halide emulsion containing a purified cysteine-glutaraldehyde polymer fraction and process of making
US5576154A (en) * 1994-06-28 1996-11-19 Sterling Diagnostic Imaging, Inc. Photographic recording materials for medical radiography

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2099374A (en) * 1934-04-07 1937-11-16 Gevaert Photo Production N V Photographic developer and a process of photographic developing

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2099374A (en) * 1934-04-07 1937-11-16 Gevaert Photo Production N V Photographic developer and a process of photographic developing

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3473924A (en) * 1967-12-11 1969-10-21 Polaroid Corp Novel photographic products and processes
DE2112728A1 (de) * 1970-03-20 1971-09-30 Eastman Kodak Co Photographisches Aufzeichnungsmaterial
US4481359A (en) * 1982-01-04 1984-11-06 E. I. Du Pont De Nemours And Company Silver halide emulsion containing a purified cysteine-glutaraldehyde polymer fraction and process of making
US4396711A (en) * 1982-03-29 1983-08-02 E. I. Du Pont De Nemours And Company Speed-increasing adjuvants for silver halide emulsions
EP0091212A1 (en) * 1982-03-29 1983-10-12 E.I. Du Pont De Nemours And Company Speed increasing adjuvant containing silver halide emulsions
US5576154A (en) * 1994-06-28 1996-11-19 Sterling Diagnostic Imaging, Inc. Photographic recording materials for medical radiography

Also Published As

Publication number Publication date
BE559754A (enrdf_load_stackoverflow)
GB873198A (en) 1961-07-19
FR1192199A (fr) 1959-10-23

Similar Documents

Publication Publication Date Title
US4157915A (en) Color photographic light-sensitive material containing development precursor
US3220839A (en) Photographic emulsions containing isothiourea derivatives
US3141771A (en) Aldehyde scavengers for photographic silver halide developers
US3945824A (en) Process for forming optical sound track
US4155763A (en) Color photographic processing method
US2401713A (en) Color photography
US2588982A (en) Direct positive photographs using hydrazine in the emulsion
US2956876A (en) Mercapto heterocyclic addenda for reversal color development
US3499761A (en) Silver halide emulsions containing alkyl esters of benzimidazole carbamic acid antifogging agents
US3266897A (en) Antifoggant agents for photography
US2860976A (en) Antifoggants for photographic developers
US3756821A (en) Process for the formation of color photographic images
US4634660A (en) Development-processing method for silver halide photographic light-sensitive material
GB2139370A (en) Processing of colour photographic silver halide light-sensitive material
US3775128A (en) Silver halide emulsion containing a triazine as antifoggant
US3652278A (en) Pre-development process for reducing fog in silver halide photographic materials
US3046130A (en) Photographic materials containing a chemical sensitizer
US4473635A (en) Silver halide photographic light-sensitive material
US3930860A (en) Spectrally sensitized color photographic materials suitable for high temperature rapid development
US4038081A (en) Development method
US3910790A (en) Color photographic materials processed in the presence of anti-color fogging agents
US2232707A (en) Stabilized photographic sensitive material
US5776666A (en) Triazolium thiolate baths for silver halide development acceleration
US3650760A (en) Alkoxy mercaptophenols as photographic addenda for photographic elements
US3396022A (en) Quinone stabilizers and antifoggants for silver halide emulsions