US2899306A - Yh hci - Google Patents

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US2899306A
US2899306A US2899306DA US2899306A US 2899306 A US2899306 A US 2899306A US 2899306D A US2899306D A US 2899306DA US 2899306 A US2899306 A US 2899306A
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color
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compound
phenyl
pyrazolone
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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers

Definitions

  • the blue-sensitive and green-sensitive layers is a filter layer for absorbing blue radiation which may be transmitted through the blue-sensitive layer.
  • the multi-layer coating can also have other interlayers for specialized purposes. Such multi-layer materials have been previously described in the prior art, such as Mannes et al. US. Patent 2,252,718, issued August 19, 1941.
  • Color materials of the type employed in the instant invention are those intended primarily for reversal processes, wherein the exposed material is given a conventional black-and-white development, followed by a reversal exposure, or exposures, and color development.
  • the color materials used in my invention comprise emulsions which can contain color-forming materials or couplers, or these color couplers can be used instead in the color developers.
  • fog centers are introduced into the unexposed regions, and upon reversal exposure and subsequent color development, these unexposed areas have deposited therein coupled color-forming materials, resulting in severe loss of color quality.
  • color developer containing a cyan coupler results not only in development of the red-sensitive layer, but also in development of cyan fog in the blueand green-sensitive layers.
  • This fog is particularly severe in emulsions which contain conventional chemical sensitizers, such as gold sensitizers, sulfur sensitizers, or polyethyleneglycol type chemical sensitizers.
  • a colored image can be formed by adding to certain color developing solutions, or by incorporating in the silver halide emulsion, a compound which couples during development with the oxidation product of the developing agent, thus forming a colored compound which is deposited adjacent to the silver grains of the silver image during such development.
  • a compound which is employed in conjunction with the developing agent for the silver and which couples with the oxidation product of the developing agent during development is referred to as a color-forming compound or coupler.
  • Such compounds usually belong to one of three widely known types, i.e., pyrazolone couplers, phenol couplers, or open-chain ketomethylene couplers. These couplers produce, respectively, magenta, cyan and yellow images.
  • the formamidinothiomethyl compounds useful in practicing my invention include compounds represented by the following general formula:
  • R represents a carbalkoxyl group (e.g., carbomethoxy, carb-ethoxyl, carbobutoxyl, etc., especially a carbalkoxyl group containing from 2 to 5 carbon atoms), an alkyl group (e.g., ethyl, n-propyl, n-butyl, p-sulfoethyl, etc., especially an alkyl group containing from 1 to 4 carbon atoms), a heterocyclyl group (e.g., tetrazaindenyl, pyridyl, etc.), or an amido group
  • carbalkoxyl group e.g., carbomethoxy, carb-ethoxyl, carbobutoxyl, etc., especially a carbalkoxyl group containing from 2 to 5 carbon atoms
  • an alkyl group e.g., ethyl, n-propyl, n-butyl, p-sulfoeth
  • the formamidinothiomethyl compounds employed in the color developers of my invention can be utilized in various concentrations depending upon the particular emulsions employed, the concentration of silver halides in the emulsions, and the concentration of the developing agents in the developers. In general, not less than about mg. per liter of developer of formamidinothiomethyl compound should be employed. The most advantageous concentration can be determined by developing a series of test strips of silver halide emulsions wherein the concentration of formamidinothiomethyl compound is varied, as well as the concentration of the developing agent.
  • the usual addenda can be employed in the developers, such as strongly alkaline agents, sodium carbonate, potassium carbonate, sodium hydroxide, etc., restraining agents, such as potassium bromide, stain preventives, such as alkali metal sulfites, etc.
  • My invention is primarilydirected to the development of the ordinarily employed gelatino-silver-halide developing-out emulsions, e.g., gelatino-silver-chloride,v -chlorobromide, -chloroiodide, -chlorobrorniodide, -bromide and -bromiodide developing-out emulsions. Whilethe results in the following examples were obtained using gelatinosilver-bromiodide emulsions, excellent results can alsobe obtained using other silverhalide emulsions. These emulsions can be coated in the usual manner on any suitable support, e.g., glass, cellulose nitrate film, cellulose acetate film, polyvinyl acetal resin film, paper or metal.
  • any suitable support e.g., glass, cellulose nitrate film, cellulose acetate film, polyvinyl acetal resin film, paper or metal.
  • Photographic silver halide emulsions useful in my invention can also contain such addendaas chemical sen- 75 sitizers, e.g., sulfur sensitizers (e.g., allyl thiocarbamide, 'thiourea, allyl isothiocyanate, cystine, etc), various gold processes.
  • Addendaas chemical sen- 75 sitizers e.g., sulfur sensitizers (e.g., allyl thiocarbamide, 'thiourea, allyl isothiocyanate, cystine, etc)
  • couplers or color-forming compounds which are soluble in the strongly alkaline developing solutions are well known to those skilled in the art. Typical couplers include the following:
  • Acetoacetaminobenzenesulfon-fl-naphthalide 5 7.' p Furoylacetaminobenzenesulfon-N-cyclohexylamide 58. p (4 ethoxybenzoylacetamino)benzenesulfonamide 59. Terephthaloyl bis[ (p-N-amylsulfonamido) acetanilide] 60. p (Quinoline 8 sulfonarnino) -w-benzoylacetanilide 61. p Acetoacetamino-o-methylbenzenesulfon N- anilide 62.
  • Typical couplers that are primarily useful in the photographic silver halide emulsion layers of my invention comprise the following:
  • amylphenoxyacetanilide 77 4 benzoylacetamido 3-methoxy-2,4-di-tert.-
  • the color-forming developers useful in my invention have been previously described in the prior art, and my invention is not to be restricted to the use of any particular color-forming developer.
  • the color-forming, developers previously mentioned which I have found to be especially useful in my invention comprise aromatic primary amines containing an amino (substituted or not) or hydroxyl substituent. Phenylenediamines and substituted derivatives thereof containing a primary amino group have been found to provide excellent results when employed in combination with the formamidinothiomethyl compounds of my invention.
  • Typical of such color-forming developers are the sulfonamido substituted p-phenylenediamines disclosed in Weissberger U.S.
  • Patent 2,548,- 574 issued April 10, 1951, the substituted p-phenylenediamines disclosed in Weissberger et al. U.S. Patent 2,566,- 271, issued August 28, 1951.
  • Other phenylenediamine color-forming developers can be employed to like advantage in the process of my invention.
  • the first developer employed in the process of my invention is generally a rapid developer of the MQ type, i.e., a combination of hydroquinone and Elon (p-N- methylaminophenyl) developer.
  • the photographic silver halide emulsions useful in the process of my invention can be prepared according to known methods, such as those described in Hewitson and McClintock U.S. Patent 2,618,556, issued November 18, 1952. Of course, emulsions prepared by other methods can be used to equal advantage in my invention. These emulsions can be chemically sensitized or not, as mentioned above. Additional chemical sensitizers useful in my invention comprise those disclosed in the c0- pending application Serial No. 550,495, filed December 1, 1955 (now U.S. Patent 2,886,437, issued May 12, 1958), in the name of D. E. Piper.
  • Example 1 weight greater than 300 was added to a second portion of the same emulsion at a concentration of 5 gms. of the oleyl ether per mole of silver halide, and the emulsion coated onto a cellulose acetate support.
  • the dried coating was then cut into several strips, identified coating series B below.
  • One strip of each coating was exposed for. second to a SOO-Watt, 3000 K. light source on an -Eastman Type Ib sensitometer.
  • the exposed coatings '7 were then developed for 3 minutes in adevelop'er having the following composition:
  • the coatings were then washed for two minutes.
  • the coatings were washed for ten minutes and treated for two minutes in a silver bleach bath having the following composition:
  • Example 2 i In a manner similar to that illustrated in Example 1 above, a portion of a' gelatino-silver-bromiodide emulsion which had been sensitized with a sulfur compound and a gold compound of the type described above, and the oleyl ether of a polyethyleneglycol having a molecular weight greater than 300 (5 g./mole of AgX), was coated on a cellulose acetate support. The coating was exposed for second to a -watt, 5400 K. light source on an Eastman Type Ib sensitometer. The exposed coating was then developed for 4 minutes in a developer having the following composition:
  • the coating was then washed for two minutes.
  • the coating was washed for 10 minutes and treated for 2 minutes in a silver bleach bath having the composition given above.
  • the coating was then rinsed and treated for 2 minutes in a fixing bath having the composition given above, washed and dried.
  • a second strip was given the same treatment except that the flash re-exposure was omitted.
  • the D-max. and color (magenta) fog for the coating were then measured.
  • Example 3 An ordinary gelatino-silver-bromiodide emulsion sensitized with a sulfur sensitizer, a gold compound, and the oleyl ether of a polyethyleneglycol having a molecular weight greater than 300 (5.0 g./mole of AgX) was processed in exactly the manner described in Example 2 above, except that a yellow color-forming coupler was employed in place of the magenta developer of Example 2, while the concentration of compound (a) was reduced to 0.075 g./ liter for the processing of the second coating. The time of color development for the first coating, the color developer containing no formamidinothiomethyl compound, was 8 minuts, while the development time for the processing of the second coating in the color developer containing compound (a) was 30 min- Water to make one liter.
  • alkylene oxide polymers the alkylene oxides generally containing from 2 to 4 carbon atoms.
  • alkylene oxide polymers include polyalkylene glycols and condensation products of alkylene oxides with organic compounds containing an active hydrogen atom, such as alcohols, amines, mercaptans, acids, amides, etc.
  • alkylene oxide polymers have a molecular weight of at least 300, as shown in U.
  • the formamidinothiomethyl compounds useful in my invention can be added to the color developers either in the form of their free bases or in the form of acidaddition salts of these bases. Since the color developing solutions of my invention are strongly alkaline, the acidaddition salts are converted to the free bases, in which form they manifest their activity. It is to be understood that the term formamidinothiomethyl compound includes not only the free bases but also acid-addition salts of these bases.
  • Example A S-carbethoxymethyl 1 phenyl 3 (4H- 1,2,4-triaz0l-3-yl)isothiourea 3-amino-1,2,4-triazole was boiled in dry dioxane with an equimolecular amount of phenyl isothiocyanate. There was obtained a 50 to 60 percent yield of the desired 1-phenyl-3-(3-triazolyl)thiourea as a white solid which was only slightly soluble in water and dioxane, but was readily soluble in dimethylformamide. It was recrystallized from its solution in dimethylformamide by addition of water to give white crystals melting at 230- 234 C.
  • the color-forming compounds of my invention can be prepared according to methods previously described in the literature.
  • the following two examples will serve to illustrate methods of preparing two typical couplers useful in my invention.
  • Example B N-benzoylaceto-o-anisidine
  • a two-liter flask was fitted with a one-holed rubber stopper and a steam-jacketed Friedrichs condenser.
  • a standard distillation head, thermometer and downward pointing Liebig condenser cooled with water.
  • the flask was then charged with 600 cc. of neutral histological xylene, 74 g. (0.6 mol.) of o-anisidine and 115 g. (0.6 mol.) of ethyl benzoylacetate.
  • the flask was refluxed for minutes at such a rate that most of the boiling xylene condensed in the steam-jacketed condenser, but some distillate was condensed in the cold condenser.
  • the temperature at the top of the hot condenser was C. at the beginning of the reflux period, but slowly dropped to 70 C. at the end of the period. During this time, 45 cc. of distillate was collected from the cold condenser.
  • the heating mantle was turned ofli, 500 cc. of ligroin was added to the hot solution, and the material allowed to cool for 16 hours. The resulting crystalline product was broken up, filtered olf and air-dried.
  • a yield of 90 g. of crude product was obtained, M.P. 868 C. Recrystallization of the product from 520 cc. of methanol yielded 76.3 g. of product, M.P. 86-8 C. Yield was 47.4 percent of theory.
  • Example C 3- (p-nitrophenoxyacetylamino) -1- (2',4',6'- trichlorophenyl) -5-pyraz0l0ne
  • the p-nitrophenoxyacetyl chloride used above was prepared as follows: In a SOD-ml. flask were mixed 19.7 g. (0.1 mole) of p-nitrophenoxyacetic acid and 100 ml. of thionyl chloride. The mixture was refluxed for hours on a steam bath and the excess thionyl chloride removed under reducdpressure. The removal of the thionyl chloride wascontinued until the residue had reached constant weight. The acid chloride was used without purification and gave good results. It can be crystallized from dried ligroin to obtain a white crystalline material melting at 86-87 C.
  • the p-nitrophenoxyacetic acid used above was prepared as follows: In a 5-liter flask were placed 278 g. (2 moles) of p-nitrophenol, 190 g. (2 moles) of chloroacetic acid, 168 g. (4.2 moles) of sodium hydroxide and 2 liters of water. The mixture was boiled in the open flask until it showed a neutral reaction to litmus paper. The reaction temperature reached 115 C. and some water was evaporated. When the neutral point had been reached (2.5-3 hours) an additional 84 g. (2.05 moles) of sodium hydroxide and 95 g. (1 mole) of chloroacetic acid were added to the flask and the heating continued until a neutral reaction again resulted.
  • a developing composition for color photography comprising an arylenediamine color developer and a compound selected from those represented by the following general formula:
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 3 carbon atoms, and a monocyclic aryl group of the benzene series containing from 6 to 7 carbon atoms
  • R represents an amino group
  • R represents a member selected from the group consisting of a carbalkoxyl group containing from 2 to 5 carbon atoms, an alkyl group containing from 1 to 4 carbon atoms, a tetrazaindenyl group, a pyridyl group, and an amino carbonyl group.
  • a developing composition for color photography comprising alkali, an alkaline sulfite, a p-phenylenediamine color developer, and a compound selected from those represented by the following general formula:
  • R represents an amino group, and R;
  • a'member selected from the group consisting of a carbalkoxylgroup containing from 2 to 5 carbon atoms, an alkyl group containing from '1 to 4 carbon atoms,a tetrazaindenyl group, a pyridyl group, and an aminocarbonyl group.
  • a photographic developer for color photography comprising a strongly alkaline solution of a p-phenylenediamine photographic developing agent, an alkali metal sulfite and a compound selected from those represented by the following general formula:
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 3 carbon atoms, and a monocyclic aryl group of thebenzene series containing from 6 to ,7 carbon atoms
  • R represents an amino group
  • R represents a'member'selected from the group consisting of a carbalkoxy group containing from 2 to 5 carbon atoms, an alkyl group containing from '1 to 4 carbon atoms, a tetrazaindenyl group, a pyridyl group, and an aminocarbonyl "group.
  • a developing composition for color photography comprising a p-phenylenediamine color developer, an alkali metal sulfite, and a compound selected from those represented by the following general formula:
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 3'carbon atoms, and a'monocyclic aryl group of the benzene series containing from 6 to 7 carbon atoms
  • R represents an amino group
  • R represents a member selected from the group consisting of a carbalkoxyl group containing from 2 to 5 carbon atoms, an alkyl group containing from 1 to 4 carbon atoms, a tetrazaindenyl group, 'a pyridyl group, and an aminocarbonyl group.
  • a developing composition for color photography comprising a p-phenylenediamine color developer, an alkali metal sulfite, and a compound selected from those represented by the following general formula:
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 3 carhon atoms, and a monocyclic aryl group of the benzene series containing from 6 to 7 carbon atoms, R represents an amino group, and R represents a tetrazaindenyl group.
  • a photographic developing composition for color photography comprising a p-phenylenediamine color developer, an alkali metal sulfite, and 2-formamidinothiomethyl-4-hydroxy-6-methyl-l,3,3a,7-tetrazaindene.
  • a developing composition for color photography comprising a p-phenylenediamine color developer, an alkali metal sulfite, and bis(2-formamidinothiornethyl- G-methyl-l,3,3a,7-tetrazainden-4-yl)sulfide.
  • a developing composition for color photography comprising a p-phenylenediamine color developer, an alkali metal sulfite, and 2-S-thiouroniumethanesulfonate.
  • a developing composition for color photography comprising a p-phenylenediamin'e color developer, an alkali metal sulfite, and S-carbethoxymethyl-l-phenyl-3- (4H-1,2,4-triazol-3-yl)isothiourea.
  • a developing composition for color photography comprising a p-phenylenediamine color developing cornpou'nd,'an alkali metal sulfite, a color-forming compound capable of coupling with the oxidation products of said p-phenylenediamine color developing compound to produce a colored image selected from the group consisting of cyan, magenta and yellow, and a compound selected balkoxyl group containing from 2 to 5 carbon atoms, from those represented by the following general formula: an alkyl group containing from 1 to 4 carbon atoms, a
  • R 5 wherein R represents a member selected from the group References Cited in the file of this patent consisting of a hydrogen atom, an alkyl group containing UNITED STATES PATENTS from 1 to 3 carbon atoms, and a monocyclic aryl group of the benzene series containing from 6 to 7 carbon gig Mannes et 1941 atoms, R represents an amino group, and R represents 10 3,087 Dersch et a1 1948 a member selected from the group consisting of a car- 2,514,650 Knott et July 1950

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3113864A (en) * 1959-06-11 1963-12-10 Eastman Kodak Co Reducing fog in reversal color films processed in developers containing couplers
US3220839A (en) * 1961-08-25 1965-11-30 Eastman Kodak Co Photographic emulsions containing isothiourea derivatives

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2252718A (en) * 1937-11-19 1941-08-19 Eastman Kodak Co Reversal process of color photography
US2453087A (en) * 1946-11-07 1948-11-02 Gen Aniline & Film Corp Photographic developers containing tetrazolyl disulfides as antifogging agents
US2514650A (en) * 1946-04-05 1950-07-11 Eastman Kodak Co Photographic developing with addition products to improve image quality

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2252718A (en) * 1937-11-19 1941-08-19 Eastman Kodak Co Reversal process of color photography
US2514650A (en) * 1946-04-05 1950-07-11 Eastman Kodak Co Photographic developing with addition products to improve image quality
US2453087A (en) * 1946-11-07 1948-11-02 Gen Aniline & Film Corp Photographic developers containing tetrazolyl disulfides as antifogging agents

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3113864A (en) * 1959-06-11 1963-12-10 Eastman Kodak Co Reducing fog in reversal color films processed in developers containing couplers
US3220839A (en) * 1961-08-25 1965-11-30 Eastman Kodak Co Photographic emulsions containing isothiourea derivatives

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BE564174A (en, 2012)

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