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
  • 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
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/39292—Dyes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes
  • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes
  • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
  • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
• • 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
  • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor

Definitions

• This invention relates to spectrally- (optically) sensitized photographic silverhalide: emulsions containing'color couplers.
• a weprepare an emulsion for color photography comprising a red-sensitive silverhalide emulsion containing a; color-former (coupler) for thecyan-image (i.- e'; arcoIon-iormer. capable offorming a quinoneiinine dye with a phenylenediamine developer), said redesensitivo emulsion being sensitized with atleast one sensitizing dye selected from the group consisting of those.
• R4 each represents a member selected from theegroup; consisting; ofhydrogen atom and. an: alkyli group. containing; from 1 tor-4. carbon; atoms,x g-:-.methy ethyl, neprcpyl, isobutyl and.nsbutylu Z and? Z1 eachrepresents non-metallic. atoms-- necessary to complete a. heterocyclic nucleus; selected: from the group, consisting of: hetero. cyclidanucleiofthe benzothiazole series; hetero.- cyclic; nuclei-of; thebenzoselenazme series, hetero:-- cyclic; nuclei; of.
• silver halide emulsion being sensitized with at;-
• R4 and R each represents an alkyl group containing from 1 to 4 carbon atoms, e. g. methyl, ethyl, n-propyl, n-butyl, isobutyl, etc.
• X1 represents an anion, e. g. benzenesulfonate, p-toluenesulfonate, chloride, bromide, iodide, perchlorate, methylsulfate, ethylsulfate, thiocyanate, acetate, propionate, etc
• D2 and D3 each represents a divalent hydrocarbon radical containing from 1 to 4 carbon atoms, e. g.
• Z3 represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the quinoline series, e. g. the quinoline nucleus, the fi-methylquinoline nucleus, the G-ethylquinoline nucleus, the G-methoxyquinoline nucleus, the 6- ethoxyquinoline nucleus, the G-chloroquinoline nucleus, etc.
• the emulsions can be coated on a support as separate layers, e. g. a support (of cellulose acetate film, resin film, paper, etc.) can be coated with a layer of the red-sensitive emulsion containing a color former (as described above) and upon this, a layer of the yellow-green sensitive emulsion containing a color former (as described above) can be coated.
• a yellow filter layer can then be coated and upon the filter layer a layer of a blue sensitive emulsion containing a colorformer which produces a yellow image or picture.
• our invention is also applicable to color photographic emulsion material wherein the emulsions are mixed instead of disposed in separate layers. Moreover, our invention is also applicable for producing single emulsions containing colorformers for making component color pictures.
• the emulsions employed in our invention can also contain the usual additions to emulsions, e. g. stabilizers, etc.
• our invention is especially useful where the emulsions contain, in addition to a color-former, a dispersing agent for the color-former, e. g. the water-insoluble but water-permeable materials set forth in U. S. Patents 2,304,940 and 2,322,027, such as water-insoluble but water-permeable cellulose esters, e. g.
• butyl phenyl phosphate monophenyl di-o-chlorophenyl phosphate, tri-o-phenylphenyl phosphate, ptoluenesulfonyl methyl-o-toluidine, p-toluenesulfonyl dimethylamide, p,p'-di-n-amylbenzenesulfonamide, p-toluenesulfonyl di-n-butyl amide, N,N'-diethyl-N,N'-diphenyl urea, N,N-di-n-butyl urea, etc.
• Our invention is especially useful with emulsions in which the color-former is dispersed in one or more of the aforesaid substantially waterinsoluble, high-boiling crystalloidal materials.
• These crystalloidal materials are organic and have boiling points above about 175 C. These crystalloidal materials have a high solvent action for the color-formers and for the dyes formed therefrom and are permeable to photographic processing solutions.
• These crystallcidal materials have been referred to as oil formers because they have the property of producing an oily or liquid solution when mixed with the coupler, even though the coupler is a solid.
• the crystalloidal materials are generally liquid at ordinary temperatures or low melting solids (below 0.).
• the most useful compounds contain one or more polar groups such as halogen, hydroxyl, carboxylic acid, amide, ketone, etc.
• Couplers producing cyan images 5- 11:-amylphenoxybenzenesulfonamino) -1-naph- 5-(N benzyl N naphthalenesulfonamino)-1- naphthol 5- (n-benzyl-N-n-valerylamino) l-naphthol 5-caproylamino-1-naphthol 2-chloro-5-(N-n-valeryl N pisopropylbenzylamino) -1-naphthol 2,4 dichloro-5- (p-nitrobenzoylB-o-hydroxyeth- .vlamino) -1-naphthol 2,4-dichl0ro-5-palmithylaminol-naphthol 2,2'-dihydroXy-5,5'-dibromostilbene 5-diphenylethersulfonamido-1-naphthol l-hydroxy-Z-
• Couplers producing yellow images The aforesaid couplers give color development with color developers, such as N,N-dimethyl-pphenylenediamine, N,N-diethyl p phenylenediamine, N-carbamidomethyl-N-methyl-p-phenylenediamine, N -carbamidomethyl-W-tetrahydrofurfuryl-2-methy1-p-phenylenediamine, N ethyl-N -carboxymethyl2-methyl-p-phenylenediamine, N -carbamidomethyl-4 -ethy1-2-methyl- 8 EXAMPLE 1 VIII.
• color developers such as N,N-dimethyl-pphenylenediamine, N,N-diethyl p phenylenediamine, N-carbamidomethyl-N-methyl-p-phenylenediamine, N -carbamidomethyl-W-tetrahydrofurfuryl-2-methy
• dyes VIII and IX do not give emulsions which are sufficiently stable to be coated in the presence of color formers, whereas dyes VIII-A and IX-A give emulsions of satisfactory stability.
• EXAMPLE 5 E osure throu h red filter which transmits substantially no light xp 51 wavelength shorter than 580 11311.]
• the resulting solution of the water-soluble salt is then dispersed in the emulsions,
• the water-soluble salts are advantageously formed by adding to the dye or dyes (Wet with a little water, methyl alcohol or ethyl alcohol), an alkali metal hydroxide, e. g. sodium or potassium hydroxide, or ammonium hydroxide, or an amine, e. g. methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, pyridine, N-methylpiperidine, npropylamine, isopropylamine, n-butylamine, ethoxyethylamine, etc.
• an alkali metal hydroxide e. g. sodium or potassium hydroxide, or ammonium hydroxide
• an amine e. g. methylamine, ethylamine, dimethylamine, diethylamine
• the salt which forms is then taken up in a suitable solvent, e. g. water, methyl alcohol, ethyl alcohol, a mixture of methyl alcohol and water, a mixture of ethyl alcohol and water, etc.
• a suitable solvent e. g. water, methyl alcohol, ethyl alcohol, a mixture of methyl alcohol and water, a mixture of ethyl alcohol and water, etc.
• the dyes of Formulas II, III and IV are ordinarily employed in a concentration of from 5 to 100 mg. per liter of emulsion.
• the optimum sensitizing effect is ordinarily obtained at a concentration of from 5 to mg. of dye per liter of emulsion.
• the sensitizing dyes in most cases should be added to the emulsions before the coupler of coupler dispersion is added.
• the color-formers are incorporated in the emulsions in the customary manner, e. g. by adding a dispersion of the coupler in a waterinsoluble but Water-permeable material (see above) to the emulsion, or by adding a dispersion of the alkali metal of the coupler in water.
• the coupler (color former) which has been mixed with the highboiling organic crystalloidal material to produce an oil-like mixture can be dispersed in water or gelatin solution or in any aqueous binder of col-' loidal character which is miscible with the silver halide emulsion.
• the dispersion can be effected with the aid of a homogenizer, colloid mill or the like, and the dispersions can be stabilized by the addition of emulsifying agents such as those of the well-known higher fatty alcohol sulfate type.
• the dispersion may also be formed by dispersing a solution of coupler and crystalloidal material in a solvent of low boiling point such as butyl acetate with Water or gelatin solution and subsegives a fairly stable emulsion in the presence of color couplers for the cyan image.
• the sensitizing dyes can be added to the emulsions in accordance with customary pro.- cedures, i. e. by adding a solution of' the dye inan apropriate solvent to the emulsions.
• the dyes of Formulas II, III and IV the dyes of Formulas II, III and IV, the
• dyes are advantageously dissolved in methyl alcoquently removing the low-boiling solvent by evaporation.
• I-lere also an emulsifying agent can be used. It is important that the mixture of coupler and crystalloidal material be a liquid at ordinary r temperatures, so that liquid particles are formed when the mixture of coupler and crystalloidal material is emulsified in water and mixed with the emulsion, the particles retaining the couplerin solution, yet being readily penetrated by the photographic developing solution and other processing baths.
• the nature and proportions of the coupler and the crystalloidal material should be chosen so that the particles are liquid under the conditions of coating and processing the emulsion.; With the aforesaid crystalloidal materials, there is little or no tendency to crystallization even when the coupler is present in a proportion amounting to 50% or more of the high-boiling crystalloidal material.
• the crystalloidal ma- *terials'shou1d also hesubstantially"colorlessand stable *toward light, "heatand moisture, in addition to-b eing" in'ertto thevarious'processingbaths which may be "encountered, .”suh as developers,
• brorriide and bromiodide developing-out :emul- 'sions.
• the dyes set forthunder Formulal above can be prepared as "describedin United States Patent”'2;2'3 lififisydated 'flebruary 11, 1941, by condensing a -.cyclammonium arearboxyalkyl quaternary salt containing a reactive methyl group :with ethyl -orthc'iformate, tethyl orthoacetate;'ethyl'orthopropionate, ethylconthobdtyrate or ethyl orthovalerate.
• the dyes set forth under Formulas IV-VIII above are prepared as described in the copending application of Gertrude Van Zandtrand Leslie G. S. Brooker, Serial No. 711,816, filed November 22, 1946, now U. S. Patent 21'51559153, issued 31115 1 811950.
• R :and :R4 represent a member selected; fromathe; group :consistingto'fa; hydrogen atom and; anzvalkyl-groupccontaining .from l -130
• R4 and R each represents an alkyl group containing from 1 to 4 carbon atoms
• X1 represents an anion
• D2 and D3 each represents a divalent aliphatic hydrocarbon radical containing from 1 to 4 carbon atoms
• Z: represents the non-metallic atoms necessary to complete a beterocyclic nucleus of the quinoline series.
• a red sensitive gelatino-silver-halide emulsion for color photography containing dispersed therein finely divided liquid particles of a mixture of an o-acylaminophenol color-former for the cyan image capable of forming a quinoneimine dye with a phenylenediamine developer, and a substantially water-insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C., said crystalloidal material having a high solvent action for the color-former and for the dye formed therefrom, and being ermeable to photographic processing solutions, the nature and proportions of the color-former and crystalloidal material being so chosen that particles thereof are liquid under conditions of coating and processing the emulsion, said red sensitive emulsion being sensitized to the red with at least one sensitizing dye represented by the following general formulas:
• D and D1 each represents a divalent aliphatic hydrocarbon radical containing from 1 to 4 carbon atoms
• R and R4 represent a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 4 carbon atoms
• Z and Z1 each represents the non-metallic atoms necessary to complete a beterocyclic nucleus selected from the group consisting of heterocyclic nuclei of the benzothiazole series, heterocyclic nuclei of the benzoselenazole series, heterocyclic nuclei of the naphthothiazole series and heterocyclic nuclei of the naphthoselenazole series
• R1 and R3 each represents an alkyl group containing from 1 to 2 carbon atoms
• R2 represents a monocyclic aryl group of the benzene series
• X represents an anion.
• a red sensitive gelatino-silver-halide emulsion for color photography containing dispersed therein finely divided liquid particles of a mixture of an o-acylaminophenol color-former for the cyan image capable of forming a quinoneimine dye with a phenylenediamine developer, and a substantially water-insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 0., said crystalloidal material having a high solvent action for the color-former and for the dye formed therefrom, and being permeable to photographic processing solutions, the nature and proportions of the color-former and crystalloidal material being so chosen that particles thereof are liquid under conditions of coating and processing the emulsion, said red sensitive emulsion being sensitized to the red with at least one sensitizing dye selected from the group consisting of those dyes represented by the following general formula:
• D represents a'saturated divalent aliphatic hydrocarbon radical containing from 1 to 4 carbon atoms
• R represents a member selected from the group consisting of a hydrogen atom and a primary allrvl group containing from 1 to 4 carbon atoms
• Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series.
• a red sensitive gelatino-silver-halide emulsion for color photography containing dispersed therein finely divided liquid. particles of a mix-; ture of an 'o-acylaminophenol color-former for the cyan image capable of forming a quinoneimine dye with a phenylenediamine developer, and a substantially water-insoluble, low molecular weight, organic crystalloidal material having a boiling point above about C., said crystalloidal material having a high solvent action for the color-former and for the dye formed therefrom and being permeable to photographic processing solutions, the nature and proportions of the the color-former and crystalloidal material being so chosen that particles thereof are liquid under conditions of coating and processing the emulsion, said red sensitive emulsion being sensitized to the red with at least one sensitizing dye selected from the group consisting of those dyes represented by the following formula:
• a red sensitive gelatino-silver-halide emulsion for color photography containing dispersed therein finely divided liquid particles of a mixture of an o-acylaminophenol color-former for the cyan image capable of forming a quinoneimine dye with a phenylenediamine developer, and a substantially water-insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C., said crystalloidal material having a high solvent action for the color-former and for the dye formed therefrom and being permeable to photographic processing solutions, the nature and proportions of the color-former and crystalloidal material being so chosen that particles thereof are liquid under conditions of coating and processing the emulsion, said red sensitive emulsion being sensitized to the red with at least one sensitizing dye selected from the group consisting of those dyes represented by the following general formula:
• cyclic aryh groups on the: benzeneseries Zr naps-ea sents; the nonemetallim atoms; necessary: to: come plate: a: heteroeyclie nucleus; of; the.- benzoislaiazale;v
• crystalloidal material having, a. high; solvent; ace tion for the color-former and for the dye formed therefrom and being permeable to photographic processing solutions, the nature and proportions of the color-former and crystalloidal material being so chosen that particles thereofare liquid under conditions of coating. and processing the emulsion, said red sensitive 8111111510111 being sensitized to the red with at least one sensitizing dye selected from the group consisting of those dyes represented by the following formula:
• a yellow-green sensitive gelatino-silverhalide emulsion for color photography containing dispersed therein finely divided liquid particles of a mixture of a 5-pyrazolone color-former for the magenta image capable of. forming an azomethine dye with. a phenylenediamine developer, and a substantially water-insoluble, low molecular weight, organic, crystalloi'dal material having a boiling point above about 175" C., said crystalloidal material having a high. solvent action for the color-former and for the dye formed therefrom, and being permeable to photographic pronessingvsolutions, the natuiseiandspmportions: of the" color-former, and crystalloidal.
• D2 represents a divalent saturated all-- phatic radical containing from 1' to 4' carbon atoms
• X1 represents an anion
• Z3 represents. the non-metallic, atoms, necessary to; complete, a. heterocyclic: nucleus of the quinoiine: series.
• a yellow-green sensitive gelatino-silverhalide emulsion for color photography contain-- ingv dispersed therein finely divided-1 liquid particles ofi amixture of a. 5-pyrazolone color-former tor the magentaimage capable of forming an: azomethine dye with av phenylenediamine developer; and a substantially water-insoluble, low molecular weight, organic, crystalloidal material: having: aboilings point above. about 1:75" 0., said crystalloidal material having a, high solvent action for te color-former and for the dye formed therefrom, and being! permeable to photographic processing solutions, the natur and proporti ns.
• said yellow-green sensitive emulsion being sensitized to the yellow-green with at least one sensitizing dye selected from the group consisting of those dyes represented by the following formula:
• a sensitive silver halide emulsion for color photography selected from the group consisting of (I) a red sensitive silver halide emulsion con taining dispersed therein finely divided liquid particles of a mixture of a phenolic color-former for the cyan image capable of forming a quinoneimine dye with a phenylenediamine developer, and a substantially water-insoluble, low molecular weight, organic, crystalloidal material having a boiling point above about 175 C., said crystalloidal material having a high solvent action for the color-former and for the dye formed therefrom, and being permeable to photographic processing solutions, the nature and proportions of the color-former and crystalloidal material being so chosen that particles thereof are liquid under conditions of coating and processing the emulsion, said red sensitive emulsion being sensitized to the red with at least one sensitizing dye selected from the group consisting of those dyes represented by the following general formulas:
• D and D1 each represents a divalent aliphatic hydrocarbon radical containing from 1 to 4 carbon atoms
• R and R4 represent a member selected from the group consisting of a hydrogen atom and an alkyl group consisting from 1 to 4 carbon atoms
• Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of heterocyclic nuclei of the benzothiazole series, heterocyclic nuclei of the benzoselenazole series, heterocyclic nuclei of the naphthothiazole series and heterocyclic nuclei of the naphthoselenazole series
• R1 and R3 each represents an alkyl group containing from 1 to 2 carbon atoms
• R2 represents a monocyclic aryl group of the benzene series
• X represents an anion
• (II) a yellow-green sensitive silver halide emulsion containing dispersed therein finely divided liquid particles of a mixture
• R4 and R5 each represents an alkyl group containing from 1 to 4 carbon atoms
• X1 represents an anion
• D2 and D3 each represents a divalent aliphatic hydrocarbon radical containing from 1 to 4 carbon atoms
• Z3 represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the quinoline series.

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

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• 0
  • BE BE484580D patent/BE484580A/xx unknown
• 1947
  • 1947-08-29 US US771380A patent/US2640776A/en not_active Expired - Lifetime
• 1948
  • 1948-08-26 GB GB22555/48A patent/GB674161A/en not_active Expired
  • 1948-08-26 GB GB22554/48A patent/GB660012A/en not_active Expired
  • 1948-08-27 FR FR980390D patent/FR980390A/fr not_active Expired
• 1950
  • 1950-10-03 DE DEE2749A patent/DE972811C/de not_active Expired

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