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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
  • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines

Definitions

• This invention relates to spectrally (optically) sensitized photographic silver halide emulsions containing color couplers, i.e., color-forming compounds which couple with the oxidation products of a color developer, such as a phenylenediamine developer, to provide a colored image.
• color couplers i.e., color-forming compounds which couple with the oxidation products of a color developer, such as a phenylenediamine developer
• sensitizing dyes are particularly useful in combination with photographic silver halide emulsions containing color couplers in that no interference takes place between the color couplers and the sensitizing dyes, insofar as displacement of the sensitizing dye forn the silver halide grains by the color coupler is concerned. See, for example, Spence and Carroll U.S. Patent 2,640,776.
• sensitizing dyes which can be employed in combination with color couplers are useful in color photography, inasmuch as a number of such dyes give rise to or contribute to the formation of undesirable fog.
• Another object is to provide green sensitization without undesirable fog for color emulsions containing color couplers. Still another object is to provide a method for making an improved green sensitized photographic emul- 'sion. Other objects will become apparent from a consideration of the following examples and description.
• Couplers for the magenta image which have been found particularly useful in our invention comprise the well-known class of color-forming compounds known as pyrazolone couplers.
• the structure of the couplers is not as critical, however, as the nature of the particular sensitizing dyes employed, insofar as we have been able to. determine. This is mentioned in somewhat greater detail below.
• the spectral sensitizing dyes of Formula I are quite unique in that they contain both an anion and cation (i.e., a zwitterion); Such dyes are usually named anhydro dyes, as though water had been split from the hydrogen of a sulfo group and a hypothetical hydroxyl group attached to one of the heterocyclic nitrogen atoms.
• the separate emulsions can 1e coated on a support as separate layers, e.g., a support f cellulose acetate film, resin film, paper, etc., can be oated with a layer of a red-sensitive emulsion containng a color coupler, and upon this, a layer of a greenensitive emulsion of our invention containing a color ormer or coupler can be coated.
• a yellow filter layer Upon the green-sensiive layer, a yellow filter layer can be coated, and upon he filter layer, a layer of a blue-sensitive emulsion conaining a color former which produces a yellow image an be coated.
• Typical multi-emulsion photographic lements involving color couplers or color formers in he emulsion, to which our invention is applicable, are
• 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 color-formers for making component color pictures.
• the emulsions employed in our invention can also contain the usual additions to emulsions, e.g., stabilizers, etc.
• the emulsions contain, in addition to a color-former, a dispersing agent for the color-former, e.g., the water-insoluble but waterpermeable materials set forth in US. Patents 2,304,940 and 2,322,027, such as water-insoluble but water-permeable cellulose esters, e.g., Water-insoluble, but waterpermeable cellulose acetate, cellulose acetate-phthalate, cellulose nitrate, etc., water-insoluble, but water-permeable cellulose ethers, water-insoluble but Water-permeable natural and synthetic resins, high-boiling, substantially water-insoluble crystalloidal materials, such as N-n-amylphthalimide, tetrahydrofurfuryl benzoate, triphenyl phosphate, n-butyl sulfone, ethyl-N,N-di-n-butylcarbamate, ethyl
• butyl phenyl phosphate monophenyl di-ochlorophenyl phosphate, tri-o-phenylphenyl phosphate, ptoluenesulfonyl methyl-o-toluidine, p-toluenesulfonyl dimethylamicle, p,p-di-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 water-insoluble, 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 crystalloidal 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 C.).
• the most useful compounds contain one or more polar groups such as halogen,'hydroxyl, carboxylic acid, amide, ketone, etc.
• the above-mentioned color couplers provide a magenta image upon development with color developers, such as N,Ndimethyl p phenylenediamine, N,I l diethyl p phenylenediamine, N carbamidomelhyl N- methyl p phenylenediamine, N carbamidomethyl- N tetrahydrofurfuryl 2 methyl pphenylenediamine, N ethyl N carboxymethyl 2 methylp phenylenediamine, N carbamidomethyl N ethyl- 2 methyl p phenylenediamine, N ethyl N tetrahydrofurfuryl 2 methyl p phenylenediamine, N ethyl N tetrahydrofurfuryl 2 methyl p aminophenol, 3 acetylamino 4 aminodimethylaniline, N- ethyl N B methanesulfonamidoeth
• Table A the unique effect obtained with one of the dyes of Formula I above is illustrated.
• the table also illustrates the elfect provided by a similar dye containing only ethyl groups attached to the nitrogen atoms of the chlorinated benzimidazole nuclei. The results were obtained as follows: 1
• a spectral sensitizing dye (0.132 g./rnol. AgX)'as identified in the table in methanol solution.
• mnylpheno-xyacetamido)-benzamidol-5-pyrazolone (0.142 g./mol. AgX) in dibutylphthala-te was then added.
• a spreading agent such as saponin, and hardener, such as formaldehyde, were thenad ded.
• the emulsions were then divided into several batches and each batch coated on a cellulose acetate support, chilled, set and dried.
• a Wratten Filter No. 61 i.e., a filter which transmits visible radiation only between 4-80 and 560 mg, with a maximum between 520 and 5 30 mp
• the film strips were processed through the Kodak Color Negative Process for the times indicated. This process is described indetail in an article by W. T. Hanson and W. I. Kisner in. Soc. Mot. Pic. TV Eng, vol. 61, No. 6. pages 667-701, December 1953.
• the coupler which has been mixed with the high-boiling or game crystalloidal material to produce an oil-like mix ture
• the coupler can be dispersed in water c r-gelatin solution or 1.] any aqueous binder of colloidal character which i miscible with the silver halide emulsion.
• the dispersioi can be effected with the aid of a homogenizer, colloir mill or the like, and the dispersions can be stabilize by the addition of emulsifying agents such as those 0 the Well-known higher fatty alcohol sulfate type.
• Th dispersion may also be formed by dispersing a solutioi of coupler and crystalloidal material in a solvent of lov boiling point such as butyl acetate with water or gelatii solution and subsequently removing the low-boiling sol vent by evaporation.
• a solvent of lov boiling point such as butyl acetate with water or gelatii solution
• an emulsifying agen can beused. It is important that the mixture of couple: and crystalloidal material be a liquid at ordinary tem peratures, so that liquid particles are formed when tht mixture of coupler and crystalloidal mate-rial is emulsi tied in water and mixed with the emulsion, the particle: retaining the coupler in solution, yet being readily "pene trated by the photographic developing solution and othei processing baths.
• the crystalloidal materials should also be substantially colorless and stable towarC light, heat and moisture, in addition to being inert tr the various processing baths which may be encountered such as developers, oxidized developers, silver remova baths and fixing baths. They should have a sufficiently flow refractive index so that solutions of the couplers it droxide, can be used in combination with color couplers,
• the sensitizing dyes canbe added to the emulsions in accordance with customary procedures, i.e., by adding a solution of the dye in an appropriate solvent to the emulsions, such as illustrated in preparing the coatings ofv Table A above.
• Solvents other than the methyl alcohol illustrated above can also be used; such solvents include pyridine, acetone, etc., or mixtures of such solvents.
• the amount of sensitizing dye employed can be varied, depending upon the characteristics of the particular emulsion employed, results desired, etc. In general, fromabout 5 to 100 mg. of dye per liter of emul sion issufiicient to obtain maximum sensitization.
• Our invention is directed primarily to the ordinarily employed gelatino-silver-halide developing-out emulsions.
• These ordinarily employed silver halide developing-out emulsions are emulsions which form surface latent image (see British Patent 581,772, accepted October 24, 1946).
• silver halide emulsions which form-latent image mostly inside the silver halide grains see British Patent 581,772 supra) can also be employed in practicing our invention.
• the dyes of general Fonnula I above can be prepared according to methods previously described in the prior art, such as illustrated in Van Lare U.S. Patent 2,739,149, issued March 20,1956.
• the preparation of one of the dyes useful in our invention is illustrated in the following examples ple .4-i0a0butane sulfonic acid, sodium. salt to 50 ml. and diluted with 200 ml. of acetone. After chilling, the solid was filtered off and washed with acetone. A second crop of 23 g. 20% of slightly yellowish solid was obtained. On evaporating the filtrates and washings to dryness, a residue of 19 g. 16% of quite yellow solid was obtained.
• Example 2.5,6-dichlr0-1-ethyl-2-methyl-3-(l-sulfabufyl)benzimidazolium iodide, sodium salt An intimate mixture of 22.9 g. (1 mol.) of 5,6-dichlorol-ethyl-Z-methylbenzimidazole and 28.6 g. (1 mol.) of 4- .odobutane-sulfonic acid, sodium salt was heated at 170- l80 C. for 2 hours. The hard glassy solid became :rystalline after boiling with acetone for four hours. The arge pieces were ground in a mortar and total solid efluxed an additional 2 hours with fresh acetone. The :olid was filtered off and washed with acetone. A yield )f 48 g. 93% of yellowish powder was obtained.
• a green-sensitive photographic silver halide emulion for color photography containing a color-former for he magenta image capable of reacting with the oxidaion products of a phenylenediamine developer to form .n azomethine dye, and a spectral sensitizing dye selected rom those represented by the following general formula:
• R represents an alkyl group containing from 1 a 2 carbon atoms, n represents a positive integer of from (01),.
• R represents an alkyl group containing from 1 to 2 carbon atoms
• n represents a positive integer of from 1 to 2
• D represents an alkylene group containing from 2 to 4 carbon atoms.
• a green-sensitive gelatino-silver-halide emulsion for color photography containing dispersed therein finelydivided liquid particles of a mixture of a S-pyrazolone color-former for the magenta image capable of forming an azomethine dye with the oxidation products of a phenylenediarnine developer, and a substantially waterinsoluble, 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 color-former and crystalloidal material being so chosen that particles thereof are liquid under conditions of coating and processing the emulsion, said green-sensitive emulsion being sensitized to the green with at least one spectral sensitizing dye selected from the group consisting of those dyes represented by the following general formula:
• n represents a positive integer of from 1 to 2 and D represents an alkylene group containing from 2 to 4 carbon atoms.
• a green-sensitive gelatino-silver-halide emulsion for color photography containing dispersed therein finelydivided liquid particles of a mixture of a 5-pyrazolone color-former for the magenta image capable of forming an azomethine dye with the oxidation products of a phenylenediamine developer, and a substantially Waterinsoluble, 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 are liquid under conditions of coating and processing the emulsion, said green-sensitive emulsion being sensitized to the green with anhydro-5,5',6,6'-tetrachloro-1,1-diethyl 3,3 di(4 sulfobutyl)benzimidazolocarbocyanine
• a green-sensitive gelatino-silver-halide emulsion for color photography containing dispersed therein'finelydivided liquid particles of a mixture of 1-(2',4,6'-tetrachlorophenyl) -3- 3 2 ',4-di-tert.
• said green-sensitive emulsion being sensitized to the gree with anhydro-5,S',6,6'-tetrachloro-1,1-diethyl-3,3'-di( sulfobutyl)benzimidazolocarbocyanine hydroxide.

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• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Cited By (27)

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Citations (4)

• 0
  • BE BE570512D patent/BE570512A/xx unknown
• 1957
  • 1957-08-23 US US680003A patent/US2912329A/en not_active Expired - Lifetime
• 1958
  • 1958-08-19 FR FR772767A patent/FR1222454A/fr not_active Expired
  • 1958-08-22 GB GB27021/58A patent/GB871936A/en not_active Expired

Patent Citations (4)

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