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Sensitized photographic emulsion containing color couplers

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US2640776A
US2640776A US77138047A US2640776A US 2640776 A US2640776 A US 2640776A US 77138047 A US77138047 A US 77138047A US 2640776 A US2640776 A US 2640776A
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color
emulsion
dye
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Spence John
Burt H Carroll
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Eastman Kodak Co
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Eastman Kodak Co
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392Additives
    • G03C7/39208Organic compounds
    • G03C7/39292Dyes
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/10Organic substances
    • G03C1/12Methine and polymethine dyes
    • G03C1/14Methine and polymethine dyes with an odd number of CH groups
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/10Organic substances
    • G03C1/12Methine and polymethine dyes
    • G03C1/14Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/388Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor

Description

Patented June 2, 1953 SENSITI-ZED;BHQEBOGRAPHIC EMULSION CONTAINING. GOLOR COUPLERS J'olin Spence' and- Burt H. Carroll, Rochester, N; Y.', assignots= to- Eastman Kodak Company, Rochester; N. 13., a corporationofi New. Jersey No,.Drawing, Application August 29, 1947, Serial/BNO. 771,380

This inventionrelates to spectrally- (optically) sensitized photographic silverhalide: emulsions containing'color couplers.

In general, in subtractive color photography" blue; green and red sensitive photographic silver halide: emulsions-are employed; The green and red-sensitivities are obtained bythe use offs-ensi: tizing dyes adsorbed; to the silver halidegrain-s. When couplers or dispersions of couplers" are incorporated'inthe dye-sensitizedemulsions; it is necessary that; they do not alter the spectral; (optical) sensitization produced by the dyes;

With the: very great: majority of sensitizing dyes; themolten sensitized silver halide emulsions in combination with the color couplers or dispersions of color couplers are not stable enough" to permit? the obtaining of" uniform sensitivitythroughout the" period of coating;.the* emulsions losing; the sensitivity conferred" by the dye-to a considerable degree during'the coating: operation;

We have now "found that certain combinations: of silver halide emulsions sensitizing dyes and color couplers are, in fact, stable and". thatithe melted-emulsions can be coatedwithoutappre ciable loss in dye-sensitivity;

It is, accordingly, an object of our 'inventiontoprovide stable combinations of silver halide emulsions sensitizing dyes and-color couplers: A further object is to provide a process for preparing such: combinations. Still other. objects will become apparent hereinafter.

' In: accordance with our invention 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. dyes: represented by the fol- 3 lowing general formulas:

and 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. thenaphthothiazole; series anda heterocyclic nuclei-1 of the naphthoselenazole; series. e; g. the benzothiazole nucleus, the:v 5;methylbenzothiazole= nucleus, the 5methoXy, benzothiazole nucleus, the 5-ethy1benzothiazole, nucleus,-, the: 5-ethoxybenzo.thiazo1enucleus;. the 5 .-phenylbenzothiazolenucleus, the. 5-chloro.- benzothiazole nucleus; the-5r-bromobenzothiazole nucleus, the benzoselenazole nucleus, the 5. OhlOIObGI'lZOSBIEIIflZOlB? nucleus; the. aenaphthothiazole, nucleus, the; fl-naphthothiazole nucleus,, the a-naphthoselenazo1e-- nucleus,,' the ;3-naph.-:--- thoselenazole nucleus, etc;, R1 andvRa each reprersents: an alkyl group; containing from: 1' to, 2, carloon. atomsmi e, methylandethyl, R2--.I'61D1'6.-- sents; a: monocyclic aryl; group" of the benzene. series; e: g;.nheny;l-,- p-methoX yphenyl, mi-tolyl, pechloropheny-h, prethoxyphenyl, p-tolyh. pebromophenyl, and; X, represents ananion, e,-. g, chloride, bromide, iodide,. methylsulfata. ethyl-- sulfate; p-toluenesulfonatm. benzenesulfonate acetate-,- propionate,-, thiooyanate; perchlorate, etc;

In accordancewith; our invention, we. prepare: a. yellow-greensensitiveT silver halide. emulsion; containing a:, color-former (coupler) for. the: magenta. image? (ii er. a color-former capable, of= forming: an; azomethine dye" with. a, phenylenea diamine; developer), said yellow-green sensitive,

silver halide emulsion being sensitized with at;-

least'.onesensitizingdyeselected from the group consistinggof; thosezdyes'represented by the fol-.

lowing, general formulas:

wherein 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. methylene, ethylene, ethylidene, trimethylene, tetramethylene, etc., and 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.

In the preparation of photographic elements for color photography employing our new emulsions, any of the customary procedures can be used. Thus, 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. Upon the yellowgreen sensitive layer, 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. Typical multi-emulsion photographic elements (involving color-formers in the emulsion) to which our invention is applicable are described in United States Patents 1,055,155, dated March 4, 1913; 2,304,940, dated December 15, 1942, and 2,322,027, dated June 15, 1943.

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. In addition to the sensitizing dyes and color-formers 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. water-insoluble, but waterpermeable cellulose acetate, cellulose acetatephthalate, cellulose nitrate, etc., water-insoluble, but water-permeable cellulose ethers, water-insoluble but water-permeable natural and synthetic resins, high-boiling, substantially waterinsoluble crystalloidal materials, such as N-namylphthalimide, tetrahydrofurfuryl benzoate, triphenyl phosphate, n-butyl sulfone, ethyl-N,N- di-n-butylcarbamate, ethyl-N-phenylcarbamate, tetrahydrofurfuryl succinate, ethyl benzyl malonate, methyl phthalate, n-butyl phthalate, namyl phthalate, p-methoxyethyl phthalate, pethoxyethyl phthalate, fi-butoxyethyl phthalate, butyl o-methoxybenzoate, n-hexyl benzoate, benzophenone, p sec amylbenzophenone, tricresyl phosphate, diphenyl mono-p-tert. 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.

The following couplers are suitable for use in our invention. It is to be understood that this list is not exhaustive, but merely to typify compounds which may be used.

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- (N-isoamyl-N-phenyl) naphthamide l-hgdroxy-2- (N-p-sec. amylphenyl) -naphtham- 8 hydroxy-l-a-naphthoyl 1,2,3,4 tetrahydroquinoline 2-lauryl-4-chlorophenol 1-naphthol-2-carboxylic-a-naphthalide 1-naphthol-5-sulfo-cyclohexylamide 5-phenoxyacetamino-l-naphthol 5-,6-phenylpropionylamino-1-naphthol Monochlor-5-(N-'yphenylpropylN-p-sec.-amylbenzoylamino) -1-naphthol Z-acetylamino-5-methylphenol 2-benzoylamino-3,5-dimethylphenol 2 s(p tert. amylphenoxy') -'n butyrylamino-5- methylphenol any of the color-formers producing yellow-images can be used, e. g.

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.

OOH

VIII-A.

CH; IX-A.

TABLE A [Exposure through red filter which transmits substantially no light of wavelength shorter than 530 m,u.]

Dye

VIII vI II-A IX IX-A Speed Speed 7 Speed Speed tized with same dye and containing a dispersion of an o-acylaminophenol coupler for cyan image, held 2 hrs. at C 2 Red speed too low to measure.

p-phenylenediamine, N -ethyl-N -tetrahydrofurto Fr m t e d in the a e table it s app t fury1-2-methyl-p-aminophenol, 3-acetylamino- 4-aminodimethylaniline, N-ethyl-N-fi-methanesulfonamidoethyll-aminoaniline, N-ethyl-N-flmethanesulfonamidoethy1-3-methyl 4 aminoaniline, the sodium salt of N-methyl-N-fi-sulfoethyl-p-phenylenediamine, etc.

The following examples demonstrate the that two otherwise excellent red sensitizers (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 2 stability of emulsions containing color formers s prepared in accordance with our invention. The

dyes hereinafter formulated will be referred to C1 C CH=CH CH=C in the subsequent examples by the Roman numerals assigned to the dyes. In certain of the exl amples comparisons with other sensitizing dyes E show the greatly superior stability of our new CH; emulsions.

1.1 The data in the above Table show two yellowgreen sensitizers either of which gives an emulsion containing a coupler for the magenta image,

which emulsions are satisfactory for coating purposes.

EXAMPLE 4 XIV.

TABLE D [Exposure through red filter which transmits substantially no light of wavelength shorter than 580 m n] Dye Speed 7 gelatino-silver-bromoiodide emulsion sensitized with dye XIV gelatino-silver-broxniodide emulsion sensitized with dye XIV and containing a dispersion of an o-acylaminophenol coupler for cyan image, held at 1 hr. for 40 C gclatindsilvenbromiodide emulsion sensitized wlth dye XIV and containing a dispersion of an o-acylaminophenol coupler for cyan lmage, held at 2 hrs. for 40 C 1 Concentration of sensitizing dye is mg. per liter of emulsion in all cases. In the above Table D it is shown that dye XIV gives a stable emulsion in the presence of color couplers for the cyan image.

EXAMPLE 5 E osure throu h red filter which transmits substantially no light xp 51 wavelength shorter than 580 11311.]

Dye Speed 7 gelatino-silver-bromoiodide emulsion sensltized with dye XV 1 same gelati o-silver-bromolodlde emulsion sensitized with same dye and containing a dispersion of an oacylaminophenol color coupler for cyan image, held at C. for l hr same gelatino'silver-bromolodlde emulsion sensitized with same dye and containing a dispersion of an o-acylaminophenol color coupler for cyan image, held at 40 C. for 2 hrs. 0.55

v 1 Concentration of dye in all cases, 30 mg. per liter of emulsion. In the above Table E it is shown that dye XV hol and a volume of the methyl alcoholic solution (which may be diluted with water) containing from 5 to 100 mg. of the dye or dyes is slowly added to 1000 cc. of emulsion with stir-ring. In the case of the dyes of Formulas I, V, VI and VII, a water-soluble salt of the dyes is advantageously formed and dissolved in Water, methyl alcohol or ethyl alcohol. 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. 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. As in the case of the dyes of Formulas II, III and IV, the dyes of Formulas I, V, VI and VII are ordinarily employed in a concentration of from 5 to 100 mg. per liter of emulsion. In the case of any of the sensitizing dyes employed in our invention, 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 (couplers) 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. When employing dispersions of couplers in the aforesaid crystalloidal materials, 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.

In preparing emulsions in accordance with our invention, 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. In the case of 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,

"ozddizeddevelopers;silverremoval baths'and fixohlorobromide, tzhlorobromiodide, '-"iddochloride,-

brorriide and bromiodide "developing-out :emul- 'sions. These "ordinarily employed "silver halide developing out "emulsions "are '--emi'1lsions "which "form surface latent image- (see '-'-British1atent 581L772, accepted OtOb-er "24, 194-6) iI-Iowever, l

silver "halide emulsions which 1 form latent image mostly inside the silver 'hali'de'grains see'British Patent 581,772 supra) "can also "be employed in praetiing our invention.

-The dyes set forth urider-Formula-II above are deseribed in the copending 'applieationo-fheslie S. "Brooker and Frank L. -White, Serial "No. 5191354, filed J anuary 22, 19'44, now '11. SR-Patent 25478;.3'66, issued Aug-inst ll, 1949. The "dyes-set forth 1 under Formulalll above are described in Unitedstates Patent 252 ISEZSBfiiateWSeptember -3," 1940. "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.

Vlrhat"weclairrras our mvention am'didesirefito beisecured byLetters Patenttdf'tthe UnitedTStates is:

1. "A red sensitive gelatino=silver halide femulsion for"color' photography-containing dispersed therein finely divided liquid partioles of "a".mixture of "a phenolic "icolorifornrer for "the 'fcyan image "capable :of forming 1a, rquinoneimine tr lye with i a 'jphenylene'diamine developer, raifd'ra rsnb- 'stantially water-insoluble,- Iow"molecular weight, organic, crystalloidal' material "having .a'bo'iling point "above'about t175"C.,"said crystalloidahmatei-ial having a "hiE'hSOIVEHT;i2IOti0n"fOr' 'thecolor former and for the "dye formed therfrom, :and being; permeable'tophotographic processing-solutions, "the nature and proportions'i'o'f the color formerand"crystalloidalmaterialtbeingso.chosen that particles thereof are liquid'underrconditi'ons of coatingandprooessin'gthe "emuison safd red sensitive emulsion being sensitizedato the red with at least one sensitizing dye selected from the group consisting of those dyes represented by the following general formulas:

ienwon gphatim-hydro carhonzradicalac'ontainingrom $1 '"to z-ldtcarbon atoms, R :and :R4 :represent a member selected; fromathe; group :consistingto'fa; hydrogen atom and; anzvalkyl-groupccontaining .from l -130 cazrbomatomsrZtsandzzr'mchirepresents the non- :metallio. atoms ."necessary "to complete a, hetero- EGYOHCZIIHOIGHSrfSElEGti-Bd.fflf'fimltheJg'I'Ou'pCOIlSiStiflg piifiheterocyclicrnnlei ofrthesbenzothiazole series, lheterooyclicsnucleizoftthellaenzoselenazole-lseries; heterocyolicmuolei 30f the inaphthothiazoletser'ies andxheterocyelic miclei'of'lthe naph'thoselenazole .series Rl and Rszeaohmepresents: anual'kylggroup containing'zfrom 1 to 2Jcarbonsatoms,iRzrrepre- 'sents 15a :monooyclic :;aryl groupof the benzene series, and.Xxrepresentsamanion.

A yellowegreenxsensitivevgelatino silver T-halide tiemulsion for :color aphotography 2 containing dispersed :ztherein 'sf'fine'ly divided 1 liquid ip'artieles .of satmixturerof-ia ketomethylene color-formeriior the magentaimage capableof forming:aiquinoneimine idye :with a phenylenediamine developer, and a substantially watersinsoluble, low molecular :weight, organic, zcrystalloidalrmaterialrhaving a, boiling point .cabove 53130-1113 1 C1, zisaid tony-stalloidal 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 colonformewandicrystalloidatmaterial being so chosen that particles thereof are liquid under conditions oflcoating and processing the emulsion, said yellow-green sensitive emulsion being sensitizdto the yellow-greemwith at least onessensitizingdyesselectedzfrometlaezgrou :conv sisting of those dyes represented by .the followinglgeneral formula:

iv-m-ooon wherein 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, and Z: represents the non-metallic atoms necessary to complete a beterocyclic nucleus of the quinoline series.

3. 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:

wherein 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, and X represents an anion.

4. 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:

ooCn-1:oon=d-on= iI-nooon wherein 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, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series.

5. 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:

' c00- OOH 6. 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

series: and X represents; am anion=..

'72. A. red; sensitive: gelatino siluer-halide emul sion: foncQlor: photegraphy' cfintaining; dispersed: therein; finely divided. liquid particles of a. mix? ture off an; o.-aey1am-inophenol colon-former; ion the; cyan image capable ot fOFIIliHg; a q uinoner' imine. dye with a phenylenediamine; developer;, and a.- substantiallywater-insoluble; 10W: molecs ula-r weight, organic; crystalloidalmaterial have ing; a boiling point. aboyt about 1'75? said. 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:

8. 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. material being: so chosen that particles; i'zhereof are.- liquicl' under conditions of: coating and. DIQOW essing the emulsion, 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 general formulas:

r x o e legu e-1237c one;

, heterocyclicxnuoleus Of the: quinoline series;

9:. A1; yellow-green; sensitive gelatino-silvers halide: emulsion ioncolorphotography contain-,- in dispersed therein: finely divided: liquid particles; of: azmixture: of a, Fz-IJYrazolonaeolor-iorm-' er for: the magenta image capable of forming; an. azomethine dye with; a phenylenediamine. de-v velopen, and a substantially Water-insoluble low molecular weight, organic, crystal-lodial materialhaving a. boiling point above about 1-75 said crystalloidala material having a high solvent. 346: tion ior-theoolOr-former and for the dye-formed therefrom, andzbeing permeable to photo laphia processing.- solutions, the, nature and proportions, of: the color-former and crystalloidal. materialbeing; so chosen: that particles thereofare liquid under conditions of coating and processing the emulsion, said yellow-green sensitive emulsion being sensitized to, the yellow-green with at least one sensitizing d'ye selected from the group" consisting of those dyes represented by the following general formula;

iI-R,

wherein D2 represents a divalent saturated all-- phatic radical containing from 1' to 4' carbon atoms, Re -represents a primary alkyl group: con;- taining from I tore carbon atoms, X1 represents an anion and: Z3 represents. the non-metallic, atoms, necessary to; complete, a. heterocyclic: nucleus of the quinoiine: series.

I02 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. of the color-former and crystalloidal material belng so chosen that particles thereof are liquid under conditions of coating and processing the emulsion, 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:

IH2 COOH 11. 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:

wherein 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, and X represents an anion, and (II) a yellow-green sensitive silver halide emulsion containing dispersed therein finely divided liquid particles of a mixture of a ketomethylene colorformer for the magenta image capable of forming a quinoneimine dye with a phenylenediamine developer, and a substantially water-insoluble,

iv-p 1-0 H 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 yellow-green sensitive silver halide 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 general formulas:

wherein 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, and Z3 represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the quinoline series.

JOHN SPENCE.

BURT H. CARROLL.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,148,979 Dieterle Feb. 28, 1939 2,148,980 Dieterle Feb. 28, 1939 2,213,238 Broolcer et al. Sept. 3, 1940 2,231,658 Brooker et al. Feb. 11, 1941 2,304,940 Mannes et al Dec. 15, 1942 2,322,027 Jelley et al June 15, 1943 2,478,366 Brooker et a1 Aug. 9, 1949 2,515,913 Van Zandt et al. July 18, 1950

Claims (1)

11. A SENSITIVE SILVER HALIDE EMULSION FOR COLOR PHOTOGRAPHY SELECTED FROM THE GROUP CONSISTING OF (I) A RED SENSITIVE SILVER HALIDE EMULSION CONTAINING 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 HAVING 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:
US2640776A 1947-08-29 1947-08-29 Sensitized photographic emulsion containing color couplers Expired - Lifetime US2640776A (en)

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GB2255448A GB660012A (en) 1947-08-29 1948-08-26 Improvements in photographic emulsions
GB2255548A GB674161A (en) 1947-08-29 1948-08-26 Improvements in photographic emulsions
FR980390A FR980390A (en) 1947-08-29 1948-08-27 A method of making photographic emulsions sensitized containing color couplers and products made by this process
DE1950E0002749 DE972811C (en) 1947-08-29 1950-10-03 Silver halide emulsion for color photography

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US2930694A (en) * 1956-03-19 1960-03-29 Agfa Ag Optical sensitization of direct positive emulsions
US3057724A (en) * 1959-12-11 1962-10-09 Eastman Kodak Co Internal amide, nonpolymeric thioether sensitizers for photographic emulsions
US3255012A (en) * 1960-08-20 1966-06-07 Agfa Ag Sensitized color photographic emulsions and processes containing color couplers
US4080209A (en) * 1975-07-03 1978-03-21 Fuji Photo Film Co., Ltd. Photographic light-sensitive material
US4777122A (en) * 1986-02-24 1988-10-11 Minnesota Mining And Manufacturing Company Silver halide multilayer color photographic material containing couplers having different coupling rates

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL127569C (en) * 1963-08-30
GB1128840A (en) * 1965-11-06 1968-10-02 Fuji Photo Film Co Ltd Supersensitised silver halide emulsions
FR2019427B1 (en) * 1968-09-12 1973-05-11 Fuji Photo Film Co Ltd

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US2148980A (en) * 1936-07-17 1939-02-28 Agfa Ansco Corp Photographic material for color photography
US2148979A (en) * 1936-05-29 1939-02-28 Agfa Ansco Corp Color photography
US2213239A (en) * 1936-09-16 1940-09-03 Eugene V Camp Highway guardrail
US2231658A (en) * 1937-12-16 1941-02-11 Eastman Kodak Co Photographic emulsion
US2304940A (en) * 1939-01-23 1942-12-15 Eastman Kodak Co Color photography
US2322027A (en) * 1940-02-24 1943-06-15 Eastman Kodak Co Color photography
US2478366A (en) * 1944-01-22 1949-08-09 Eastman Kodak Co Polymethine dyes
US2515913A (en) * 1946-11-22 1950-07-18 Eastman Kodak Co 2-methyl-5-phenylbenzothiazole and quaternary salts thereof

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US2148979A (en) * 1936-05-29 1939-02-28 Agfa Ansco Corp Color photography
US2148980A (en) * 1936-07-17 1939-02-28 Agfa Ansco Corp Photographic material for color photography
US2213239A (en) * 1936-09-16 1940-09-03 Eugene V Camp Highway guardrail
US2231658A (en) * 1937-12-16 1941-02-11 Eastman Kodak Co Photographic emulsion
US2304940A (en) * 1939-01-23 1942-12-15 Eastman Kodak Co Color photography
US2322027A (en) * 1940-02-24 1943-06-15 Eastman Kodak Co Color photography
US2478366A (en) * 1944-01-22 1949-08-09 Eastman Kodak Co Polymethine dyes
US2515913A (en) * 1946-11-22 1950-07-18 Eastman Kodak Co 2-methyl-5-phenylbenzothiazole and quaternary salts thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2930694A (en) * 1956-03-19 1960-03-29 Agfa Ag Optical sensitization of direct positive emulsions
US3057724A (en) * 1959-12-11 1962-10-09 Eastman Kodak Co Internal amide, nonpolymeric thioether sensitizers for photographic emulsions
US3255012A (en) * 1960-08-20 1966-06-07 Agfa Ag Sensitized color photographic emulsions and processes containing color couplers
US4080209A (en) * 1975-07-03 1978-03-21 Fuji Photo Film Co., Ltd. Photographic light-sensitive material
US4777122A (en) * 1986-02-24 1988-10-11 Minnesota Mining And Manufacturing Company Silver halide multilayer color photographic material containing couplers having different coupling rates

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GB660012A (en) 1951-10-31 application
GB674161A (en) 1952-06-18 application
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DE972811C (en) 1959-10-01 grant
BE484580A (en) grant

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