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
  • 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
  • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
• • 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
• • 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
  • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
• • 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
  • 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
  • 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
  • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
  • G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed
• • 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
  • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
• • 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
  • G03C7/32—Colour coupling substances

Definitions

• Silver halide emulsions are advantageously green-sensitized with a supersensitizing combination of (1) certain oxacarbocyanine dyes that have no more than one phenyl substituent and (2) certain benzimidazolocarbocyanine dyes and further sensitized by processing them in the presence of certain silver halide thioether sensitizers that are incorporated in the immediate green-sensitized emulsion layer, another layer in the photographic element containing the green-sensitized emulsion layer or incorporated in a color developing solution containing a p-phenylenediamine used to process the immediate emulsion, provided the thioether is present in the emulsion during color development.
• the immediate supersensitized emulsions containing the thioether sensitizer are especially advantageous when processed in a color developer solution containing a dialkylamino-p-phenylenedian1ine color developin g agent because of synergistic increases in green speed of up to about 336%.
• This invention relates to photographic silver halide emulsions and, in particular, one aspect of this invention relates to an improved means for sensitizing photographic silver halide emulsions containing color-forming compounds or couplers.
• the sensitization produced by a given dye varies somewhat with the type of emulsion in which the dye is incorporated or by varying the conditions in the emulsion.
• the sensitization may be increased by increasing the silver ion concentration or decreasing the hydrogen ion concentration (i.e., increasing the alkalinity), or both.
• Sensitization can also be increased by bathing supports coated with a spectrally sensitized emulsion in water or in aqueous solutions of ammonia.
• hypersensitization Such a process of altering the sensitivity of a sensitized emulsion by increasing the silver ion concentration and/or by decreasing the hydrogen ion concentration is commonly called hypersensitization. Hypersensitized emulsions have generally exhibited poor keeping qualities.
• Another object is to provide a novel multicolor, multilayer photographic element containing incorporated color-forming couplers.
• Another object is to provide a novel multilayer, multicolor element process combination for increasing the speed of the green-sensitive emulsion layer as much or more than the speed of the red-sensitive emulsion layer and blue-sensitive emulsion layers of said element.
• Another object is to provide a synergistic speed increase in the green-sensitive layer of my novel multilayer color-forming coupler incorporating element by using my color development process.
• the use of the preferred green-sensitizers in conjunction with a thioether sensitizer in an incorporated-coupler color element processed in a dialkyl-p-phenylenediamine color developer appears to produce synergistic effects in that the speed obtained in this manner is significantly greater than the speeds obtained (1) when elements containing conventional green sensitizers plus a thioether sensitizer are processed in a dialkyl-p-phenylenediamine color developer, or (2) when elements containing the preferred green sensitizers plus a thioether sensitizer are processed in a sulfonamido-pphenylenediamine color developer.
• part or all of the thioether can be in layers other than the greensensitive layer or can be in the color developer provided the thioether is present in the element during color development.
• oxacarbocyanine dyes utilized in my invention include these represented by the formula:
• G and G each represents a group, such as, a halogen atom (e.g., chloride, bromide, iodine, fluorine), the hydroxyl group, an alkoxy group (e.g., methoxy, ethoxy, propoxy, butoxy, etc.), an amino group (e.g., amino, methylamino, dimethylamino, diethylamino, etc.), an acylamido group (e.g., acetamido, propionamido, butyramido, etc.), an acyloxy group (e.g., acetoxy, propionoxy, etc.), a carbalkoxy group (e.g., carbethoxy, carbopropoxy, carbobutoxy, etc.), an alkoxycarbonylamino, group (e.g., ethoxycarbonylamino propoxycarbonylamino, butoxycarbonylamino, etc.),
• W and Y each represents the same or difierent group, such as, the hydrogen atom, a halogen atom (e.g., chlorine, bromine, iodine, fluorine), an alkoxy group (methoxy, ethoxy, butoxy, etc.), an amino group (e.g., amino, methylamino, dimethylamino, diethylamino, etc.), an acylamido group (e.g., acetamido, propionamido, butyramido, etc.), an acyloxy group (e.g., acetoxy, propionoxy, etc.), an alkoxycarbonylamino group (e.g., ethoxycarbonylamino, propoxycarboxylamino, etc.); W and Y each represents the same or different group, such as, the hydrogen atom, and a halogen atom (e.g., chlorine, bromine, iodine, and fluorine);
• Typical examples illustrating the dyes of Formula I include those in which the substituents of the said formula are defined by the following table.
• G G, G2 G; R; R Z X6 5-(31 H suliopropyL. sultopropyl" ethyl none. 5-pheuy1 H suliobutyl sulfopropyL- ethyl none. 5-phenyl. H sulfobutyl sulfopropyL. ethyl none.
• R is an aliphatic radical having from 2 to 20 carbon atoms and e represents a positive integer of at least 2, the depicted sulfur atom being attached to a carbon atom of R said carbon atom having directly attached thereto the hydrogen atom.
• the terminal groups of such polymers are generally hydrogen atoms, halogen atoms, alkenyl groups (e.g., vinyl, allyl, etc.), carboxylic groups (e.g. carboxyl, carboxylic amide, carboxylic ester, such as carbomethoxyl, carbethoxyl, etc.), hydroxyl groups (or salts thereof, e.g., sodium, potassium, etc.), or combinations of these.
• linear polymers represented by Formula III above comprise a well-known class of polymeric materials.
• Typical of the polymers embraced by Formula III are those polymers represented by the following formula:
• R R R and R each represents a hydrocarbon alkylene group containing from about 2 to 20 carbon atoms (e.g., ethylene, trimethylene, 1,2-propylene, tetrabutylene, pentamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, etc.), L and L each represents an oxygen atom, a sulfur atom, an amino group (substituted or not) such as amino, methylamino, ethylamino, etc., carbamyl (-NHCO), carbonylamido (CONH-), carbonyl, oxycarbonyloxy, oxycarbonyl (OOC), carbonyloxy (-COO), etc., provided that L does not represent an oxycarbonyl group when L represents a carbonyloxy group and L does not represent a carbamyl group when L represents a carbonylamido group, and p and 7 each represents a positive integer of from 1 to 5, and g represents the values given
• a, b, c, and d each represents a positive integer of from 2 to 20 and g, f, and p each have the values given above.
• Typical thioether sensitizers useful in my invention are: (1) Poly-2-2-thiodiethyl succinate [IO-(f CH2 GH2E-O-CH2 CH2S CH2 CH2] (2) 1,17-di[N-ethyl carbamyl] 6,12 dithia-9-oxaheptadecane [C2H5NH C CH2) 5-S CH2)2-]2O (3 6,l2-dithia-1,17-heptadecanediol HO( CH S-( CH S-(CH ,-,OH (4) 3,6-dithia-l,8-octanediol (5) Pentamethylene bis[(2-hydroxyethyl)-methylsulfonium p-toluenesulfonate] (6) Poly[thiodiethylene glutarate] CO(CH2)2S(CH2)2OC(CHz) [ll 1.
• my sensitizing combinations can be employed in photographic silver halide emulsions in which the carrier or vehicle is a hydrophilic colloid other than gelatin or utilized with gelatin, such as, for example, albumin, agaragar, gum arabic, alginic acid, etc., or a hydrophilic resin such as polyvinyl alcohol, polyvinyl pyrrolidone, a cellulose ether, a partially hydrolyzed cellulose acetate, an alkyl a-crylate-acrylic acid resin, etc., which has no deleterious effect upon the light-sensitive silver halide.
• a hydrophilic colloid other than gelatin or utilized with gelatin such as, for example, albumin, agaragar, gum arabic, alginic acid, etc.
• a hydrophilic resin such as polyvinyl alcohol, polyvinyl pyrrolidone, a cellulose ether, a partially hydrolyzed cellulose acetate, an alkyl a-cry
• the dyes of Formula I and Formula II can be employed in the combinations of the invention in various concentrations depending upon the particular emulsion, concentration of the silver halide, particular results desired, etc.
• the optimum concentration of a sensitizing dye can be determined in a manner well known to those skilled in the art by measuring the sensitivity of a series of test portions of the same emulsion, each portion containing a different concentration of the sensitizing dye.
• the optimum concentration of my sensitizing combinations can, of course, be readily determined in the same manner, by measuring the sensitivity of a series of test portions of the same emulsion, each portion containing different concentrations of the. individual components in the combination.
• concentrations of the individual dyes less than their optimum concentrations.
• concentrations of the individual dyes can then be increased until the optimum concentration of the supersensitizing combination is determined.
• sensitizing dyes in silver halide emulsions are well known to those skilled in the art and these known techniques are employed in dispersing the dyes of my invention in the emulsions.
• These sensitizing dyes can be directly dispersed in the emulsions, or they can first be dissolved in some convenient solvent, such as pyridine, methyl alcohol, acetone, etc. (or mixtures of such solvents), or diluted with Water in some instances, and added to the emulsions in the form of these solutions.
• the dyes can be separately dissolved in an appropriate solvent and added separately to the emulsion, or they can be dissolved in the same or different solvent and these solutions mixed together before addition is made to the silver halide emulsions.
• the dyes can be dispersed in the finished emulsions and should be uniformly distributed throughout the emulsions before the emulsions are coated on a suitable support, such as, paper, glass, cellulose ester film, polyvinyl resin film (e.g., polystyrene film, polyvinyl chloride film, etc.) polyester film, etc.
• the sensitized emulsions can then be coated on a suitable support and the coating allowed to dry. In some instances, it may be desirable to heat the emulsion for a few minutes before coating onto the suitable support.
• the details of such coating techniques are well known to those skilled in the art. The foregoing procedure and proportions are to be regarded only as illustrative.
• my invention is directed to any silver halide emulsion containing a combination of the afor said dyes with a thioether sensitizer whereby a supersensitizing effect is obtained.
• the color-formers are incorporated in the emulsions in the customary manner, e.g., by adding a dispersion of the coupler in a water-insoluable but Waterpermeable material to the emulsion, or by adding a dispersion of the alkali metal salt of the coupler in water.
• the coupler (color former) which has been mixed with the high-boiling organic crystalloidal material to produce an oil-like mixture can be dispersed in water or gelatin solution or in any aqueous binder of colloidal 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 subsequently removing the low-boiling solvent by evaporation.
• a solvent of low boiling point such as butyl acetate with water or gelatin solution
• an emulsifying agent can be used.
• the mixture of coupler and crystalloidal material may be dissolved in a solvent of low boiling point such as butyl acetate with water or gelatin solution and subsequently the low-boiling solvent is removed by evaporation.
• a solvent of low boiling point such as butyl acetate with water or gelatin solution
• an emulsifying agent can be used. It is important that the mixture of coupler and crystalloidal material be a liquid at ordinary temperatures so that liquid particles are formed
• the mixture of coupler and crystalloidal material is emulsified in water and mixed with the emulsion, the particles retaining the coupler in solution, yet being readily penetrated by the photographic developing solution and other processing baths.
• the nature and propotrions 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.
• crystalloidal materials 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 materials should also be substantially colorless and stable toward light, heat and moisture, in addition to being inert to the various processing baths which may be encountered, such as developers, oxidized developers, silver removal baths and fixing baths. They should have a sufficiently low refractive index so that solutions of the couplers in them have approximately the same refractive index as gelatin, thereby minimizing the opacity or light scattering of the coating.
• the crystalloidal materials should be easily dis persible in the emulsions and should be chemically inert toward the couplers and dyes formed therefrom.
• My invention is directed primarily to the ordinarily employed gelatino silver halide developing-out emulsions in which the silver halide can be silver chloride, silver chlorobromide, silver chlorobromoiodide, silver iodochloride, silver bromide and silver bromiodide.
• These ordinarily employed silver halide developing-out emulsions are emulsions which form surface latent image (see British Patent 581,772, accepted Oct. 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 my invention.
• the coupler compounds used in the emulsion layers sensitized according to my invention are any of the wellknown compounds which combine with the oxidation product of primary aromatic amino silver halide color developing agents to form dyes, for example, the cyanforming phenolic couplers of US. Patents 2,266,452; 2,362,598; 2,589,004; 2,474,293; 2,521,908; 2,423,730; the magenta-forming pyrazolone couplers of US. Patents 1,969,479; 2,369,489; 2,600,788; 2,618,641; 2,511,231 and the yellow-forming open-chain reactive methylene couplers of US.
• the emulsions may contain colored color-forming couplers as described in US. Patents 2,521,908; 2,706,684; 2,455,169; 2,694,703; 2,455,170; 2,453,661; 3,034,892; and 2,983,608.
• the emulsions can be chemically sensitized by any of the accepted procedures.
• the emulsions can be digested with naturally active gelatin, or sulfur compounds can be added such as those described in Sheppard US. Patents 1,574,944 and 1,623,499, and Sheppard and Brigham US. Patent 2,410,689.
• the emulsions can also be treated with salts of the noble metals such as ruthenium, rhodium, palladium, iridium and platinum, all of which belong to Group VIII of the Periodic Table of elements and have an atomic weight greater than 100.
• Rrepresentative compounds are ammonium chloropalladate, potassium chloroplatinate and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli US. Patent 2,448,060, and as antifoggants in higher amounts as described in Trivelli and Smith US. Patents 2,566,245 and 2,566,263.
• the emulsions can also be chemically sensitized with gold salts as described in Waller and Dodd US. Patent 2,399,083 or stabilized with gold salts as described in Damschroder US. Patent 2,597,856 and Yutzy and Leermakers US. Patent 2,597,915.
• Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2-aurosulfobenzothiazole methochloride.
• any undesirable fog in the sensitized emulsions of my invention can be suppressed and reduced to normal levels by using various compounds such as the mercury compounds of Allen, Byers and Murray US. Patent 2,728,663; Carroll and Murray US. Patent 2,728,664; Leubner and Murray U.S. Patent 2,728,665; the ballasted hydroquinones of Thirtle et a1.
• any of the well known primary aromatic amino colorforming silver halide developing agents such as the pphenylenediamines (e.g., diethyl-p-phenylenediamine, dimethyl-p-phenylenediamien, 2 amino-5-diethylaminotoluene, monomethyl-p-phenylenediamine, 2 amino 5- (n-ethyl-N-laurylamino)toluene, N ethyl-N-(fi-methanesulfonamidoethyl) 4 aminoaniline, 4 [N ethyl N- (6 hydroxyethyl)amino]aniline, etc.), the p-aminophenols and their substittution products where the amino group is unsubstituted can be used to advantage in the color development of my color elements.
• the p-aminophenols and their substittution products where the amino group is unsubstituted can be used to advantage in
• the aqueous alkaline color developer solution used to advantage contain, in addition to the color developing agent, any of the usual components, e.g., alkali metal carbonates, sulfites, iodides, bromides, phosphates, etc.,
• EXAMPLE 1 Single layer coatings of the incorporated coupler type which varied only in the green sensitizers therein were prepared.
• Two coatings were made in which the indicated sensitizers were used. Two samples of each coating were exposed in an intensity scale sensitometer with one sample processed, as indicated below, in the Eastman Color Negative (ECN) film process and the other processed in the Eastman Color Print (ECP) process.
• ECN Eastman Color Negative
• ECP Eastman Color Print
• Dye I 3-carboxymethyl 1 ethylthia 2' cyanine iodide (.0875 g./silver mole).
• Dye II 9-ethyl 3,3 di( ⁇ 3 methoxyethyl 5,5 diphenyl)- oxacarbocyanine iodide (.0875 g./silver mole).
• Dye III Anhydro 5,5 dichloro 9 ethyl 3,3 di(3-sulfopropyl)-oxacarbocyanine hydroxide, sodium salt (.300 g./ silver mole), and
• Dye V Anhydro 5,5,6,6 -tetrachloro 1,1,3 triethyl-3-(3- sulfobutyl)-benzimidazocarbocyanine hydroxide (.120 g./ silver mole).
• Coating C outside the invention was similar to Coating B but contained no 1,17-di[N-ethylcarbamy1]- 6,12-dithia-9-oxaheptadecane or other thioethers.
• Coating E outside my invention used as control, was similar to Coating C of Example 2.
• Coating F was the control +0.25 g. of poly[thiodiethylene glutarate] per silver mole.
• Coating G was the control +0.5 g. of poly [thiodiethylene glutarate] per silver mole.
• Coating H was the control +0.75 g. of poly[thiodiethylene glutarate] per silver mole.
• Coating I was the control +0.12 g. of l,l7di-[N-ethylcarbamyl]-6,l2-dithia-9-oxaheptadecane per silver mole.
• Coating I was the control +0.25 g. of 1,17-di-[N- ethylcarbamyl]-6,l2-dithia-9-0xaheptadecane per silver mole.
• Coating K was the control +0.12 g. of 6,12-dithia-l, 17-heptadecane diol per silver mole.
• EXAMPLE 4 The following basic multilayer color elements structure was utilized in this example.
• Blue-sensitive gelatino silver halide emulsion layer containing an open-chain coupler compound of the type described in US. Patent 2,875,057 containing a reactive methylene group for formation of a yellow image.
• Element A (control for Elements B, C and D) contained the following combination of Dyes I, II and II in Layer 3:
• Element B was the same as Element A, but in addition to Dyes I, H and III contained 0.5 g./silver mole of the linear thioether compound poly[thiodiethylene glutarate];
• Element C was the same as Element B but had 0.5 g./silver mole of poly[thiodiethylene glutarate] in Layer 1.
• Element D was the same as Element C but had 0.5 g./ silver mole of poly[thiodiethylene glutarate] in Layer 5.
• Element E (control for Elements F, G and H) contained the following combination of Dyes IV and V in Layer 3:
• Dye V.l g./silver mole Element F was the same as Element E but in addition to Dyes IV and V contained 0.5 g./silver mole of poly[thiodiethylene glutarate] in Layer 3.
• Element G was the same as Element F but contained 0.5 g./silver mole of poly[thiodiethylene glutarate] in Layer 1.
• Element H was the same as Element G but contained 0.5 g./silver mole of poly[thiodiethylene glutarate] in Layer 5.
• Elements F to H are elenmts of my invention, Elements A to E represent elements of the prior art and are included for comparative purposes.
• A (control for B, C and D) 100 100 100 B 110 91 105 110 80 102 110 126 100 100 94 132 105 107 135 110 97 132 132 is used.
• the following data were obtained by processing Elements A through H in the ECP Process.
• Table II shows that when the thioether sensitized Elements, B, C and D that are outside my invention are processed according to my invention with a dialkylsubstituted-p-phenylenediamine color developing agent, the green-speed is increased by more than 100%. This is unexpected from the results shown in Table I for these same elements.
• Table II shows the apparent synergistic green speed increase of from 289 to 336% produced in my Elements F, G and H when they are processed with a dialkyl-substituted p-phenylene-diamine color developing agent. Similar results are obtained when other dialkyl-substituted pphenylene diamine color developing agents are used in place of Color Developing Agent I. As stated before, similar results are obtained by incorporating all or part of the thioether compound in one or more layers of the element continguous to the green-sensitive layer or incorporating all or part of the thioether compound in the color developer solution.
• My invention provides valuable methods for increasing the green speed in green-sensitized photographic silver halide emulsion layers which have been sensitized with thioether compounds by using a preferred combination of sensitizing dyes and color developing with any of the color developing agents or where the preferred combination of sensitizing dyes is not user, color developing with a dialkyl-substituted-p-phenylenediamine color developing agent.
• Substantial and unexpected increases in green speed are obtained by using my color element-color process system. Synergistic increases in green speed of up to 336% are obtained by color developing my preferred color elements with a dialkyl-substituted-p-phenylcne diamine color developing agent.
• G and G each represent a group selected from the class consisting of a halogen atom, the hydroxyl group, an alkoxy group, an amino group, an acylamido group, an acyloxy group, a carbalkoxy group, an alkoxycarbamylamino group, and a phenyl group, such that not more than one of G and G represents a phenyl group;
• G and G each represent a group selected from the class consisting of the hydrogen atom and a halogen atom;
• R represents an alkyl group;
• R represents an alkyl group;
• n represents an integer of from 1 to 2, such that n represents the integer 1 when at least one of R and R represents a group selected from the class consisting of a sulfoalkyl group and a carboxyalkyl group;
• W and Y each represents a group selected from the class consisting of the hydrogen atom, a halogen atom, an alkoxy group, an amino group, an acylamido group, an acyloxy group, and an alkoxycarbonylamino group;
• W and Y each represents a group selected from the class consisting of the hydrogen atom and a halogen atom;
• R represents an alkyl group;
• R represents an alkyl group;
• R and R each represents a group selected from the class consisting of an alkyl group, a sulfoalkyl group and a carboxyalkyl group;
• X represents an acid anion;
• m represents an integer of from 1 to 2, such that m represents the integer 1 when at least one of R and R represents a group selected from the class consisting of a sulfoalkyl group and a carboxyalkyl group;
• R is an aliphatic radical having from 2 to 20 carbon atoms, and 2 represents a positive integer of at least 2, the depicted sulfur atom being attached to a carbon atom of said R radical, said carbon atom having directly attached thereto the hydrogen atom.
• At least one oxacarbocyanine dye having the forwherein G and G each represent a group selected from the class consisting of a halogen atom, the hydroxyl group, an alkoxy group, an amino group, an acylamido group, an acyloxy group, a carbalkoxy group, an alkoxycarbamylarnino group, and a phenyl group, such that not more than one of G and G represents a phenyl group;
• G and G each represent a group selected from the class consisting of the hydrogen atom and a halogen atom;
• R represents an alkyl group;
• R represents an alkyl group;
• Z represents a group selected from the class consisting of the hydrogen atom, an alkyl group and an aryl group;
• X represents an acid anion;
• n represents an integer of from 1 to 2, such that n represents the integer 1 when at least one of R and R represents a group selected from the class consisting of a
• W and Y each represents a group selected from the class consisting of the hydrogen atom, a halogen atom, an alkoxy group, an amino group, an acylamido group, an acyloxy group, and an alkoxycarbonylamino group;
• W and Y each represents a group selected from the class consisting of the hydrogen atom and a halogen atom;
• R represents an alkyl group;
• R represents an alkyl group;
• R and R each represents a group selected from the class consisting of an alkyl group, a sulfoalkyl group and a carboxyalkyl group
• X represents an acid anion; and
• m represents an integer of from 1 to 2, such that m represents an integer 1 when at least one of R and R represents a group selected from the class consisting of a sulfoalkyl group and a carboxyalkyl group;
• R represents a hydrocarbon alkylene group containing from about 2 to 20 carbon atoms;
• R represents a hydrocarbon alkylene group containing from about 2 to 20 carbon atoms;
• R represents a hydrocarbon alkylcne group containing from about 2 to carbon atoms;
• R represents a hydrocarbon alkylene group containing from about 2 to 20 carbon atoms;
• L and L each represents a member selected from the class consisting of oxygen, sulfur, the amino group, an alkylamino group, the carbamyl group, the carbonylamido group, the carbonyl group, the oxycarbonyloxy group, the oxycarbonyl group, the carbonyloxy group, such that L does not represent an oxycarbonyl group when L represents the carbonyloXy group, and L does not represent the carbamyl group when L represents the carbonylamido group;
• p and 7 each represents a positive integer of from 1 to 5 and g represents a positive integer of at least 2.
• R represents a hydrocarbon alkylene group containing from about 2 to 20 carbon atoms
• R represents a hydrocarbon alkylene group containing from about 2 to 20 carbon atoms
• It represents an integer of from 1 to 3.
• a multicolor, multilayer light-sensitive element for color photography containing a green-sensitized silver halide emulsion layer having incorporated therein a magenta-forming coupler, the improvement comprising the addition to said emulsion of:
• G and G each represent a group selected from the class consisting of a halogen atom, the hydroXyl group, an alkoxy group, an amino group an acylamido group, an acyloxy group, a carbalkoxy group, an alkoxycarbonyl amino group, and a phenyl group, such that not more than one of G and G represents a phenyl group;
• G and G each represent a group selected from the class consisting of the hydrogen atom and a halogen atom;
• R represents an alkyl group;
• R represents an alkyl group;
• Z represents a group selected from the class consisting of the hydrogen atom, an alkyl group and an aryl group;
• X represents an acid anion;
• n represents an integer of from 1 to 2, such that n represents the integer 1 when at least one of R and R represents a group selected from the class consisting of a sulfoalkyl group and a carboxyalkyl group;
• W and Y each represents a group selected from the class consisting of the hydrogen atom, a halogen atom, an alkoxy group, an amino group, an acylamido group, an acyloxy group, and an alkoXycar-bonylamino group
• W and Y each represents a group selected from the class consisting of the hydrogen atom and a halogen atom
• R represents an alkyl group
• R represents an alkyl group
• R and R each represents a group selected from the class consisting of an alkyl group, a sulfoalkyl group and a carboxyalkyl group
• X represents an acid anion
• m represents an integer of from 1 to 2, such that m represents the integer 1 when at least one of R and R represents a group selected from the class consisting of a sulfoalkyl group and a carboxyalkyl group; and theaddition to at least one layer of
• R is an aliphatic radical having from 2 to 20 carbon atoms
• e represents a positive integer of at least 2
• the depicted sulfur atom being attached to a carbon atom of said R radical, said carbon atom having directly attached thereto the hydrogen atom.
• a process for color photography comprising the step of contacting an image exposed multilayer, multicolor photographic silver halide element having as the green-sensitive layer a silver halide emulsion containing:
• X represents an acid anion
• m represents an integer of from 1 to 2, such that m represents the integer 1 when at least one of R and R represents a group selected from the class consisting of a sulfoalkyl group and a carboxyalkyl group; with an aqueous alkaline color developer containing a p-phenylene-diamine color developing agent in the presence of a thioether sensitizer for silver halide having the formula:
• R is an aliphatic radical having from 2 to carbon atoms, and e represents a positive integer of at least 2, the depicted sulfur atom being attached to a carbon atom of said R radical, said carbon atom having directly attached thereto the hydrogen atom.
• R represents an alkyl group
• Z represents a group selected from the class consisting of 20 the hydrogen atom, an alkyl group and an aryl group
• X represents an acid anion
• n represents an integer of from 1 to 2, such that n represents the integer 1 when at least one of R and R represents a group selected from the class consisting of a sulfoalkyl group and a carboxyalkyl group;
• oxacarbocyanine dye is anhydro-5,5'-dichloro- 9-ethyl-3,3-di(3-sulfopropyl) -oxacarbocyanine hydroxide, sodium salt.
• Eolumn 6, line 14.6, delete the second "S” in that part of the formula which reads "-S-S(CH -S" so that this part of the formula will read ----S-(GH S Column 12, line 6, between "and” and “in”, delete "II” and substitute in its place ---III--.

Landscapes

• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=24023349

Family Applications (1)

Country Status (5)

Cited By (5)

Families Citing this family (5)

Citations (7)

• 1965
  • 1965-11-18 US US508596A patent/US3506443A/en not_active Expired - Lifetime
• 1966
  • 1966-11-17 FR FR83933A patent/FR1499805A/fr not_active Expired
  • 1966-11-17 DE DE1966E0032861 patent/DE1547751B2/de active Granted
  • 1966-11-17 GB GB51518/66A patent/GB1163429A/en not_active Expired
  • 1966-11-17 BE BE689856D patent/BE689856A/xx unknown

Patent Citations (7)

Also Published As

Similar Documents