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
  • G03C7/32—Colour coupling substances
  • G03C7/36—Couplers containing compounds with active methylene groups
  • G03C7/362—Benzoyl-acetanilide couplers

Definitions

• This invention relates to the production of photographic color images, to yellow forming color couplers used therein and to photographic materials containing such color couplers.
• a light-sensitive photographic color material containing a red-sensitized, a green-sensitized and a blue-sensitive silver halide emulsion layer wherein on color development, by use of appropriate color couplers, a cyan, magenta and yellow dyestuff image are formed respectively.
• the color couplers should meet various requirements; they should possess favorable spectral properties and produce on color development dyes having a high stability against light, heat and humidity.
• novel photographic coupler compounds of the benzoylacetamide type yielding yellow dyes upon coupling with the oxidized aromatic primary amino developing agent are provided corresponding to the following general formula:
• Ar stands for phenylene including substituted phenylene.
• X stands for hydrogen or a substituent that exhibits two equivalent character on color development e.g. a halogen atom, a -S-R, group wherein R, stands for alkyl including substituted alkyl, aryl including substituted aryl, or a heterocycle including a substituted heterocycle, or an -OR group wherein R stands for alkyl including substituted alkyl, aryl including substituted aryl or acyl including substituted acyl such as acetyl and benzoyl, Y stands for a chemical bond, oxygen,
• R hydrogen or alkyl
• D represents a residue rendering the molecule fast to diffusion e.g. an acyclic aliphatic hydrocarbon residue with from five to 20 carbon atoms.
• the benzene nucleus of the arylide part of the molecule may comprise in addition to the ballasting group V-D any substituent that favorably influences the physical, spectral or sensitometric properties of the color couplers e.g. alkyl including substituted alkyl such as sulphoalkyl and carboxyalkyl, aryl including substituted aryl, halogen such as chlorine, a water-solubilizing group suchas a sulpho or carboxyl group in acid or salt form, a fluorosulphonyl group, an alkoxycarbonyl group such as ethoxycarbonyl, a sulfamoyl group including a substituted sulfamoyl group such as diethylsulphamoyl, phenylsulphamoyl, etc., a dialkylamino group e.g.
• an alkylsulphonyl group such as methylsulphonyl
• an alkoxy group such as methoxy
• an alkylthio group such as methyltio
• an aryloxy group including a substituted aryloxy group an arylthio group including a substituted arylthio group.
• the color couplers according to the present invention have a high coupling activity i.e. they furnish dye images with high color density.
• the dye images formed upon color development have a gradation and maximum density exceeding that of the dyes formed with benzoylacetamide color couplers according to the US. Pat. Specification No. 3,056,675 carrying a halogen atom in the ortho-position of the benzoyl part of the molecule.
• the yellow forming benzoylacetamide color couplers according to the present invention can be prepared according to the methods known in the art of preparing benzoylacetamide color couplers by condensing a p-fluorobenzoylacetic acid ester with an aromatic amine containing a diffusion-fast making group.
• the preparation of the amino compounds containinga diffusion-fast making group can be prepared analogously to the preparation technique illustrated hereinafter.
• a detailed description of the preparation of all aromatic amino compounds suitable for being condensed with the pfluorobenzoylacetic acid ester is not deemed necessary since the preparation will not cause difficulties to those skilled in the art of preparative organic chemistry.
• a whole series of aromatic amines which comprise a group rendering the molecule nonmigratory in hydrophilic colloid compositions and which are suitable for being condensed with the pfiuorobenzoylacetic acid ester to form color couplers according to the present invention can be found in United Kingdom Pat. Specifications Nos. 939,030, 983,648, 990,627, 1,039,965, 1,062,203, 1,075,084, 1,099,418, and 1,104,729 and in Belgian Pat. Specification No. 736,253.
• Refractive index (n l of the light yellow oil obtained: 1.51 18.
• b. Z-dodecyloxyaniline was prepared as described in United Kingdom Pat. Specification No. 1,099,418.
• Preparation 7-compound 8 a. 2-hexadecyloxy-5-fluorosulphonylaniline was prepared as described in United Kingdom Pat. Specification No. 983,648. b. 4-fluorobenzoyl-2'-hexadecyloxy-5'-fluorosulphonylacetanilide was prepared according to the method of preparation 1.0) starting from 21 g. of the B-ketoester and 41.5 g. of 2-hexadecyloxy-5-fluorosulphonylaniline. The crude product was recrystallized from cyclohexane and the white crystalline product obtained had a melting point of 100 C. c. The potassium salt of 4-fluorobenzoyl-2'-hexadecyloxy- 5 -sulphoacetanilide was prepared as follows:
• This compound was prepared according to the method of preparation l.c) starting from 21 g. of the B-ketoester and 42.6 g. of the amine of step b).
• the crude product was recrystallized from a mixture of methanol and water and the white crystalline product had a melting point of 98 C.
• the yellow color formers according to the present invention are of the nondiffusible type i.e. they comprise in their molecule an organic radical sufficiently large from preventing the color coupler of wandering from the colloid layer, in which the coupler is incorporated, to another colloid layer.
• the nondiffusing color couplers for each color separation image are usually incorporated into the coating compositions of the differently sensitized silver halide emulsion layers.
• the nondiffusing color couplers may also be added to the coating compositions of nonlight-sensitive colloid layers which are in water-permeable relationship with the light-sensitive silver halide emulsion layers.
• the nonmigratory yellow forming color couplers can be incorporated in the coating composition of the silver halide emulsion layers or other colloid layers in water-permeable relationship therewith according to any technique known by those skilled in the art for incorporating photographic ingredients, more particularly color couplers, into colloid compositions.
• the watersoluble color couplers i.e.
• those containing one or more watersolubilizing groups such as sulpho or carboxyl groups (in acid or salt form) can be incorporated into the coating composition of the layer in question from an aqueous solution and the water-insoluble or insufficiently water-soluble color couplers from a solution in the appropriate water-miscible or water-immiscible high-boiling or low-boiling organic solvents or mixtures thereof whereupon the solution obtained is dispersed, occasionally in the presence of a wetting or dispersing agent, in a hydrophilic colloid composition forming or forming part of the binding agent of the colloid layer.
• the hydrophilic colloid composition may of course comprise in addition to the colloid carrier all other sorts of ingredients.
• the water-insoluble color couplers carrying fluorosulphonyl groups or carboxylic acid ester groups such as ethoxycarbonyl groups can also be converted by alkaline hydrolysis (e.g. as described in United Kingdom Pat. Specification No. 939,030) in the corresponding sulfonic acids or carboxylic acids respectively which in their turn can be incorporated in hydrophilic colloid compositions in the form of their alkali salts from aqueous solutions.
• the solution of said color coupler need not necessarily be dispersed or dissolved directly in the coating composition of the silver halide emulsion layer or other water-permeable layer.
• Said solution may advantageously be first dispersed or dissolved in an aqueous nonlight-sensitive hydrophilic colloid solution whereupon the resultant mixture, after the occasional removal of the organic solvents employed, is intimately mixed with the said coating composition of the light-sensitive silver halide emulsion layer or other water-permeable layer just before coating.
• particularly suitable dispersing techniques that can be employed for incorporating the color couplers of the invention into a hydrophilic colloid layer of a photographic material there can be referred to United Kingdom Pat. Specifications Nos.
• the couplers according to the invention may be used in conjunction with various kinds of photographic emulsions.
• Various silver salts may be used as the sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide, silver bromo-iodide and silver chlorobromoeiodide.
• the couplers can be used in emulsions of the mixed packet type as described in U.S. Pat. Specification No. 2,698,794 or emulsions of the mixed grain type as described in U.S. Pat. Specification No. 2,592,243.
• the color couplers can be used with emulsions wherein latent images are formed predominantly on the surface of the silver halide crystal, or with emulsions wherein latent images are formed predominantly inside the silver halide crystal.
• the hydrophilic colloid used as the vehicle for the silver halide may be, for example, gelatin, colloidal albumin, zein, casein, a cellulose derivative, a synthetic hydrophilic colloid such as polyvinyl alcohol, poly-N-vinyl pyrrolidone, etc. if desired, compatible mixtures of two or more of these colloids may be employed for dispersing the silver halide.
• the light-sensitive silver halide emulsions of use in the preparation of a photographic material according to the present invention may be chemically as well as optically sensitized. They may be chemically sensitized be effecting the ripening in the presence of small amounts of sulfur containing compounds such as allyl thiocyanate, allyl thiourea, sodium thiosulphate, etc.
• the emulsions may also be sensitized by means of reductors for instance tin compounds as described in French Pat. Specification No. 1,146,955 and in Belgian Pat. Specification No. 568,687, imino-amino methane sulfinic acid compounds as described in United Kingdom Pat. Specification No. 789,823 and small amounts of noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium compounds. They may be optically sensitized by means of cyanine and merocyanine dyes.
• the said emulsions may also comprise compounds which sensitize the emulsions be development acceleration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in U.S. Pat. Specifications Nos. 2,531,832 and 2,533,990, in United Kingdom Pat. Specifications Nos. 920,637, 940,051, 945,340 and 991,608 and in Belgian Pat. Specification No. 648,710 and onium derivatives of amino-N-oxides as described in United Kingdom Pat. Specification No. 1,121,696.
• compounds which sensitize the emulsions be development acceleration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in U.S. Pat. Specifications Nos. 2,531,832 and 2,533,990, in United Kingdom Pat. Specifications Nos. 920,637, 940,051, 945,340 and 991,608 and in Belgian Pat. Specification No. 648,710 and on
• the emulsions may comprise stabilizers e.g. heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline -2-thione and l-phenyl-2-tetrazoline-5-thione and compounds of the hydroxytriazolopyrimidine type.
• stabilizers e.g. heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline -2-thione and l-phenyl-2-tetrazoline-5-thione and compounds of the hydroxytriazolopyrimidine type.
• The can also be stabilized with mercury compounds such as the mercury compounds described in Belgian Pat. Specifications Nos. 524,121 and 677,337, United Kingdom Pat. Application No. l,l73,609 and in U.S. Pat. Specification No. 3,179,520.
• the light-sensitive emulsions may also comprise all other kinds of ingredients such as plasticizers, hardening agents, wetting agents, etc.
• the nondifi'using yellow color formers described in the present invention are usually incorporated into a blue-sensitive silver halide emulsion for forming one of the differently sensitized silver halide emulsion layers of a photographic multilayer color material.
• a photographic multilayer color material usually comprises a support, a red-sensitized silver halide emulsion layer with a cyan color former, a green-sensitized silver halide emulsion layer with a magenta color former and a blue-sensitive silver halide emulsion layer with a yellow color former.
• the emulsions can be coated on a wide variety of photographic emulsion supports.
• Typical supports include cellulose ester film. polyvinylacetal film, polystyrene film, polyethylene terephthalate film and related films or resinous materials as well as paper and glass.
• an exposed silver halide emulsion layer is developed with an aromatic primary amino developing substance in the presence of a color coupler according to the present invention.
• All color developing agents capable of forming azomethine dyes can be utilized as developers.
• Suitable developing agents are aromatic compounds such as p- EXAMPLE 1 1 17 g. of a blue-sensitive silver bromoiodide emulsion (2.3 mole percent of iodide) which comprises per kg. 73.4 g. of gelatin and an amount of silver halide equivalent to 47 g. of silver nitrate, are composition: 192.5 g. of a 7.5% aqueous solution of gelatin and g. of distilled water.
• color coupler 5 of the above list of color couplers prepared by dissolving at 55 C. 0.006 mole of the color coupler in 54 ml. of distilled water, 6 ml. of 2 N sodium hydroxide and 18 ml. of ethanol.
• the common additives such as stabilizers, wetting agents, and hardeners
• the necessary amount of distilled water to obtain 575 g. of emulsion is added whereupon the emulsion is coated on a cellulose triacetate support pro rate of g. per sq. m.
• the emulsion layer is dried and overcoated with a gelatin antistress layer.
• the material formed is exposed for l/20 sec. through a continuous wedge with constant 0.30 and then developed for 8 min. at 20 C. in a developing bath of the following composition:
• N:N-diethyl-p-phenylene diamine sulfate 2.75 g. hydroxylamine sulfate [.2 g. sodium hexamethaphosphate 4 g. anhydrous sodium sulfite 2 g. anhydrous potassium carbonate 75 g. potassium bromide 2.5 g
• the developed material is treated for 2 min. at 18-20 C. in an intermediate bath comprising 30 g. of sodium sulfate in 1 liter of water.
• the material is rinsed for 15 min. with water and treated in a bleach bath of the following composition:
• a yellow colored wedge image is obtained having an absorption maximum of 426 nm.
• Example 1 is repeated with the difference that color coupler 5 is replaced by 0.006 mole of color coupler 9.
• a yellow colored wedge image is obtained having an absorption maximum of 448 nm.
• EXAMPLE 3 1 17 g. of a blue-sensitive silver bromo-iodide emulsion (2.3 mole percent of iodide) containing per kg. 73.4 g. of gelatin and an amount of silver halide equivalent to 47 g. of silver nitrate are melted and diluted with 192.5 g. of a 7.5 percent aqueous solution of gelatin and 100 g. of distilled water. To the emulsion obtained is added a gelatin gel comprising a dispersion of color coupler 6 prepared by admixing by means of an ultrasonic wave generator a solution of 0.006 mole of said color coupler in a mixture of 14 ml. of ethyl acetate, 1.5 ml.
• EXAMPLE 4 I I? g. of a blue-sensitive silver bromo-iodide emulsion (2.3 mole percent of iodide) containing per kg. 73.4 g. of gelatin and an amount of silver halide equivalent to 47 g. of silver nitrate are melted and diluted with 192.5 g. of a 7.5 percent aqueous solution of gelatin and W g. of distilled water. To the emulsion obtained is added a gelatin gel comprising a dispersion of color coupler 1 prepared by admixing by means of an ultrasonic wave generator a solution of 0.006 mole of said color coupler in 14 ml. of ethyl acetate with l00 ml.
• Example 4 is repeated with the difference that color coupler l is replaced by 0.006 mole of color couplers 4 and 7 respectively.
• Yellow colored wedge images are obtained having absorption maxima of446 nm. and 438 nm. respectively.
• EXAMPLE 7 Material containing Gradation Maximum Absorption density maximum color cou ler 8 of U.S. Patent color coupler 2 L09 2.55 424
• the yellow forming color couplers of the invention form on color development yellow dye images with improved gradation and maximum density as compared with the dye images formed from the yellow forming color couplers according to U.S. Pat. Specification No. 3,056,675.
• Ar stands for a phenylene group
• X stands for hydrogen or a substituent that exhibits two equivalent character on color development
• D stands for an acyclic aliphatic hydrocarbon residue with from five to 20 carbon atoms
• Y stands for a chemical bond, oxygen, sulfur, sulphonyl, N
• Photographic light-sensitive silver halide material comprises, in addition to the group -YD. a substituent selected from an alkyl group, an aryl group, a halogen atom, a sulpho group in acid or salt form, a carboxyl group in acid or salt form, a fluorosulphonyl group, an alkoxycarbonyl group, a sulfamoyl group, an alkylsulphonyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, and a dialkylamino group.
• a substituent selected from an alkyl group, an aryl group, a halogen atom, a sulpho group in acid or salt form, a carboxyl group in acid or salt form, a fluorosulphonyl group, an alkoxycarbonyl group, a sulfamoyl group, an alkylsulphonyl group, an alk
• Photographic material according to claim 1 wherein said material is a multilayer color material containing one of the light-sensitive silver halide emulsion layers or in a nonlightsensitive water-permeable colloid layer in water-permeable relationship with the light-sensitive silver halide emulsion layer the said color coupler.
• Photographic material according to claim I wherein said material is a multilayer color material comprising three silver halide emulsion layers which are differently optically sensitized, the blue-sensitive silver halide emulsion layer or a nonlight-sensitive colloid layer in water-permeable relationship therewith containing the said color coupler.
• Ar stands for a phenylene group
• X stands for hydrogen or a substituent that exhibits two equivalent character on color development
• D stands for an acydic aliphatic hydrocarbon residue with from five to 20 carbon atoms
• the benzene nucleus of the arylide part of the said color coupler comprises, in addition to the group Y-D, a substituent selected from an alkyl group, an aryl group, a halogen atom, a sulpho group in acid or salt form. a carboxyl group in acid or salt form, a fluorosulphonyl group, an alkoxycarbonyl group, a sulfamoyl group, an alkyl-sulphonyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group and a dialkylamino group.

Landscapes

• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=10041891

Family Applications (1)

Country Status (7)

Cited By (1)

Citations (3)

• 1969
  • 1969-03-19 GB GB04476/69A patent/GB1292462A/en not_active Expired
• 1970
  • 1970-02-16 US US11816A patent/US3619190A/en not_active Expired - Lifetime
  • 1970-02-23 FR FR7006453A patent/FR2037410A5/fr not_active Expired
  • 1970-02-27 CH CH280570A patent/CH532800A/de not_active IP Right Cessation
  • 1970-02-28 DE DE19702009495 patent/DE2009495A1/de active Pending
  • 1970-03-16 JP JP45022563A patent/JPS4816375B1/ja active Pending
  • 1970-03-19 BE BE747588D patent/BE747588A/fr unknown

Patent Citations (3)

Also Published As

Similar Documents