US3843365A - Yellow forming colour couplers for photographic silver halide material - Google Patents

Yellow forming colour couplers for photographic silver halide material Download PDF

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Publication number
US3843365A
US3843365A US00232184A US23218472A US3843365A US 3843365 A US3843365 A US 3843365A US 00232184 A US00232184 A US 00232184A US 23218472 A US23218472 A US 23218472A US 3843365 A US3843365 A US 3843365A
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colour
silver halide
coupler
photographic
stands
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US00232184A
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English (en)
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Poucke R Van
Cat A De
G Benoy
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
    • C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/59—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
    • 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

  • Ar stands for phenyl or substituted phenyl X stands for hydrogen or a substituent that exhibits two equivalent character
  • R stands for a straight-chain or branched-chain alkyl group having from 1 to about 20 C-atoms.
  • This invention relates to the production of photographic colour images, to colour couplers for yellow used therein and to photographic materials containing such colour couplers.
  • a lightsensitive photographic colour material containing a red-sensitized, a green-sensitized and a blue-sensitive silver halide emulsion layer wherein on colour development, by use of appropriate colour couplers, a cyan, magenta and yellow dyestuff image are formed respectively.
  • Colour couplers for yellow of the benzoylacetanilide type which produce upon colour development yellow azomethine dyes with little side absorption in the green and red region of the spectrum, can be obtained by introducing an alkoxy group in the ortho-position of the anilide part of the molecule.
  • the main disadvantage of the above colour couplers is that they have a low coupling activity which results in 3,843,365 Patented Oct. 22, 1974 a low gradation value and low maximum density of the dye images formed upon colour development.
  • Another object of the present invention is to provide colour couplers for yellow having favourable spectral properties i.e. colour couplers which produce upon colour development yellow azomethine dyes with very low sideabsorption in the green and red region of the spectrum.
  • a further object of the present invention is to provide colour couplers which produce upon colour development yellow azomethine dyes with hypsochromic absorption maxima.
  • R stands for a straight-chain or branched-chain alkyl having from 1 to about 20 C-atoms
  • X represents a hydrogen atom or a substituent that exhibits two-equivalent character on colour development, e.g., a halogen atom, a S-R' group wherein R is alkyl, substituted alkyl, aryl, substituted aryl, a heterocycle or a substituted heterocycle, or a O-R" group wherein R" represents alkyl, substituted alkyl, aryl, substituted aryl, acyl or substituted acyl, e.g., acetyl and benzoyl, and
  • Ar stands for phenyl or substituted phenyl, e.g., phenyl substituted by halogen, alkoxy for example methoxy and hexadecyloxy, substituted alkoxy, e.g., halogen substituted alkoxy, acyl-amino groups and aminosulphonyl groups,
  • PREPARATION l COLOUR COUPLER 1
  • 2-hexadecyloxy-4-carboxy-nitrobenzene 138 g. of sodium were dissolved in litres of ethylene glycol monomethyl ether whereupon 1182 g. of 2-hydroxy-4-carbomethoxy nitrobenzene and 1830 g. of hexadecylbromide were added. The mixture was refluxed for 5 hours and then 584 g. of potassium hydroxide in 2 litres of Water were added at a temperature of 110 C. The mixture was left standing overnight at room temperature whereupon it was heated to 85 C. After addition of 1.5 litre of concentrated hydrochloride acid the mixture was poured into 12 litres of water. The precipitate was filtered oif and recrystallized from ethylacetate. Yield: 1700 g. Melting point: 152 C.
  • Colour coupler 1 4 PREPARATION 2 COLOUR COUPLER 2 This colour coupler was prepared in a similar way as colour coupler 1 from 42 g. of p-fiuorobenzoylacetic acid ethyl ester, prepared as described in co-pending application 14,476/69, and 75.4 g. of 2-hexadecyloxy-4-carboxyaniline acid. Yield: 86 g. Melting point: 158 C.
  • PREPARATION 3 COLOUR COUPLER 3 This colour coupler was prepared in a similar way as colour coupler 1 by condensation of 113 g. of 2-hexadecyloxy-4-carboxyaniline and 92 g. of p-methoxybenzoyl acetic acid ethyl ester in 225 ml. of xylene and 1 ml. of triethanol amine. Yield: 131 g. Melting point: 175- 176 C.
  • PREPARATION 4 COLOUR COUPLER 4 According to the method described for the preparation of colour coupler 1, 94 g. of 2-hexadecyloxy-4-carboxyaniline and 56.6 g. of o-chlorobenzoylacetic acid ethyl ester, prepared according to US. Pat. 3,056,675, were condensed in 200 ml. of xylene. 50 ml. of the solvent were distilled 011 in 1% hour. The precipitate formed was recrystallized from 750* ml. acetonitrile. Melting point: 106 C.
  • PREPARATION 5 COLOUR COUPLER 5 This colour coupler was prepared by condensation in 200 ml. of xylene of 83 g. of o-methoxybenzoylacetic acid ethyl ester and 94 g. of 2-hexadecyloxy-4-carboxyaniline according to the method described in preparation 1. Yield: 113 g. Melting point: C.
  • PREPARATION 6 COLOUR COUPLER 6 This colour coupler was prepared by condensation of 75.4 g. of 2-hexadecyloxy-4-carboxyaniline and 38.4 g. of benzoylacetic acid ethyl ester according to the method of preparation 1. The precipitate formed was recrystallized from ethylene glycol monomethyl ether. Yield: 75 g. Melting point: 151 C.
  • PREPARATION 7 COLOUR COUPLER 7 According to the method of preparation 1, 81 g. of o- (l,l,2-trifluoro-Z-chloroethoxy)benzoylacetic acid ethyl ester, prepared as described in British patent application 34,341/ 68, and 94 g. of Z-hexadecyloxy-4-carboxyaniline were condensed. The precipitate formed was recrystallized from acetonitrile. Yield: 126 g. Melting point: 126 C.
  • PREPARATION 8 COLOUR COUPLER 8 This colour coupler was prepared according to the method of preparation 1 by condensation of 65 g. of p- (l,1,Z-trifluoro-Z-chloroethoxy)benzoylacetic acid ethyl ester and 75 .4 g. of 2-hexadecyloxy-4-carboxyaniline. The precipitate formed was recrystallized from a mixture of dioxan and methanol. Melting point: 185 C.
  • PREPARATION 9 COLOUR COUPLER 9 This colour coupler was prepared by condensation of 75.4 g. of 2-hexadecyloxy-4-carboxy aniline and 45.3 g. of p-chlorobenzoylacetic acid ethyl ester, prepared in an analogous way as the o-chloro compound and having a boiling point of 139 C./l mm., in 200 ml. of xylene. Yield: 96.5 g. Melting point: 152 C.
  • PREPARATION 10 COLOUR COUPLER 10 (a) 2-methoxy-4-carboxy-nitrobenzene g. of 2-methoxy-4-carbomethoxy-nitrobenzene were refluxed for 1 hour in 750 ml. of methanol in the presence of 300 ml. of 5 N potassium hydroxide. The
  • PREPARATION 11 COLOUR COUPLER 11 55.3 g. of colour coupler 4 in 200 ml. of chloroform were treated with 8.1 ml. of sulphuryl chloride dissolved in 50 ml. of chloroform. The reaction mixture was concentrated by evaporation and the residue recrystallized from acetonitrile. Yield: 53 g. Melting point: 73 C.
  • PREPARATION l2 COLOUR COUPLER 12 Colour coupler 12 was prepared from colour coupler 9 in a similar way as colour coupler 11. The product was recrystallized from methanol. Melting point: 105 C.
  • PREPARATION 13 COLOUR COUPLER 13 Colour coupler 13 was prepared from colour coupler 7 in a similar way as colour coupler 11. The product was recrystallized from methanol. Melting point: 83 C.
  • the yellow colour formers according to the present invention are of the non-diffusible type; they comprise in their molecule at last one acyclic aliphatic hydrocarbon group sufiiciently large for preventing the colour coupler of wandering from the colloid layer, in which the coupler is incorporated, to another colloid layer.
  • the non-difiusing colour couplers for each colour separation image are usually incorporated into the coating compositions of the diiferently sensitized silver halide emulsion layers.
  • the non-difiusing colour couplers may also be added to the coating compositions of non-light-sensitive colloid layers which are in waterpermeable relationship with the light-sensitive silver halide emulson layers, e.g., in layers which are in direct contact with the light-sensitive layers or which are separated from said light-sensitive layers by water-permeable nonlight-sensitive layers.
  • the non-migratory yellow forming colour 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 colour couplers, into colloid compositions.
  • they can be incorporated into the coating composition of the layer in question from an aqueous alkaline solution, if necessary in the presence of a Water-miscible solvent, e.g., ethanol.
  • the solution of said colour coupler need not necessarily be added directly to the coating composition of the silver halide emulsion layer or other water-permeable layer.
  • Said solution may be first added to an aqueous non-light-sensitive hydrophilic colloid solution whereupon the resultant mixture, is intimately mixed with the said coating composition of the light-sensitive silver halide emulsion layer or other water-permeable layer just before coating.
  • 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 bromoiodide and silver chlorobromoiodide.
  • the couplers can be used in emulsions of the mixed packet type as described in United States patent specification 2,698,794 or emulsions of the mixed grain type as described in United States patent specification 2,592,243.
  • the colour 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 by effecting the ripening in the presence of small amounts of sulphur 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 patent specification 1,146,955 and in Belgian patent specification 568,687, iminoamino methane sulphinic acid compounds as described in United Kingdom patent specification 789,823 and small amounts of noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium. They may be optically sensitized by means of cyanine and merocyanine dyes.
  • reductors for instance tin compounds as described in French patent specification 1,146,955 and in Belgian patent specification 568,687, iminoamino methane sulphinic acid compounds as described in United Kingdom patent specification 789,823 and small amounts of noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium. They may be optically sensitized by means of cyanine and merocyanine dyes.
  • the said emulsions may also comprise compounds which sensitize the emulsions by development acceleration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in United States patent specifications 2,531,832 and 2,533,990, in United Kingdom patent specications 920,637, 940,051, 945,340 and 991,608 and in Belgian patent specification 648,710 and onium deriva tives of amino-N-oxides as described in United Kingdom patent specification 1,121,696.
  • compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in United States patent specifications 2,531,832 and 2,533,990
  • United Kingdom patent specications 920,637, 940,051, 945,340 and 991,608 and in Belgian patent specification 648,710 and onium deriva tives of amino-N-oxides as described in United Kingdom patent specification 1,121,696.
  • the emulsions may comprise stabilizers, e.g., heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline-Zthione and l-phenyl-2-tetrazoline-5- thione and compounds of the hydroxytriazolopyrimidine type. They can also be stabilized with mercury compounds such as the mercury compounds described in Belgian patent specifications 524,121, 677,337, 707,386 and in United States patent specification 3,179,520.
  • stabilizers e.g., heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline-Zthione and l-phenyl-2-tetrazoline-5- thione and compounds of the hydroxytriazolopyrimidine type.
  • mercury compounds such as the mercury compounds described in Belgian patent specifications 524,121, 677,337, 707,386 and in United States patent specification 3,179,520.
  • the light-sensitive emulsions may also comprise all other kinds of ingredients such as plasticizers, hardening agents, wetting agents, etc.
  • non-diifusion yellow colour 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 colour material.
  • Such photographic multilayer colour material usually comprises a support, a red-sensitized silver halide emulsion layer with a cyan colour former, a green-sensitized silver halide emulsion layer with a magenta colour former and a blue-sensitive silver halide emulsion layer with a yellow colour 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 of 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 colour coupler according to the present invention.
  • All colour developing agents capable of forming azomethine dyes can be utilized as developers.
  • Suitable developing agents are aromatic primary amino compounds for example N,N- di-alkyl-p-phenylene diamines and derivatives thereof, e.g., the toluene analogues.
  • aromatic primary amino colour developing agents are: N,N-diethylp-phenylene diamine, 2-amino-5-diethylaminotoluene, N- butyl-N-sulphobutyl-p-phenylene diamine, 2-amino-5-[N- ethyl-N- (fl-methylsulphonamido) ethyl] aminotoluene, N- ethyl-N-B-hydroxyethyl-p-phenylenediamine etc.
  • These developing agents are usually used in their salt form such as the hydrochloride or sulphate.
  • the yellow colour formers according to the invention form on colour development with aromatic primary amines yellow dyes which excell by their favourable light absorption in the blue region of the spectrum and little absorption in the other regions. Furthermore, the colour couplers of the invention manifest a high coupling activity during development. The gradation and maximum density obtained with the colour couplers of the invention is markedly higher than that obtained with the structural isomeric S-carboxy derivatives.
  • N,N-diethyl-p-phenylene diamine sulphate 2.75 Hydroxylamine sulphate 1.2 Sodium hexametaphosphate 4 Anhydrous sodium sulphite 2 Anhydrous potassium carbonate 75 Potassium bromide 2 2.5 Water to make 1 litre.
  • the developed materials were treated for 2 min. at 18 20 C. in an intermediate bath comprising 30 g. of sodium sulphate in 1 litre of water.
  • Borax 20 Anhydrous potassium bromide 15 Anhydrous sodium bisulphate a 4.2 Potassium hexacyanoferrate (III) 100 Water to make 1 litre.
  • Ar stands for phenyl
  • X stands for hydrogen, halogen, SR' and OR" wherein R is alkyl, aryl, or heterocycle, and R is alkyl, aryl, or acyl, and
  • R stands for a straight-chain or branched-chain alkyl group having from 1 to about 20 C-atoms
  • the colour coupler molecular comprising at least one straight-chain or branched-chain alkyl group rendering the molecule fast to diflusion in hydrophilic colloid media.
  • Photographic colour material according to claim 1 wherein the said material is a multilayer colour material comprising three silver halide emulsion layers which have a different spectral sensitivity including a blue-sensitive silver halide emulsion layer, the said blue-sensitive silver halide emulsion layer or a non-light-sensitive water-permeable colloid layer adjacent thereto incorporating the said colour coupler(s).
  • Ar stands for phenyl
  • X stands for hydrogen halogen, -SR and OR" wherein R is alkyl, aryl, or heterocycle, and R is alkyl, aryl, or acyl, and
  • R stands for a straight-chain or branched-chain alkyl group having from 1 to about 20 C-atoms
  • the said colour coupler(s) being present in a blue-sensitive silver halide emulsion layer or other colloid layer in water-permeable relationship therewith of the said photographic element.
  • X is S-R' wherein R is alkyl, aryl, or a heterocycle.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00232184A 1971-03-25 1972-03-06 Yellow forming colour couplers for photographic silver halide material Expired - Lifetime US3843365A (en)

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DE19712114576 DE2114576A1 (de) 1971-03-25 1971-03-25 Fotografischer Gelbkuppler

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US (1) US3843365A (de)
BE (1) BE780163A (de)
DE (1) DE2114576A1 (de)
FR (1) FR2130155B3 (de)
GB (1) GB1378675A (de)
IT (1) IT960349B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4012258A (en) * 1974-04-12 1977-03-15 Konishiroku Photo Industry Co., Ltd. Process for forming color photographic images

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4012258A (en) * 1974-04-12 1977-03-15 Konishiroku Photo Industry Co., Ltd. Process for forming color photographic images

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Publication number Publication date
DE2114576A1 (de) 1972-10-05
BE780163A (nl) 1972-09-04
FR2130155B3 (de) 1974-06-07
IT960349B (it) 1973-11-20
GB1378675A (en) 1974-12-27
FR2130155A3 (de) 1972-11-03

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