US3563745A - Silver halide photographic materials containing 1-arylmethyl-2-pyrazolin-5-one color couplers - Google Patents

Silver halide photographic materials containing 1-arylmethyl-2-pyrazolin-5-one color couplers Download PDF

Info

Publication number
US3563745A
US3563745A US664645A US3563745DA US3563745A US 3563745 A US3563745 A US 3563745A US 664645 A US664645 A US 664645A US 3563745D A US3563745D A US 3563745DA US 3563745 A US3563745 A US 3563745A
Authority
US
United States
Prior art keywords
radical
colour
pyrazolin
silver halide
couplers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US664645A
Inventor
Hector Alfons Vanden Eynde
Robert Joseph Pollet
Arthur Henri De Cat
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Application granted granted Critical
Publication of US3563745A publication Critical patent/US3563745A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings

Definitions

  • R represents an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, an aryloXy radical, an aralkyloxy radical, an alkylamino radical, an arylamino radical or an analkylamino radical are described.
  • This invention relates to colour photography and the production of photographic colour images by colour development. It relates more particularly to novel colourless magenta-forming colour couplers of the 2-pyrazolin-5-one type and to photographic materials and developing compositions containing such colour couplers.
  • a light-sensitive photographic colour material comprising a red-sensitized, a green-sensitized and a blue-sensitive silver halide emulsion layer wherein on development by means of suitable colour couplers, a cyan, a magenta, and a yellow dye image are formed respectively.
  • the present invention is concerned with a process for the production of photographic colour images using magenta-formin g colour couplers of the 2-pyrazolin-5-0ne type, which show an improved stability when stored in humid and warm atmospheres and do not give rise to colouring of the white image areas and which on colour development with aromatic primary amines as developing agents form azomethine magenta dyestuffs possessing favourable spectral properties and having an improved light-stability, a good colour density and good gradation.
  • the present invention also relates to photographic materials and treating solutions comprising said colour couplers, by means of which magenta dye images are formed.
  • Ar represents an aryl group, including aryl substituted by one or more non-chromophoric groups, e.g. a halogen atom such as chlorine, a cyano group, an alkoxy group such as methyloxy, an aryloxy group, a trifiuoromethyl group, an alkyl mercapto group such as methyl mercapto, an aryl mercapto group, an alkylsulphonyl group such as methylsulphonyl and an arylsulphonyl group, and
  • R represents an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, an aryloxy radical, an aralkyloxy radical, an alkylamino radical, an arylamino radical or an aralkylamino radical including the substituted derivatives of these radicals.
  • the 1-arylmethyl-3-amino-2-pyrazolin-5-one compounds used are prepared according to the method known by those skilled in the art i.e. by cyclisation of an appropriate arylmethyl-hydrazine with, -e.g., the ethyl ester of B-iminofl-ethoxypropionic acid.
  • the preparation of the arylmethyl hydrazine offers no difiiculties to the organic chemist.
  • preferred method giving good yields consists in allowing to react hydrazinehydrate with a chloromethyl-substituted aromatic compound of the benzene or naphthalene series.
  • the temperature of the reaction mixture rises slowly and is kept at 30 C. by cooling periodically. A clear solution forms but after 1 hour a white product precipitates. The reaction mixture is then kept standing overnight whereupon the solid is separated and thoroughly washed with water. The white fibrous crystalline product melts at 139140 C.
  • the reaction product is washed with water and with methanol and then recrystallized from isopropanol.
  • the colour coupler formed is a white product having a melting point of 131 C.
  • reaction product is washed with water and then treated with acetonitrile.
  • a white product is obtained, which after having been washed with isopropyl ether melts at 100 C.
  • reaction product is washed with water and with methanol and then recrystallized from a mixture of isopropanol and ethylene glycol monomethyl ether.
  • a white product is obtained having a melting point of C.
  • This benzylhydrazine is a colourless liquid with a boiling point of 93 C./ 0.35 mm.
  • 1-( 3-trifluoromethyl benzyl -3-amino-2-pyrazolin-5- one is prepared in an analogous way as described for 1-(2- chlorobenzyl)-3-amino-2-pyrazolin-5-one in preparation 2(a).
  • the product obtained after recrystallisation from a mixture of isopropyl ether and methyl acetate melts at 146 C.
  • 1,039,965 filed July 6, 1964 by Gevaert Photo-Producten N.V., in 80 ml. of pyridine and 160 ml. of benzene and in the presence of 4.5 ml. of phosphorus trichloride.
  • a white product is obtained that does not melt at a temperature lower than 200 C.
  • the colour couplers for magenta according to the present invention may be of the diffusible type as well as of the non-dilfusible type.
  • diffusible-type couplers couplers the dispersability or solubility of Which is sufficient to enable them to :be usefully incorporated in aqueous colour developing baths; an example of such a colour coupler is the colour coupler according to Formula 1.
  • non-diffusing colour couplers is meant colour couplers of such nature that they are capable of remaining during colour development in the photographic hydrophilic colloid layer(s) in which they have been incorporated.
  • the colour couplers For manufacturing an appropriate photographic multilayer colour material containing colour couplers for each colour separation image in the differently optically sensitized silver halide emulsion layers, the colour couplers must be present in the hydrophilic silver halide emulsion layers in a non-diffusible form.
  • This object can be accomplished e.g. by the use of a sufiiciently water-soluble colour coupler comprising an organic radical which is sufficiently large to prevent the colour coupler from diffusing in the hydrophilic silver halide emulsion layer, or by the utilization of a lipophilic colour coupler, which, in dissolved state in a high-boiling organic solvent, is dispersed in the silver halide emulsion layer.
  • the said radical rendering the colour coupler non-diifusible or non-migratory may be present in the radical Ar or R of the above general formula and is preferably an aliphatic radical containing. from 5 to 20 carbon atoms in straight line.
  • the couplers may be dissolved either in a low-boiling water-insoluble organic solvent or in an appreciably water-soluble organic solvent and can be finely dispersed in a photographic colloid, e.g., gelatin.
  • a photographic colloid e.g., gelatin.
  • Particularly useful dispersing techniques which can be applied are described in our British Patent Nos. 1,098,594; 1,099,414; 1,099,415; 1,099,416, and 1,099,417.
  • a particular colour coupler according to the present invention may be incorporated into a silver halide emulsion according to any other appropriate technique known in the art.
  • these colour couplers are mixed homogeneously with the lightsensitive silver halide emulsion preferably immediately before the coating of the emulsion.
  • the couplers according to the above general formula may be used in various kinds of photographic emulsions. They may be added to the emulsions before or after any sensitizing dyes are incorporated.
  • 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 and silver bromoiodide.
  • the colour couplers may be incorporated into emulsions of the mixed packet type such as described in the U.S. patent specification 2,698,794 of Leopold Godowsky, issued Jan. 4, 1955 or into emulsions of the mixed grain type, such as described in the U.S. patent specification 2,592,243 of Burt H. Carroll and Wesley T.
  • the colour couplers can be used in emulsions wherin latent images are formed predominantly on the surface of the silver halide crystal or in emulsions wherein latent images are formed predominantly inside the silver halide crystal.
  • the coupler compounds of the present invention may be dispersed in any water-permeable hydrophilic colloid material, such as gelatin, albumin, casein, zein and the like, and synthetic hydrophilic colloids, such as polyvinyl alcohol, that may be used for making photographic emulsions.
  • the emulsions usually also comprise i.a. spectrally sensitizing agents, hardeners, stabilizing agents and wetting agents, for facilitating the coating and the adhesion of the emulsion.
  • the thus prepared silver halide emulsion can be coated as one of the layers of a onelayer or multilayer colour material.
  • non-migratory colour couplers according to the present invention need not necessarily be provided in the light-sensitive silver halide emulsion layer, but they may also be incorporated into a non-light-sensitive colloid layer adjacent to a silver halide emulsion layer or into a colloid layer in water-permeable relationship therewith.
  • the non-migratory colour couplers for magenta described in the present invention are added, usually as a solution to a green-sensitized silver halide emulsion.
  • this silver halide emulsion is coated as the second colour coupler containing layer of a photographic multilayer colour material.
  • Such photographic multilayer colour material usually consists in the given sequence of a support, a red-sensitized silver halide emulsion layer with a colour coupler for cyan, a green-sensitized silver halide emulsion layer with a colour coupler for magenta and a blue-sensitive silver halide emulsion layer with a colour coupler for yellow.
  • a yellow filter layer generally comprising colloidal silver dispersed in gelatin is provided usually between the silver halide emulsion layer containing a colour coupler for yellow and the green-sensitized silver halide emulsion layer.
  • the colour couplers for magenta according to the present invention may also be applied in so-called droplet emulsions (cf. U.S. patent specification 2,304,940 of Leopold D. Mannes and Leopold Godowsky, Jr., issued Dec. 15, 1942).
  • Photographic emulsions containing these couplers may be coated on a transparent support such as glass, cellulose esters or on a non-transparent reflecting material such as paper or an opaque cellulose ester.
  • an exposed silver halide emulsion layer is developed preferably with an aromatic primary amine developing substance in the presence of a colour coupler for magenta corresponding to the above general formula.
  • Suitable developing agents are aromatic amine compounds, such as p-phenylene diamine, N,N-dialkyl-pphenylenediamines, such as N,N-diethyl-p-phenylenedi amine, and derivatives such as N,N-dialkyl-N'-sulphomethyl-p-phenylenediamines and N,N-dialkyl-N-carboxymethyl-p-phenylenediamines.
  • aromatic amine compounds such as p-phenylene diamine, N,N-dialkyl-pphenylenediamines, such as N,N-diethyl-p-phenylenedi amine, and derivatives such as N,N-dialkyl-N'-sulphomethyl-p-phenylenediamines and N,N-dialkyl-N-carboxymethyl-p-phenylenediamines.
  • magenta dye images formed on colour development show good fastness to light, an intense colour density and favourable spectral properties.
  • the pH of the emulsion is adjusted to pH 7.6 and then the usual additives are incorporated such as hardeners, coating aids, wetting agents and stabilizers.
  • the emulsion is coated on a baryta-coated paper supporting such a way that 60 sq. m. are covered and then dried.
  • the developed colour material is rinsed for 30 seconds and fixed in an acid fixing bath of the following composition:
  • Ethylene-diamine-tetraacetic acid sodium iron (III) salt 37.5 Ethylene-diamine-tetraacetic acid sodium salt 21.5 Ammonium thiocyanate (anhydrous) 110 Amonium thiocyanate (anhydrous) 5 Sodium sulphite (anhydrous) 10 Water to 1000 ccs.
  • the material is dried.
  • a magenta wedge image is obtained.
  • Method of producing a magenta coloured photographic image in a photographic light-sensitive silver halide material which comprises exposing the material and developing it in the presence of a colourless coupler compound corresponding to the general formula:
  • Ar represents an aryl group
  • R' represents an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, an aryloxy radical, an aralkyloxy radical, an alkylamino radical, an arylamino radical or an aralkylamino radical.
  • said colourless coupler compound is a non-diifusible colour coupler present in a silver halide emulsion layer or in another colloid layer which is in water-permeable relationship with said silver halide emulsion layer of said photographic material.
  • a photographic emulsion for preparing a photographic element for forming coloured images comprising a water-permeable colloid as carrier for light-sensitive silver halide and a colourless 2-pyrazolin-5-one colour coupler corresponding to the general formula:
  • Ar represents an aryl group
  • R represents an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, an aryloxy radical, an aralkyloxy radical, an alkylamino radical, an arylamino radical or an aralkylamino radical, at least one of Ar and R comprising an aliphatic radical having from 5 to 20 carbon atoms in straight line.
  • said colour coupler is present in said emulsion layer.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

COLORLESS MAGENTA FORMING COLOR COUPLERS OF THE 2PYRAZOLIN-5-ONE TYPE HAVING FORMULA:

1-(AR-CH2-),3-(R-CO-HN-)-2-PYRAZOLIN-5-ONE

WHEREIN: AR REPRESENTS AN ARYL GROUP, AND R REPRESENTS AN ALKYL RADICAL, AN ARYL RADICAL, AN ARALKYL RADICAL, AN ALKOXY RADICAL, IN ARYLOXY RADICAL, AN ARALKYLOXY RADICAL, AN ALKYLAMINO RADICAL AN ARYLAMINO RADICAL OR AN ANALKYLAMINO RADICAL ARE DESCRIBED. THESE COLOR COUPLERS HAVE IMPROVED STABILITY WHEN STORED IN HUMID AND WARM ATMOSPHERES AND THE WHITE IMAGE AREAS DO NOT UNDERGO DISCOLORATION.

Description

United States Patent Office US. Cl. 96-565 5 Claims ABSTRACT OF THE DISCLOSURE Colorless magenta forming color couplers of the 2'- pyrazolin-S-one type having the formula:
Ar a
ll H2O CNHGOR wherein Ar represents an aryl group, and
R represents an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, an aryloXy radical, an aralkyloxy radical, an alkylamino radical, an arylamino radical or an analkylamino radical are described. These color couplers have improved stability when stored in humid and warm atmospheres and the white image areas do not undergo discoloration.
This invention relates to colour photography and the production of photographic colour images by colour development. It relates more particularly to novel colourless magenta-forming colour couplers of the 2-pyrazolin-5-one type and to photographic materials and developing compositions containing such colour couplers.
It is known that for the manufacture of a photographic colour image in a light-sensitive silver halide emulsion layer the exposed silver halide is developed to a silver image by means of an aromatic primary amino compound in the presence of a colour coupler which by reaction with the oxidized developer forms a dye on the areas corresponding with the silver image.
In the subtractive three-colour photography usually a light-sensitive photographic colour material is used comprising a red-sensitized, a green-sensitized and a blue-sensitive silver halide emulsion layer wherein on development by means of suitable colour couplers, a cyan, a magenta, and a yellow dye image are formed respectively.
The present invention is concerned with a process for the production of photographic colour images using magenta-formin g colour couplers of the 2-pyrazolin-5-0ne type, which show an improved stability when stored in humid and warm atmospheres and do not give rise to colouring of the white image areas and which on colour development with aromatic primary amines as developing agents form azomethine magenta dyestuffs possessing favourable spectral properties and having an improved light-stability, a good colour density and good gradation.
The present invention also relates to photographic materials and treating solutions comprising said colour couplers, by means of which magenta dye images are formed.
The colour couplers for magenta of the 2-pyrazolin-5- 3,563,745 Patented Feb. 16, 1 971 one type of use according to the present invention correspond to the following general formula:
Ar represents an aryl group, including aryl substituted by one or more non-chromophoric groups, e.g. a halogen atom such as chlorine, a cyano group, an alkoxy group such as methyloxy, an aryloxy group, a trifiuoromethyl group, an alkyl mercapto group such as methyl mercapto, an aryl mercapto group, an alkylsulphonyl group such as methylsulphonyl and an arylsulphonyl group, and
R represents an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, an aryloxy radical, an aralkyloxy radical, an alkylamino radical, an arylamino radical or an aralkylamino radical including the substituted derivatives of these radicals.
The following is a non-limitative list of structural formulae of colour couplers corresponding to the above general formula and suitable for use according to the present invention:
0- CH CH 2)n a I w N SOaH I r N No. 1,044,959 filed Sept. 28, 1964 and No. 1,007,847 filed Oct. 10, 1963 both by Gevaert Photo-Producten NV. and in German patent application (DAS) 1,176,479 filed Dec. 20, 1963 by Perutz Photowerke G.m.b.H.
The 1-arylmethyl-3-amino-2-pyrazolin-5-one compounds used are prepared according to the method known by those skilled in the art i.e. by cyclisation of an appropriate arylmethyl-hydrazine with, -e.g., the ethyl ester of B-iminofl-ethoxypropionic acid. The preparation of the arylmethyl hydrazine offers no difiiculties to the organic chemist. A
preferred method giving good yields consists in allowing to react hydrazinehydrate with a chloromethyl-substituted aromatic compound of the benzene or naphthalene series.
The following description illustrates the preparation of the magenta-forming colour couplers corresponding to the above general formula.
PREPARATION 1 1-benzyl-3 -octadecylureido-2-pyraz0lin-5-one (Formula 2) (a) 1=benzyl-3-amino-2-pyrazolin-5-one.--To a solution of 122 g. of benzylhydrazine, prepared as described by J. H. Biel et al., J. Am. 'Chem. Soc. 81, 2805 (1959), in 570 ml. of water, 159.5 g. of fi-ethoxy-fi-iminopropionic acid ethyl ester and 1 g. of p-toluene-sulphonic acid are added while stirring. The temperature of the reaction mixture rises slowly and is kept at 30 C. by cooling periodically. A clear solution forms but after 1 hour a white product precipitates. The reaction mixture is then kept standing overnight whereupon the solid is separated and thoroughly washed with water. The white fibrous crystalline product melts at 139140 C.
(b) 1-benzyl-3 -octadecylureido-2-pyrazolin-5-one.-1 8 .9 g. of 1-benzyl-3-amino-2-pyrazolin-5-one and 29.5 g. of octadecyl isocyanate are allowed to react at 36 C. in 100 ml. of methylene chloride and in the presence of 26.7 g. of aluminium chloride (this method has been described in United Kingdom patent specification No. 1,007,847 filed Oct. 10, 1963 by Gevaert Photo-Producten N.V.).
The reaction product is washed with water and with methanol and then recrystallized from isopropanol. The colour coupler formed is a white product having a melting point of 131 C.
PREPARATION 2 1- 2-chlorob enzyl) -3 o-hexadecylsulphonylbenzamido 2-pyrazolin-5-one (Formula 5) (a) 1-(2 chlorobenzyl)-3-amino-2-pyrazolin-5-one. 156.5 g. of 2-chlorobenzylhydrazine, which is a colourless liquid with a boiling point of 85 C./ 0.25 mm. and which has been prepared analogously to the method described by J. H. Biel et al., J. Am. Chem. Soc. 81, 2805 (1959), are mixed with 159.5 g. of ,fi-ethoxy-p-imino-propionic acid ethyl ester and 2 ml. of acetic acid. The temperature of the reaction mixture rises to 45 C. The mixture is kept standing overnight whereupon the precipitate formed is filtered by suction and washed with acetonitrile. A white product with a melting point of 163 C. is obtained.
(b) 1 (2 chlorobenzyl) 3-(o-hexadecylsulphonylbenzamido)-2-pyrazolin-5-one.- 22.35 g. of 1-(2-chl0robenzyl)-3-amino-2-pyrazolin-5-one and 42.85 g. of o-hexadecylsulphonylbenzoylchloride are allowed to react at 36 C. in 100 ml. of methylene chloride and in the presence of 26.7 g. of aluminum chloride (this method has been described in United Kingdom patent specification No. 1,007,847 filed Oct. 10, 1963 by Gevaert Photo-Producten N.V.).
The reaction product is washed with water and then treated with acetonitrile. A white product is obtained, which after having been washed with isopropyl ether melts at 100 C.
PREPARATION 3 1-(4-chlorobenzyl)-3-palrnitoylarnino-2-pyrazolin-5-one (Formula 7) (a) 1-(4-chlorobenzyl)-3-amino-2-pyrazolin-5-one is prepared in an analogous way as 1-(2-chlorobenzyl)-3 amino2-pyrazolin-5-0ne (preparation 2(a)) starting, however, from 4-chlorobenzylhydrazine which is a colourless liquid having a boiling point of 99-102 C./0.7 mm. The 1 (4-chlorobcnzyl)-3-amino-2-pyrazolin-S-one obtained after recrystallisation from ethanol is a white product that melts at 138 C.
(b) 1-(4-chlorobenzyl) 3 palmitoylamino-Z-pyrazolin-5-one.-22.35 g. of 1-(4-chlorobenzyl)-3-amino-2-pyrazolin-S-one and 27.48 g. of palmitoyl chloride are allowed to react at 50 C. in ml. of nitrobenzene and in the presence of 26.7 g. of aluminium chloride (this method has been described in United Kingdom patent specification No. 1,007,847 filed Oct. 10, 1963 by Gevaert Photo-Producten N.V.).
The reaction product is washed with water and with methanol and then recrystallized from a mixture of isopropanol and ethylene glycol monomethyl ether. A white product is obtained having a melting point of C.
PREPARATION 4 1- 3-trifluoromethylbenzyl -3- ot-sulpho-stearoylamino 2-pyrazolin-5-one (Formula 8 (a) 1-(3-trifluoromethylbenzyl) 3 amino-Z-pyrazolin-5-one.3-trifiuoromethylbenzyl bromide prepared as described in J. Org. Chem. 25, 733 (1960) is converted into 3-trifiuoromethyl-benzylhydrazine analogously to the method described by J. H. Biel et al., J. Am. Chem. Soc. 81, 2805 (1959). This benzylhydrazine is a colourless liquid with a boiling point of 93 C./ 0.35 mm. From this benzylhydrazine and B-ethoxy-[3-imino-propionic acid ethyl ester, 1-( 3-trifluoromethyl benzyl -3-amino-2-pyrazolin-5- one is prepared in an analogous way as described for 1-(2- chlorobenzyl)-3-amino-2-pyrazolin-5-one in preparation 2(a). The product obtained after recrystallisation from a mixture of isopropyl ether and methyl acetate melts at 146 C.
(b) l (3 trifluoromethylbenzyl) 3 (a sulphostearoylamino)-2-pyrazolin-5-one.25.7 g. of 1-(3-trifluoromethylbenzyl)-3-amino-2-pyrazolin-5-one and 39 g. of the monosodium salt of Z-sulpho-stearic acid are allowed to react analogously to the method described in US. patent specification No. 2,829,975 of Stanley P. Popeck and Heinz Schulze, issued Apr. 8, 1958 in 80 ml. of pyridine and 160 ml. of benzene and in the presence of 4.5 ml. of phosphorus trichloride. A white product is obtained that does not melt at a temperature lower than 200 C.
PREPARATION 5 1- (2,6-dichlorobenzyl -3- 2-hexadecyloxy-5-sulphobenzamido)-2-pyrazolin-5-one (Formula 9) (a) 1-(2,6-dichlorobenzyl) 3 amino-2-pyrazolin-5- one.2,6-dichloro-benzylhydrazine, which is a colourless liquid boiling at 109 C./1 mm. and prepared analogously to the method described by I. H. Biel et al., J. Am. Chem. Soc. 81, 2805 1959), is converted into 1-(2,6-dichlorobenzyl)-3-amino-2-pyrazolin-5-one in an analogous way as 1-(2-ch1orobenzyl)-3-amino-2-pyrazolin-5-one (preparation 2(a) After recrystallisation from a mixture of isopropyl ether and acetic acid the product melts at 230232 C.
(b) 1-(2,6-dichlorobenzyl) 3 (2 hexadecyloxy-S- sulpho-benzamido)-2-pyrazolin-5-one.25.8 g. of 1-(2,6- dichlorobenzyl)-3-amino-2-pyrazolin-5-one are allowed to react, analogously to the method described in US. patent specification 2,829,975 of Stanley P. Popeck and Heinz Schulze, issued Apr. 8, 1958, with 44.2 g. of 2-hexadecyloxy-S-sulpho-benzoic acid, prepared analogously as 2-hexadecyloxy-3-sulpho-benzoic acid described in United Kingdom patent specification No. 1,039,965 filed July 6, 1964 by Gevaert Photo-Producten N.V., in 80 ml. of pyridine and 160 ml. of benzene and in the presence of 4.5 ml. of phosphorus trichloride.
A white product is obtained that does not melt at a temperature lower than 200 C.
The colour couplers for magenta according to the present invention may be of the diffusible type as well as of the non-dilfusible type. By diffusible-type couplers is meant couplers the dispersability or solubility of Which is sufficient to enable them to :be usefully incorporated in aqueous colour developing baths; an example of such a colour coupler is the colour coupler according to Formula 1. By non-diffusing colour couplers is meant colour couplers of such nature that they are capable of remaining during colour development in the photographic hydrophilic colloid layer(s) in which they have been incorporated. For manufacturing an appropriate photographic multilayer colour material containing colour couplers for each colour separation image in the differently optically sensitized silver halide emulsion layers, the colour couplers must be present in the hydrophilic silver halide emulsion layers in a non-diffusible form. This object can be accomplished e.g. by the use of a sufiiciently water-soluble colour coupler comprising an organic radical which is sufficiently large to prevent the colour coupler from diffusing in the hydrophilic silver halide emulsion layer, or by the utilization of a lipophilic colour coupler, which, in dissolved state in a high-boiling organic solvent, is dispersed in the silver halide emulsion layer. According to the present invention the said radical rendering the colour coupler non-diifusible or non-migratory may be present in the radical Ar or R of the above general formula and is preferably an aliphatic radical containing. from 5 to 20 carbon atoms in straight line.
For the purpose of incorporating the colour couplers into a photographic colloid layer the couplers may be dissolved either in a low-boiling water-insoluble organic solvent or in an appreciably water-soluble organic solvent and can be finely dispersed in a photographic colloid, e.g., gelatin. Particularly useful dispersing techniques which can be applied are described in our British Patent Nos. 1,098,594; 1,099,414; 1,099,415; 1,099,416, and 1,099,417. A particular colour coupler according to the present invention may be incorporated into a silver halide emulsion according to any other appropriate technique known in the art.
In the preparation of a light-sensitive colour material wherein non-migratory colour couplers are used these colour couplers are mixed homogeneously with the lightsensitive silver halide emulsion preferably immediately before the coating of the emulsion.
The couplers according to the above general formula may be used in various kinds of photographic emulsions. They may be added to the emulsions before or after any sensitizing dyes are incorporated. 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 and silver bromoiodide. The colour couplers may be incorporated into emulsions of the mixed packet type such as described in the U.S. patent specification 2,698,794 of Leopold Godowsky, issued Jan. 4, 1955 or into emulsions of the mixed grain type, such as described in the U.S. patent specification 2,592,243 of Burt H. Carroll and Wesley T. Hanson, Jr., issued Apr. 8, 1952. The colour couplers can be used in emulsions wherin latent images are formed predominantly on the surface of the silver halide crystal or in emulsions wherein latent images are formed predominantly inside the silver halide crystal.
The coupler compounds of the present invention may be dispersed in any water-permeable hydrophilic colloid material, such as gelatin, albumin, casein, zein and the like, and synthetic hydrophilic colloids, such as polyvinyl alcohol, that may be used for making photographic emulsions. The emulsions usually also comprise i.a. spectrally sensitizing agents, hardeners, stabilizing agents and wetting agents, for facilitating the coating and the adhesion of the emulsion. The thus prepared silver halide emulsion can be coated as one of the layers of a onelayer or multilayer colour material.
The non-migratory colour couplers according to the present invention need not necessarily be provided in the light-sensitive silver halide emulsion layer, but they may also be incorporated into a non-light-sensitive colloid layer adjacent to a silver halide emulsion layer or into a colloid layer in water-permeable relationship therewith.
The non-migratory colour couplers for magenta described in the present invention are added, usually as a solution to a green-sensitized silver halide emulsion. According to a common procedure in the art this silver halide emulsion is coated as the second colour coupler containing layer of a photographic multilayer colour material. Such photographic multilayer colour material usually consists in the given sequence of a support, a red-sensitized silver halide emulsion layer with a colour coupler for cyan, a green-sensitized silver halide emulsion layer with a colour coupler for magenta and a blue-sensitive silver halide emulsion layer with a colour coupler for yellow.
A yellow filter layer generally comprising colloidal silver dispersed in gelatin is provided usually between the silver halide emulsion layer containing a colour coupler for yellow and the green-sensitized silver halide emulsion layer.
The colour couplers for magenta according to the present invention may also be applied in so-called droplet emulsions (cf. U.S. patent specification 2,304,940 of Leopold D. Mannes and Leopold Godowsky, Jr., issued Dec. 15, 1942).
Photographic emulsions containing these couplers may be coated on a transparent support such as glass, cellulose esters or on a non-transparent reflecting material such as paper or an opaque cellulose ester.
For the production of photographic colour images according to the present invention an exposed silver halide emulsion layer is developed preferably with an aromatic primary amine developing substance in the presence of a colour coupler for magenta corresponding to the above general formula.
Suitable developing agents are aromatic amine compounds, such as p-phenylene diamine, N,N-dialkyl-pphenylenediamines, such as N,N-diethyl-p-phenylenedi amine, and derivatives such as N,N-dialkyl-N'-sulphomethyl-p-phenylenediamines and N,N-dialkyl-N-carboxymethyl-p-phenylenediamines.
The magenta dye images formed on colour development show good fastness to light, an intense colour density and favourable spectral properties.
The following example illustrates the use of the magenta forming colour couplers according to the present invention.
EXAMPLE T0 1 kg. of a green-sensitized silver chloride emulsion containing an amount of silver chloride equivalent to 20 g. of silver nitrate are added 50 g. of the colour coupler of Formula 6, dissolved in a mixture of 500 ml. of ethanol, m1. of 2 N sodium hydroxide and 425 ml. of distilled water. The pH of the emulsion is adjusted to pH 7.6 and then the usual additives are incorporated such as hardeners, coating aids, wetting agents and stabilizers. The emulsion is coated on a baryta-coated paper supporting such a way that 60 sq. m. are covered and then dried.
After exposure through a grey-wedge the light-sensitive colour material is developed in a developing bath of the following composition:
G. p-N,N-diethylaminophenyl ammonium chloride 2.75
Sodium sulphite (anhydrous) 4 Sodium carbonate (anhydrous) 50 Potassium bromide 0.65 Hydroxyammonium chloride 3 Sodium hexametaphosphate 2.0
Water to 1000 ccs. (pH: 10.6).
The developed colour material is rinsed for 30 seconds and fixed in an acid fixing bath of the following composition:
G. Sodium thiosulphate (anhydrous) 100 Sodium sulphite (anhydrous) Sodium hydrogen sulphite (anhydrous) Water to 1000 ccs.
Now the fixed material is rinsed for 10 minutes and bleached in a bath of the following composition:
Ethylene-diamine-tetraacetic acid sodium iron (III) salt 37.5 Ethylene-diamine-tetraacetic acid sodium salt 21.5 Ammonium thiocyanate (anhydrous) 110 Amonium thiocyanate (anhydrous) 5 Sodium sulphite (anhydrous) 10 Water to 1000 ccs.
Finally the bleached material is rinsed for 5 minutes and stabilized in a bath of the following composition:
Sodium diacetate (NaOOCCH -CH COOH)3 g. Sodium acetate-12 g.
40% by weight aqueous formaldehyde solution-240 ccs. Water to1000 ccs.
The material is dried.
A magenta wedge image is obtained.
We claim:
1. Method of producing a magenta coloured photographic image in a photographic light-sensitive silver halide material, which comprises exposing the material and developing it in the presence of a colourless coupler compound corresponding to the general formula:
wherein:
Ar represents an aryl group, and
5 R'represents an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, an aryloxy radical, an aralkyloxy radical, an alkylamino radical, an arylamino radical or an aralkylamino radical.
2. Method according to claim 1, wherein said colourless coupler compound is a non-diifusible colour coupler present in a silver halide emulsion layer or in another colloid layer which is in water-permeable relationship with said silver halide emulsion layer of said photographic material.
3. A photographic emulsion for preparing a photographic element for forming coloured images comprising a water-permeable colloid as carrier for light-sensitive silver halide and a colourless 2-pyrazolin-5-one colour coupler corresponding to the general formula:
wherein:
Ar represents an aryl group, and R represents an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, an aryloxy radical, an aralkyloxy radical, an alkylamino radical, an arylamino radical or an aralkylamino radical, at least one of Ar and R comprising an aliphatic radical having from 5 to 20 carbon atoms in straight line. 5. A photographic element according to claim 4, wherein said colour coupler is present in said emulsion layer.
References Cited UNITED STATES PATENTS 9/1940 Kendall et al. 96-565 5/1969 Menzel et a1 96-100 J. TRAVIS BROWN, Primary Examiner US. Cl. X.R.
US664645A 1966-09-26 1967-08-31 Silver halide photographic materials containing 1-arylmethyl-2-pyrazolin-5-one color couplers Expired - Lifetime US3563745A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB42824/66A GB1190914A (en) 1966-09-26 1966-09-26 2-Pyrazolin-5-Ones and the use thereof as Colour Couplers

Publications (1)

Publication Number Publication Date
US3563745A true US3563745A (en) 1971-02-16

Family

ID=10426139

Family Applications (1)

Application Number Title Priority Date Filing Date
US664645A Expired - Lifetime US3563745A (en) 1966-09-26 1967-08-31 Silver halide photographic materials containing 1-arylmethyl-2-pyrazolin-5-one color couplers

Country Status (5)

Country Link
US (1) US3563745A (en)
BE (1) BE704277A (en)
DE (1) DE1597480C3 (en)
GB (1) GB1190914A (en)
NL (1) NL6711915A (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3947272A (en) * 1973-04-06 1976-03-30 Agfa-Gevaert, N. V. Silver halide emulsions containing 2-pyrazolon-5-one photographic colour couplers
US3950528A (en) * 1972-06-23 1976-04-13 Bayer Aktiengesellschaft 1-Substituted-3-amino-pyrazol-5-ones
US4000294A (en) * 1973-04-17 1976-12-28 Bayer Aktiengesellschaft Pyrazol-5-ones
US4002641A (en) * 1973-12-20 1977-01-11 Bayer Aktiengesellschaft Pyrazole derivatives
US4005215A (en) * 1973-04-17 1977-01-25 Bayer Aktiengesellschaft Pyrazol-5-ones
US4032646A (en) * 1973-04-17 1977-06-28 Bayer Aktiengesellschaft Pyrazol-5-ones
US4045571A (en) * 1973-04-17 1977-08-30 Bayer Aktiengesellschaft Pyrazol-5-ones
US4053621A (en) * 1974-06-06 1977-10-11 Bayer Aktiengesellschaft 1-[2-(βNaphthyloxy)ethyl]-3-methylpyrazolone-(5) and antithrombotic and antithrombolytic compositions and methods utilizing them
US4056533A (en) * 1973-04-17 1977-11-01 Bayer Aktiengesellschaft Pyrazol-5-ones
US4061653A (en) * 1972-06-23 1977-12-06 Bayer Aktiengesellschaft 1-Substituted-3-amino-pyrazol-5-ones
US4069334A (en) * 1973-12-20 1978-01-17 Bayer Aktiengesellschaft Pyrazole derivatives
US4081596A (en) * 1973-04-17 1978-03-28 Bayer Aktiengesellschaft Pyrazol-5-ones
USRE30420E (en) * 1973-04-17 1980-10-21 Bayer Aktiengesellschaft Pyrazol-5-ones
US4288446A (en) * 1973-04-17 1981-09-08 Bayer Aktiengesellschaft Pyrazol-5-ones

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3992404A (en) 1973-04-17 1976-11-16 Bayer Aktiengesellschaft Pyrazol-5-ones

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3950528A (en) * 1972-06-23 1976-04-13 Bayer Aktiengesellschaft 1-Substituted-3-amino-pyrazol-5-ones
US4061653A (en) * 1972-06-23 1977-12-06 Bayer Aktiengesellschaft 1-Substituted-3-amino-pyrazol-5-ones
US3947272A (en) * 1973-04-06 1976-03-30 Agfa-Gevaert, N. V. Silver halide emulsions containing 2-pyrazolon-5-one photographic colour couplers
US4045571A (en) * 1973-04-17 1977-08-30 Bayer Aktiengesellschaft Pyrazol-5-ones
US4005215A (en) * 1973-04-17 1977-01-25 Bayer Aktiengesellschaft Pyrazol-5-ones
US4032646A (en) * 1973-04-17 1977-06-28 Bayer Aktiengesellschaft Pyrazol-5-ones
US4056533A (en) * 1973-04-17 1977-11-01 Bayer Aktiengesellschaft Pyrazol-5-ones
US4000294A (en) * 1973-04-17 1976-12-28 Bayer Aktiengesellschaft Pyrazol-5-ones
US4081596A (en) * 1973-04-17 1978-03-28 Bayer Aktiengesellschaft Pyrazol-5-ones
USRE30420E (en) * 1973-04-17 1980-10-21 Bayer Aktiengesellschaft Pyrazol-5-ones
US4288446A (en) * 1973-04-17 1981-09-08 Bayer Aktiengesellschaft Pyrazol-5-ones
US4002641A (en) * 1973-12-20 1977-01-11 Bayer Aktiengesellschaft Pyrazole derivatives
US4069334A (en) * 1973-12-20 1978-01-17 Bayer Aktiengesellschaft Pyrazole derivatives
US4053621A (en) * 1974-06-06 1977-10-11 Bayer Aktiengesellschaft 1-[2-(βNaphthyloxy)ethyl]-3-methylpyrazolone-(5) and antithrombotic and antithrombolytic compositions and methods utilizing them

Also Published As

Publication number Publication date
DE1597480A1 (en) 1970-10-22
BE704277A (en) 1968-03-26
DE1597480B2 (en) 1977-07-14
DE1597480C3 (en) 1978-03-23
NL6711915A (en) 1968-02-26
GB1190914A (en) 1970-05-06

Similar Documents

Publication Publication Date Title
US4556630A (en) Color photographic light-sensitive material
US3563745A (en) Silver halide photographic materials containing 1-arylmethyl-2-pyrazolin-5-one color couplers
US3558319A (en) Color photographic silver halide emulsion containing magenta couplers
US3127269A (en) Colour photography
US3615505A (en) Silver halide emulsion containing 2-pyrazolin-5-one color coupler
US2998314A (en) Color photography
US2294909A (en) Chemical process and composition
US3700453A (en) Antistain agents comprising mixtures of secondary-alkylhydroquinones
US3013879A (en) Production of color photographic images
US2933391A (en) Photographic emulsions containing 5-pyrazolone coupler compounds
US3245788A (en) Production of color photographic images
US3222176A (en) Photographic colour images from amino substituted phenols
US3623871A (en) Photographic color process utilizing 2-pyrazolin-5-one couplers
US2865748A (en) 3-acylamido-5-pyrazolone and 3-acylamido-5-acyloxypyrazole couplers for color photography
US3622328A (en) Process for producing photographic color images
US3462270A (en) Color photography utilizing 1-fluoroalkyl - 2 - pyrazoline - 5 - one colour couplers
US3676124A (en) Photographic negative material for color diffusion transfer process
US3762921A (en) Photographic colour material
US3567449A (en) Silver halide photographic colour material containing 1-(cyanoalkyl)-pyrazolone color couplers
US2865751A (en) 1-alkyl-3-acylamido-5-pyrazolone couplers for color photography
US3393040A (en) Silver halide photographic elements containing sulfonic acid substituted aroylacetarylide couplers
US2350812A (en) Diketopyrimidine coupler
US3843366A (en) Yellow forming colour couplers for photographic silver halide material
JPS62133458A (en) Color photorecording material containing color coupler
US3008827A (en) Production of colored photographic images