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
  • G03C7/3212—Couplers characterised by a group not in coupling site, e.g. ballast group, as far as the coupling rest is not specific
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
  • C07D231/52—Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa

Definitions

• color photography dye images are produced by the reaction of the oxidation products of primary amino photographic developing agents, formed by the use of such developing agents in developing silver salt images, with certain classes of organic compounds which, as the result of such action, form azomethine, indophenol or related dyes.
• the developing agents used are usually N.N-dialkyl p-phenylene diamines or simple derivatives thereof, and the organic compounds which couple with the oxidation products of those developers, formed during development, are known as color couplers. These latter may contain amino groups and fall into several classes as follows:
• a process for the production of a color photographic image which comprises subjecting a developable silver salt image to development by means of an aromatic primary amino color developing agent in the presence of a color coupler which in the form of its free acid is represented by the general formula:
• RNH-- represents the residue of a color coupler containing an amino group and either one of R and R is a hydrogen atom and the other is a group of the formula:
• RNH is the residue of a color coupler containing an amino group selected from the class consisting of (a) color couplers which contain, in addition to the amino group, a -CO-CH -CO group, (b) color couplers which contain, in addition to the amino group, a cyanacetyl group, (0) color couplers which contain in addition to the amino group a pyrazolone ring, and (d) colour couplers which contain the amino group and are phenols and l-naphthols, and either one of R and R is a hydrogen atom and the other is a group of a structure selected from the group consisting of CO N-aeyl and N/ ⁇ Z 1 13 00/ where R is selected from the class consisting of a hydrogen atom, alkyl groups containing 1 to 18 carbon atoms, cycloalkyl groups containing 5 to 10 carbon atoms, aralkyl groups of which the alkyl moiety contains 1 to 3 carbon atoms, and
• acyl groups there may be mentioned acetyl, propionyl, benzoyl, lauroyl, stearoyl, isobutyryl, caproyl, isovaleryl, ethylsulphonyl, hexadecylsulphonyl, and p-toluenesulphonyl.
• alkyl groups represented by R there may be mentioned methyl, ethyl, butyl, heptyl, dodecyl, cetyl, octadecyl, iso-butyl, iso-amyl and tert.-octyl.
• cycloalkyl groups represented by R there may be mentioned cyclopentyl, cyclohexyl, hexahydrobenzyl and cyclodecyl.
• aralkyl groups represented by R there may be mentioned benzyl, p-dodecylbenzyl, 5 benzylisopropyl, naphthyl methyl, phenyl ethyl and phenyl propyl, and as examples of aryl groups represented by R there may be mentioned phenyl, tolyl, chlorophenyl, sulphophenyl, methoxyphenyl cyanophenyl, naphthyl and dodecylphenyl.
• RNH may represent the residue of any of the specific amino color couplers which are listed above (i.e. the residue obtained by removing a hydrogen atom from the amino group), or the residue of any other amino color coupler witln'n the generic groupings specified above. It is particularly to be noted that the nature of the amino color coupler residue is not critical. Any of the types known in this art may be used. The critical feature in the applicants products is the chain referred to above which characterises the products and leads to the advantages referred to above. Nevertheless, from the standpoint of color photography in natural colors it is obviously desirable to select the amino color coupler used as starting material so that the color coupler according to the present invention is of satisfactory hue, i.e. in one of the subtractive colors, yellow, magenta and cyan.
• the aforesaid color couplers wherein R or R stands for -N.R .acyl may be prepared by reacting a color coupler containing an amino group with an anhydride of the formula:
• the reaction between the color coupler containing an amino group and the anhydride may be conveniently carried out by heating the reactants together in a suitable organic solvent, for example glacial acetic acid.
• the new color couplers may be conveniently isolated by adding Water and/or an aliphatic alcohol, for example methanol and ethanol to the solution of the color coupler in the organic solvent and filtering off the solid which is precipitated.
• an aliphatic alcohol for example methanol and ethanol
• the color coupler so obtained consists of either or both of the two isomeric compounds which are obtain-.
• the anhydrides of the above formula may be obtained by heating an amino acid of the formula:
• R has the meaning stated above with an acid chloride or an acid anhydride.
• amino acids of the above formula may themselves be obtained by treating maleic acid with ammonia, or an alkylamine or a cycloalkylamine or an aralkylamine or an arylamine.
• anhydride of the above formula may be obtained by reacting an ester of maleic acid with ammonia, or an alkylamine, or a cycloalkylamine, or an aralkylamine or an arylamine, subsequently treating with an acid chloride or an acid anhydride, hydrolysing off the ester groups and subsequently treating with a dehydrating agent, for example acetic anhydride.
• a dehydrating agent for example acetic anhydride.
• suitable anhydrides which may be used in this process of the invention there may be mentioned stearoylaminosuccinic anhydride, acetylaminosuccinic anhydride, lauroylarninosuccinic anhydride, benzoylaminosuccinic anhydride, N-benzylacetylaminosuccinic anhydride, phenylacetylarninosuccinic anhydride, butyl-isobutyrylaminosuccinic anhydride, N-cetylacetylaminosuccinic anhydride, N-n-octadecylacetylaminosuccinic anhydride, N-n-octadecylpropionylaminosuccinic anhydride, N-n-octadecyl-iso-butyrylaminosuccinic anhydride, N-noctadecyl-isovalerylammosuccinic anhydride, N-n-hexadecylbenz
• the reaction between the color coupler containing the amino group and the compound of the above formula may be conveniently carried out by heating the reactants together in a suitable organic solvent, for example glacial acetic acid, and subsequently precipitating the new color coupler by the addition of water and/or methanol and ethanol.
• a suitable organic solvent for example glacial acetic acid
• the color coupler so obtained consists of either or both of the two isomeric compounds which are obtainable by reacting the color coupler containing an amino group with a compound of the above formula.
• the compounds of the above formula may themselves be obtained by reacting aminosuccinic acid with an anhydride of an ethylene, phenylene or tetrahydrophenylene dicarboxylic acid, and subsequently treating with a dehydrating agent, for example acetic anhydride.
• a dehydrating agent for example acetic anhydride.
• Suitable compounds of the above formula which may be used in this process of the invention there may be mentioned phthalimidosuccinic anhydride.
• the color couplers containing an amino group which may be used in the production of the color couplers for use in the present invention are, for example, those listed above.
• the aforesaid color couplers may be used in the photographic developing solution used for developing a photographic emulsion, or they may be included in the photographic material, in a light-sensitive layer or in a nonlight-sensitive layer adjacent to a sensitive layer or separated therefrom by a water-permeable colloid layer.
• a light-sensitive gelatinoor gelatino-substitute silver halide emulsion layer which forms part of a multi-layer film or paper of the kind used for color photography.
• those new color couplers which contain a substituent rendering them fast to diffusion, for example an alkyl chain containing at least 12 carbon atoms.
• the new color couplers may be used in the form of their salts with an alkali metal or an organic amine.
• the multilayer color photographic material may be a natural order material in which the images are to be formed in colors complementary to those of the original object or one in which an unnatural order is used, for example one in which in the top layer there is formed a yellow image of the blue parts of the object, in one of the two lower layers there is formed a cyan image of the green parts of the object and in the other a magenta image of the red parts of the object.
• the color couplers used in the present invention have important advantages over the color couplers from which they are derived.
• a light-sensitive gelatinoor gelatino-substitute silver halide emulsion layer containing an aforesaid color coupler is exposed to light, developed in a color-forming developer, bleached and fixed, and the photographic record so formed is exposed to light, there is litle or no staining of the record due to degradation by light of unreacted color coupler residual in the layer containing the dyestufi' image.
• the invention is illustarted, but not limited, by the following examples in which the parts and percentages are by weight:
• the color formers are obtained by the reaction of A-NH with either COOH-N acyl or 0 where A, R and Z have the meanings given above.
• the color couplers are formulated in a photographic emulsion layer according to one of the following methods.
• a color developer solution containing a color developing agent which for example may be 4-amino-3-methyl-N-diethylaniline (B), 4-amino-3-methyl-N-ethyl-N-w-hydroxybutyl aniline (C) or 4amino-N-ethyl-N-hydroxyphenyl aniline (D), bleached and fixed, a magenta dye image is obtained.
• a color developing agent which for example may be 4-amino-3-methyl-N-diethylaniline (B), 4-amino-3-methyl-N-ethyl-N-w-hydroxybutyl aniline (C) or 4amino-N-ethyl-N-hydroxyphenyl aniline (D)
• color coupler does not contain a long aliphatic chain it may be incorporated in a color developer solution, for example:
• solution A parts of trisodium phosphate and 1.2 parts of hydroxylamine sulphate are dissolved in 400 parts of water
• solution B 2 parts of the color coupler are dissolved (or suspended) in parts of ethanol (B).
• B is added to solution A, solution C then being added with stirring and the volume made up to 1000 parts with water.
• No. Process Agent R R1 or R2 Where one is H 31 NH O O C H III ⁇ B 668 C 673 32 NH 0 C 1H3 III C 644 I 11C18H37 33 N ⁇ III C 644 C O CH(CH CH3 34 NHCOCnH3 III B 645 CH3O
• Y is selected from the group consisting of hydro- To 200 parts of a gelatino-silver bromide emulsion there are added 50 parts of a 5% aqueous solution of the sodium salt of 4-stearoylaminobenzoylacet-3:S-dicarboxyanilide. The blue sensitive emulsion so obtained is coated on a paper base and the coated layer dried.
• a 3% aqueous solution of gelatin is then coated on top of the blue sensitive layer to form a gelatin separation layer.
• a green sensitive emulsion obtained as described in Example 1 is then coated on top of the gelatin separation layer.
• a gelatin separation layer is then coated on top of the green sensitive emulsion layer.
• a red sensitive emulsion comprising 200 parts of a red sensitive gelatinosilver chlorobromide emulsion and 50 parts of a 5% aqueous solution of the sodium salt of l-hydroxy-4-sulpho-2-naphtho-N-octadecylamide is then coated on top of the gelatin separation layer.
• the multilayer color photographic paper so obtained is exposed to the light from a color negative, developed in a color developer containing 4-amino-3-methyl-N-diethylaniline, bleached and fixed. A color print is obtained.
• Example 36 In place of the green sensitive emulsion used in Example 35 there is used a green sensitive emulsion obtained by adding 50 parts of a 5% aqueous solution of the potassium salt of the coupler of Example 9 to 200 parts of a green sensitive gel-atino-silver chlorobnomide emulsion.
• a process for the production of a color photograph image which comprises subjecting reducible silver salt image to development by means of an aromatic primary amino-color developing agent in the presence of a color coupler of the formula gen, an alkali metal and an amine group, where R is selected from the group consisting of (a) a benzyl aceto acetanilide having the structural formula:
• color coupler is l-phenyl-3- 3- (N-n-octadecylisobutyrylamino B-carb oxypropionylamino] -pyrazolone.
• color coupler is 1-phenyl-3-[ut-(N-n-octadecylisobutyrylamino)- ,B-carboxypropionylamino]5-pyrazolone.
• color coupler is 1-phenyl-3-(5-[N-(4'-n-dodecylphenyl)acetylamino] B-carb oxypropionyl amino) 5-pyrazolone.
• color coupler is 1-phenyl-3-(ct-[N-(4'-n-dodecylphenyl)acetylamino] -,8-carboxypropionylamino 5-pyrazolone.
• a process according to claim 1 wherein the coupler is 4 methoxybenzoylacet 5 [a (N n octadecylacetylamino) [3 carboxypropionylamino] 2 methoxyanilide.
• a process according to claim 1 wherein the coupler is 4' methoxybenzoylacet 5 ⁇ u-[N-(4-n-dodecylphenyl) acetylamino] fi carhoxypropionylamino ⁇ 2 methoxyanilide.
• a photographic color developing composition which comprises an aromatic primary amino photographic developing agent and a color coupler of the formula where Y is selected from the group consisting of hydrogen, an alkali metal and an amine group, where R is se- 18 lected from the group consisting of (a) a benzyl aceto acetanilide having the structural formula;
• R is selected from the group consisting of phenyl and alkoxy phenyl and R is selected from the group consisting of phenyl, alkoxy phenyl and alkyl amino phenyl;
• R is selected from the group consisting of and R i sa phenyl group
• R is selected from the group consisting of hydrogen, halogen, alkyl and alkoxy
• R is an acyl radical selected from the group consisting of alkanyl having 1 to 18 carbon atoms, phenoyl, alkylsultonyl, alkenylsulfonyl and alkylphenylsulfonyl
• R is selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, an aralkyl group and an aryl group
• Z is selected from the group consisting of ethylene, phenylene and tetrahydrophenylene.
• a photographic element comprising a support and 19 at least one layer of a light sensitive silver halide emulsion, containing disbursed therein a color coupler of the formula where Y is selected from the group consisting of hydrogen, an alkali metal and an amine group, where R is selected from the group consisting of (a) a benzyl aceto acetanilide having the structural formula:
• R is selected from the group consisting of NH and CONH-R NH, wherein R is selected from the group consisting of alkylene and arylene, and R is selected from the group consisting of hydrogen and halogen, and where either one of R and R is a hydrogen atom and the other is a radical selected from the group consisting of wherein R is an acyl radical selected from the group consisting of alkanyl having 1 to 18 carbon atoms, phenoyl, alkylsulfonyl, alkenylsulfonyl and alkylphenylsulfonyl, R is selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, an aralkyl group and an aryl group and Z is selected from the group consisting of ethylene, phenylene and tetrahydrophenylene.
• R is an alkyl having at least 12 carbon atoms.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Citations (1)

• 0
  • BE BE565852D patent/BE565852A/xx unknown
• 1957
  • 1957-03-20 GB GB9113/57A patent/GB830797A/en not_active Expired
• 1958
  • 1958-03-19 FR FR1202940D patent/FR1202940A/fr not_active Expired
  • 1958-03-20 DE DEJ19128A patent/DE1115129B/de active Pending
• 1960
  • 1960-08-29 US US52354A patent/US3133815A/en not_active Expired - Lifetime

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