US3245788A - Production of color photographic images - Google Patents

Production of color photographic images Download PDF

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US3245788A
US3245788A US100010A US10001061A US3245788A US 3245788 A US3245788 A US 3245788A US 100010 A US100010 A US 100010A US 10001061 A US10001061 A US 10001061A US 3245788 A US3245788 A US 3245788A
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radical
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color
emulsion
mask
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Jaeken Jan
Jansseune Robert Leopold
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Gevaert Photo Producten NV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D215/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D215/38—Nitrogen atoms
    • C07D215/42—Nitrogen atoms attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/22—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems 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 carbon atoms of the nitrogen-containing ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles 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 in position 2
    • C07D235/30—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles 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 in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D277/18—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole 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
    • C07D277/38—Nitrogen atoms
    • C07D277/50—Nitrogen atoms bound to hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles 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 in position 2
    • C07D277/82—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/195—Radicals derived from nitrogen analogues of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom 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
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • 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
    • G03C7/18—Processes for the correction of the colour image in subtractive colour photography

Definitions

  • the present invention relates to the production of colored photographic images, more particularly to a process of color correction utilizing an integral masking procedure,
  • the cyan dye which should absorb red light and transmit green and blue light usually absorbs a small amount of green and blue light, as well as a major pro- United States Patent layer containing a colorcoupler which is reactive with portion of red light.
  • the magenta dye which should absorb green light and transmit blue and red light usually absorbs a considerable amount of blue light and a small amount of red light, as well as a major proportion of green light.
  • the yellow dye which should absorb blue light and transmit green-and red light is usually satisfactory, Due to the above mentioned unwanted side-absorptions of the dyes formed by color development, it is practically impossible to obtain a true reproduction of the original colors on printing multicolor-photographic transparencies containing such dyes.
  • Correction of the colors on printing is therefor desirable, and this is usually done by masking, Since separate masks are diflicult to register with the color transparency, it is desirable that the mask be integral with the colored images.
  • a color corrected image is formed in a photographic element comprising a silver halide emulsion layer and a color coupler which is reactive withthe oxidation product of an aromatic amino developing agent to form by color development a primary dye image which absorbs a major proportion of light in one region of the visible spectrum and undesirably absorbs --ar"ninor proportion of light in at least one other region of the visible spectrum, by treating the exposed and color-developed photographic element with an oxidizing solution, such as a photographic-bleaching bath, in the presence of a compound, which after oxidation couples with the residual color coupler, whereby a secondary dye image having a gradation opposite to that of said primary dye image, and absorbing light in at least one of said unwanted minor absorption regions but transmitting substantially all the light in said major absorption region is formed.
  • an oxidizing solution such as a photographic-bleaching bath
  • a method is claimed of forming a color corrected image in .a photographic element having :atlleast .one silver halide emulsion the oxidation product of the aromatic amino developing agent to form by color development a primary dye image which absorbs a major proportion of light in one region of the visible spectrum, and undesirably absorbs a minor proportion of light in at least one other region of the visible spectrum, which method comprises treating said photographic element, after image-wise exposure and color development, with an oxidizing solution in the presence of a mask forming compound containing a grouping of the following structure:
  • R represents a hydrogen atom or an acyl radical such as an acetyl radical
  • R represents a hydrogen atom or a functional substituent which is sufliciently unstable for being split off during the oxidative coupling, such as e.g. a radical of the formula -CONH or SO X wherein X represents a hydroxyl radical, an amino radical, a substituted amino radical such as a dialkylamino radical, an heterocyclic radical, an aliphatic hydrocarbon radical, a substituted aliphatic hydrocarbon radical, an aryl radical or a substituted aryl radical;
  • R represents a hydrogen atom, an alkyl radical, an aralkyl radical, an aryl radical or a substituted aryl radical
  • Z represents the non-metallic atoms necessary to com: plete a heterocyclic nucleus containing 5-6 members, -at least one of Which is a nitrogen atom.
  • color corrected images can be formed by treating an imagewise exposed photographic element comprising a silver halide emulsion layer and a color coupler which is reactive with the oxidation product of an aromatic amino developing agent to form by color development a primary dye image, after the col-or forming development, with a oxidizing solution, such as a photographic bleaching bath, in the presence of a compound (called hereinafter mask forming compound) corresponding to one of the following general formulae:
  • R represents a hydrogen atom or a functional substituent which is sufliciently unstable for being split off during the oxidative coupling, such as e.g. a radical of the formula --CONH or ,SO X wherein X represents a hydroxyl radical, an amino radical, a substituted amino radical such as aidialkylarnino radical, a heterocyclic radical such as a N-rnorpholinyl radical or a N-piperidyl radical, an aliphatic hydrocarbon radical, such as an alkyl radical cg. amethyl radical or a hexadecyl radical, a substituted aliphatic hydrocarbon radical, an aryl radical, a substituted aryl radical e.g.
  • an alkoxy substituted phenyl radical such as a methyloxy or a hexadecyloxy radical, a carbethoxy substituted phenyl radical, an alkyl substituted phenyl radical such as a tolyl radical, a carboxy substituted a en ed 15 9 phenyl radical such as a"2,5-dichloro-phenyl radical,
  • R represents a hydrogen atom, an alkyl radical such as a methyl radical, a her'adecyl radical or an allyl radical, an arallryl radical such as a benzyl radical, an alkyl radical such as a methyl radical, a her'adecyl radical or an allyl radical, an arallryl radical such as a benzyl radical, an alkyl radical such as a methyl radical, a her'adecyl radical or an allyl radical, an arallryl radical such as a benzyl radical, an alkyl radical such as a methyl radical, a her'adecyl radical or an allyl radical, an arallryl radical such as a benzyl radical, an alkyl radical such as a methyl radical, a her'adecyl radical or an allyl radical, an arallryl radical such as a benzyl radical, an alkyl radical such as a methyl radical, a her'adecy
  • aryl radical such asa phenyl or a naphthyl radical or a substituted aryl radical such as a methoxy substituted phenyl radical
  • R represents ahy'drogen ator'n, an alkyl radical such as I a methyl radical, a hxadecyl radical, or an' allyl radical, an ar-alkyl radical such as a benzyl radical, an aryl radical such as a phenyl radical or a naphthyl radical or a substituted aryl radical such as a methoxy substituted phenyl radical;
  • R represents a hydrogen atom, an amino radical, a substituted amino radical such as a methylphenyl amino radical, an alkyl radical such as a methyl radical oruan ethyl radical, an aralkyl radical such as a dihalogenated phenyl radical, an hydroxy substituted phenyl radical, an alkoxysubstituted phenyl radical such as a monoor dimethoxy phenyl radical or a hexadecyc'loxy phenyl radical, an alkyl mercaptophenyl radical, an acyloxyphenyl radical such as a palrnitoyloxyphenyl radical, an acylarninophenyl radical, a dialkyl aminophenyl radical, such'as a p-(N- rnethyl-N-pentadecyl)-arninophenyl radical, an alkylsulfonylphenyl radical, or a heterocyclic
  • L and L each represents a methine' group or a nitrogen atom, at least one of L and L being a methine group;
  • Y represents the non-metallic atoms necessary to form an 'heterocyclic nucleus such-as a morpholine nucleus or a piperidine nucleus;
  • n is an integer from 1 to 4.
  • Amidrazones which can be used as mask forming compounds in the process of the present invention and which correspond to the general Formula I are for instance the compounds listed hereinafter:
  • OCHs 11 H S02 'CH CioHu OOCHQ L bin-s0 SOzOH benzyl radical, a substituted benzyl radical such as a methoxy substituted benzyl radical, an alkylene radical such as a methoxy styryl radical, an arylradi- Amidrazones which can be used as mask forming compounds in the process of the present invention and which correspond to the general Formula II are for in cal, a substituted aryl radical such as a monoor stance the compounds listed hereinafter:
  • R R and'R have the same significance as indicated in the general Formulae I and II.
  • thioamides can be used which are prepared accordingtosuificiently known. methods. Examples ofthese methods are e.g. the method indicated as the Wilgerodt-Kindler' reaction described by M. Carmack in Org. Reactions, vol. 3, p; 83/107, edited by R. Adams, John Wiley and Sons, New York (1946), and the transformation of amides into thioamides in pyridine by means of phosphorus pentasulfide described by E. Klingsberg,
  • a solution of26g. (0.75 mol) of n-hexadecyl'sulfonyl chloride in 280 cm. of ether is added dropwise to a solution of an exoess of hydrazine hydrate (40 cm?) in 200 em. of ethanol at temperature of 25 C; After stirring for min, 120 cm. of water are added to this solution. Then-hexadecyl sulfonyl' hydrazide crystals thus obtained are suckedoff: and washed with a? mixture of water and ethanol (1:3 by weight).
  • N ,N -cyclodiethylene oxide-N -hexadecylsulfonyf benzamidrazone 9.65 g. (0.0275 mol) of 4-(alpha-methylthiobenzylidene)-morpholinium iodide prepared according to D. Peak, J. Chem. Soc. (1952), 4067-75, and 8 g. (0.025 mol) of n-hexa-decylsulfonylhydrazide prepared according to Preparation 1, are heated for 2 h. at C. in a mix-. ture of 95 cmfiof pyridine and 5 cm. of piperidine. Next the reaction mixture is poured out into 500 cm. of water.
  • the 4-carboxyphenyl sulfonyl hydrazide used in the above preparation is obtained by first dissolving 11 g. (0.05 mol) of 4-carboxyphenylsulfonyl chloride in 650 COOH ' cm. of anhydrous ether and by adding thereto at -5 C.
  • PREPARATION 8 A mixture consisting of 13.6 g. (0.1 mol) of p-methoxybenz'ald'ehyde, 4.8 g. (0.15 mol) of flowers of sulfur and 13 cm. (0.15 mol) of morphoiine is refluxed for 3 h. on a water-bath. After cooling, sucking off, washing with water and recrystallization from ethanol, 20.5 g. of 4- methoxybenzothiomorpholide are obtained. Melting point: 109 C. A further recrystallization does not alter the melting point.
  • PREPARATION 10 w N -methyl-N -pl ienyl-N -n-hexadecylsulfohyb b'enzamidrazone
  • PREPARATION 11 N ,N -cycl0diethyleneoxide-N -n-hexadecylsulf0nylz-chlorob'enzamidrazone
  • 6 g. (0.15 mol) of sodium hydroxide in 50 cm. of water are first added at 0 C. 11 g. (0.125 mol) of morpholine and then at 0 to 5 C. 22 g. (0.125 mol) of o-chlorobenzoylchloride.
  • alpha-methylthio 3,4 di-methoxy-henzylidene-methyl-nhexadecylammonium iodide are obtained. Melting point: 100 C. (with decomposition). The product is unstable and cannot be purified by recrystallization.
  • the reaction mixture is poured on ice, sucked ofi, washed with an aqueous sodium sulphide solution and with water. By boiling the washed precipitate in carbon disulphide and by recrystallizing from dichloroethane 6 g. of dibenzothiopiperazide are obtained. Melting point: 275 C. (unsharp).
  • the mask forming compound is incorporated in one of the layers present in the light sensitive photographic material, preferably in the silver halide emulsion layer whereinthe mask image is to be formed by oxidative coupling of the residual color coupler, present in that layer, with the mask forming substance; in order to prevent the diffusion of the mask forming compound out of the silver halide emulsion layer wherein this compound originally Was incorporated, preferably mask forming compounds are used containing a radical (e.g. the radical X and/or R in the above formulae) com prising a linear chain of 5 to carbon atoms.
  • a radical e.g. the radical X and/or R in the above formulae
  • the process of color correction of the present invention may be practised i.e. by using a color photographic material containing a coupler for magenta belonging to the class of the pyrazolone or indazolone color couplers and/or a coupler for cyan belonging to the class of the phenol or naphthol color couplers.
  • a color photographic material containing a coupler for magenta belonging to the class of the pyrazolone or indazolone color couplers and/or a coupler for cyan belonging to the class of the phenol or naphthol color couplers.
  • yellow to magenta colored mask images are obtained on treating the photographic material with an oxidizing substance such as present in a potassium ferricyanide bleaching bath.
  • Naphthol color couplers which are especially useful for obtaining a mask image by reaction with the mask forming substances according to the present invention are e.g. those represented by the general formula:
  • X represents a member selected from the group consisting of an oxygen atom, a sulfur atom, a NHCO group, a CONH group, a SO NH- group, a NH-SO group, a -N-alkyl group and asulfonyl group;
  • Z represents a member selected from the group consisting of a hydrogen atom and a halogen atom
  • D represents an aliphatic radical comprising a linear chain of at least 5 and at most 20 carbon atoms, preferably 14, 16 or 18 carbon atoms;
  • M represents a member selected from the group consisting of a hydrogen atom, an alkali metal atom and an ammonium group.
  • Suitable color couplers of the above general formula are for instance:
  • col'or couplers for cyan can be prepared eg by condensation of l-hydroxy-Z-naphthoic acid or its derivatives with the suitable aromatic amines according to US. patent application Serial No. 66,289, filed' October 31, 1960, by Arthur Henri de Cat, Raphael Karel Van Poucke and Hector Alfons Vanden Eynde.
  • the color couplers and mask compounds can be incorporated into a photographic silver halide emulsion prepared by means of the colloids usually employed therefor, such as for instance gelatin, polyvinyl alcohol, cl-' lodion or other natural or synthetic colloids.
  • the silver halide emulsion can be coated on a support consisting of paper, glass, nitrocellulose, cellulose esters such as cellulose triacetate, polyester, polystyrene or another natural or synthetic resin, and forms part of a photographic material with one or more emulsion layers.
  • the multilayer material usually comprises the following elements: a support, a red-sensitive emulsion layer having a color coupler for cyan, a green-sensitive emulsion layer having a color coupler for magenta and a blue-sensitive emulsion layer having a color coupler for yellow.
  • a yellow filter composed in most of the cases of a gelatin layer containing dispersed colloidal silver, located between the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
  • the color couplers are not only possible to incorporate the color couplers into the light-sensitive silver halide emulsion layer itself but they can also be incorporated into an adjacent non-light-sensitive colloid layer or into a nonlight-sensitive layer which is separated from the lightsensitive emulsion layer by a water-permeable colloid layer.
  • the process according to the invention proceeds as follows: silver halide is reduced to silver at the exposed areas in a color developing bath containing a primary amine aromatic developing agent which is at thesame time oxidized.
  • the oxidized developing agent reacts with the color coupler and forms a dyestuff, the. mask forming compound according to the invention not being affected.
  • the material comes into the bleaching bath wherein the oxidation of the mask forming compound takes place.
  • the remaining color coupler still available at the non-exposed areas of the material couples oxidatively with the oxidation product of the compound thus formed whereby the colored mask is formed.
  • the photographic color material is washed with water, fixed and dried.
  • aromatic amino-compounds can be used as developers for such material: mono-, diand triamino-aryl compounds, more especially N,N-dialkyl-pphenylenediamines, such as N,N diethyl p phenylenediamine and N,N-diethyl-2-methyl p-phenylene diamine,-
  • N,N-dialkyl-N-sulfomethylor carboxymethyl-p-phenylenediamine As useful monoamino-developers should be cited: aminophenols and aminocresols or their halogen derivatives and also the amino-naphthols.
  • the bleaching bath generally contains potassium bro- EXAMPLE I
  • a red-sensitive silver bromo-iodide (2% iodide) emulsion containing /6 mol of silver halide are added: (1) a 10% aqueous solution containing as a color coupler for cyan 7 g. of 1,2-hydroxy-naphthoic acid-4- sulfo-2-n-hexadecylsulfonyl anilide, prepared according to a method described in our Belgian patent specification No. 584,846, and cm. of 2 N sodium hydroxide, and (2) 2 g.
  • N ,N .-cyclodiethylene oxide-N -n-hexa decylsulfonyl benzamidrazone prepared as described in Preparation 4, dissolved in 10 cm. of ethylene glycol monomethylether.
  • This material is rinsed for 30 minutes at 18 to 20 C. and fixed for 5 minutes at 20. C. in a fixing bath of the following composition:
  • the strip of finished light-sensitive color material shows in addition to a cyan wedge 21 redmasking wedge of opposite gradation, by which the side-absorptions of the cyan image are compensated.
  • EXAMPLE 2 To /2 kg. of a green-sensitive silver'bromo-iodide (2% iodide) emulsion containing mol ofsilverhalide is added an alcoholic solution of 6 g. of 1-(4-sulfophenyl)- 3-pentadecyl-pyrazolone-(5), prepared analogously to the method of Example 2 of British specification 502,665, and 2 g. of N ,N -cyclodiethylene oxide-N -hexadecyb sulfonyl benzamidrazone prepared according to Preparation 4. After-adding the usual additives the emulsion is coated, exposed, developed and further treated as indicated in Example 1. The finished strip shows in addition to a magenta wedge a yellow masking wedge of opposite gradation reducing the disturbing influence of the side adsorption in the formed magenta image.
  • the usual additives such as hardeners, wetting agents and stabilizers and the necessary quantity of distilled water are addedto the emulsion in order to obtain 1 kg. of flowable emulsion.
  • the emulsion is coated on a suit- 21 ablesupport and-dried.
  • the photographic material composed in this way is developed and further treated as in Example 1.
  • In the exposed and processed strip in addition to a cyan image also an orange to yellow mask image is formed, with a gradation opposed to that of the cyan image, and which compensates the side-absorptions of the cyan image in the blue as well as in the green region of the spectrum.
  • the usual additives such as hardeners, wetting agents and stabilizers, and the necessary quantity of distilled water are added to the emulsion in order to obtain 1 kg. of flowable emulsion.
  • the emulsion is coated on a suitable support and dried. After exposure through a grey-wedge with a constant 0.15, the photographic material composed in this way is developed and further treated as in Example 1.
  • the exposed .and processed strip in addition to a cyan image also an orange to yellow mask image is formed, with a gradation opposed to that of the cyan image, and which compensates the side-absorptions of the cyan image chiefly in the blue region of the spectrum.
  • the usual additives such as hardeners, wetting agents and stabilizers and the necessary quantity of distilled water are added to the emulsion in order to obtain 1 kg. of flowable emulsion.
  • the emulsion is coated on a suitable support and dried. After exposure through a greywedge with a constant 0.15, the photographic material composed in this way is developed and further treated as in Example 1.
  • an orange to yellow mask image is. formed, with a. gradation opposed to that of the cyan image, and which compensates the side-absorption of the cyan image in the blue as well as in the green region of the. spectrum.
  • the usual additives such as hardeners, wetting agents and stabilizers and the necessary quantity of distilled water are added to the emulsion in order to obtain 1 kg. of flowable emulsion.
  • the emulsion is coated on a suitable support and dried. After exposure through a grey-wedge With a constant 0.15, the photographic material composed this way is developed. and further treated as in Example 1.
  • Inthe exposed and processed strip in addition to a cyan image also an orange one is formed, with a gradation opposed to that of the cyan image, and which compensates the side-absorptions of the cyan image in the blue as well as in the green region of the spectrum.
  • EXAMPLE 7 To /2 kg. of a red-sensitive bromo-iodide emulsion (3% iodide) containing /6 mol of silver halide are added: (1) 9 g. of N-(6-n-hexadecylsulfonylphenyl)-1- hydroxy-2rnaphthoic acid amide-3'-sodium sulfonate dissolved in a mixture of 193 cm. of Water and 7 cm. of aqueous 2 N sodium hydroxide, and (2) 6 g. of the mask compound prepared according to Preparation 8, dissolved in a mixture of 6 cm. of 2 N sodium hydroxide and 24 cm. of ethanol.
  • the usual additives such as hardeners, wetting agents and stabilizers and the necessary quantity of distilled water are added to the emulsion in order to obtain 1 kg. of flowable emulsion.
  • the emulsion is coated on a suitable support and dried.
  • the photographic material composed in this way is developed and further treated as in Example 1.
  • In the exposed and processed strip in addition to a cyan image also an orange to magenta mask image is formed, with a gradation opposed to that of the cyan image, and which compensates the side-absorptions of the cyan image in the blue and the green region of the spectrum.
  • EXAMPLE 8 To /2 kg. of a red-sensitive bromo-iodide emulsion (3% iodide) containing /6 mol of silver halide are added: (1) 9 g. of N-(6'-n-hexadecylsulfonylphenyl)-1-hydroxy- 2-naphthoic acid amide-3'-sodium sulfonate dissolved in a mixture of 193 cm. of Water and 7 cm. of aqueous 2 N sodium hydroxide, and (2) 3 g. of the mask compound prepared according to Preparation 6, dissolved in a mixture of 3 cm. of 2 N sodium hydroxide, 3 cm. of ethanol, and 9 cm? of distilled water.
  • the usual additives such as hardeners, wetting agents and stabilizers, and the necessary quantity of distilled water are added to the emulsion in order to obtain 1 kg. of flowable emulsion.
  • the emulsion is coated on a suitable support and dried.
  • the photographic material composed in this way is developed and further treated as in Example 1.
  • In the exposed and processed strip in addition to a cyan image also an orange to magenta mask image is formed, with a gradation opposed to that of the cyan image, and which compensates the side-absorptions of the cyan image in the blue and the green regions of the spectrum.
  • EXAMPLE 9 To a /2 kg. of red-sensitive silver bromo-iodide emulsion (2% iodide) containing /6 mol of silver halide are added: (1) 10 g. of N-(6-n-hexadecylsulfonylphenyl)-lhydroxy-Z-naphthoic acid amide-3-sodium sulfonate dissolved in a mixture of 193 cm. of Water and 7 cm. of aqueous 2 N sodium hydroxide, and (2) 6 g. of the mask compound prepared according to Preparation 11, dissolved in a mixture of 6 cm. of 2 N. sodium hydroxide, 6 cm. of ethanol and 18 cm. of distilled Water.
  • this emulsion forms part of a multilayer photographic material consisting of the following superposed layers in the indicated sequence: a support, an anti-halation layer, a gelatin insulating layer, the above-mentioned red-sensitive emulsion.
  • EXAMPLE A photographic multilayer material consisting of the following superposed layers in the indicated sequence: a support, an anti-halation layer, a gelatin insulating layer, a red-sensitive emulsion layer containing a color coupler for cyan, a gelatin interlayer, a green-sensitive emulsion layer containing a color coupler for magenta, a yellow filter layer, a blue-sensitive emulsion layer containing a color coupler for yellow and at last a gelatin overcoat as antistress layer.
  • the red-sensitive emulsion layer is coated starting from a red-sensitized gelatino silver bromo-iodide emulsion. This emulsion is prepared as follows: to /2 kg.
  • this emulsion is acidified with acetic acid to pH 6, and after adding the usual additives such as hardeners, wetting agents, stabilizers and the necessary quantity of distilled water, 1 kg. of fiowable emulsion is obtained.
  • the greensensitive emulsion layer is coated starting from a greensensitized gelatino silver bromo-iodide emulsion.
  • This emulsion is prepared by adding to /2 kg. of gelatino silver bromo-iodide emulsion (2% iodide) containing /6 mol of silver halide, 9 g.
  • red-sensitive emulsion layer in addition to a cyan To /2 kg. of a red-sensitive broino-iodide emulsion (3% of iodide) containing /6 mol of silver halide are added: (1) 10 g. of N-(6'-n-hexadecylsulfonyl-phenyl)- 1-hydroxy-2-naphthoic acid amide-3-sodium sultonate dissolved in a mixture of 193 cm. of water and 7 cm.
  • an orange mask image is formed, with a gradation opposed to that of the cyan image, and which compensates the side-absorptions of the cyan image in the blue as well as in the green region of the spectrum.
  • R is a member of the group consisting of a hydrogen atom and an acyl radical
  • R is a member of the group consistingof a hydrogen atom, an'amino radical, an alkyl radical, an alkylene radical, an aryl radical, and a heterocyclic radical,
  • Y represents the non-metallic atoms necessary to complete a nitrogen-containing heterocyclic nucleus
  • said color coupler for magenta is a member of the group consisting of the indazolone and pyrazolone color couplers.
  • Y represents the non-metallic atoms necessary to complete a nitrogen-containing heterocyclic nucleus
  • R is a member of the group consisting of a hydrogen atom; an amino radical, an alkyl radical, an alkylene radical, an aryl radical, and a heterocyclic radical, and
  • X is a member of the group consisting of an hydroxyl radical, an amino radical, an aliphatic hydrocarbon radical, an aryl radical, and a heterocyclic radical;
  • said color coupler for magenta also being reactive with the oxidation product of said mask-forming compound to form a secondary dye image having a gradation opposite to that of said magenta primary dye image, and absorbing light in at least one of said unwanted minor absorption regions but transmitting substantially all the light in said major absorption region.
  • said color coupler for magenta is a member of the group consisting of the indazolone and pyrazolone color couplers.
  • R is a member of the group consisting of a hydrogen atom and an acyl radical
  • R is a member of the group consisting of a hydrogen atom, an amino radical, an alkyl radical, an alkylene radical, an aryl radical, and a heterocyclic radical,
  • R and R are each a member of the group consisting of a hydrogen atom, an alkyl radical, and an aryl radical,
  • Y represents the non-metallic atoms necessary to complete a nitrogen-containing heterocyclic nucleus
  • X is a member of the group consisting of an hydroxyl radical, an amino radical, an aliphatic hydrogen radical, an aryl radical, and a hetercyclic radical;
  • the residual color coupler oxidatively couples with said mask-forming compound to form a secondary dye image having a gradation opposite to that of said cyan primary dye image, said secondary image absorbing light in at least one of said undesirable minor absorption regions but transmitting substantially all the light in said major absorption region.
  • said color coupler 26 for cyan is a member of the group consisting o-tthe phenol and naphthol color couplers.
  • X is a radical of the group consisting of O', -S-,
  • SO Z is a member of the group consisting of a hydrogen atom and a halogen atom
  • D is an aliphatic radical comprising a linear chain-of 5-20 carbon atoms
  • M is a member of the group consisting of a hydrogen atom, an alkali atom, and an ammonium group.
  • R is a member of the group consisting of a hydrogen atom and an acyl radical
  • Y represents the non-metallic atoms necessary to complete a nitrogen-containing hetero-cyclic nucleus
  • R is a member of the group consisting of a hydrogenation, an amino radical, an alkyl radical, an alkylene radical, an aryl radical, and a heterocyclic radical,
  • R and R are each selected :from the group consisting of a hydrogen atom, an alkyl radical, and an aryl radical, and
  • X is a member of the group consisting of an hydroxyl radical, an amino radical, an aliphatic hydrogen radical, an aryl radical, and a heterocyclic radical;
  • said color coupler for magenta also being reactive with the oxidation product of said mask-forming compound to form a secondary dye image having a gradation opposite to that of said cyan primary dye image, and absorbing light in at least one of said unwanted minor absorption
  • X is a radical of the group consisting of O
  • Z is a member of the group consisting of a hydrogen atom and a halogen atom
  • D is an aliphatic radical comprising a linear chain of 520 carbon atoms
  • M is a member of the group consisting of a hydrogen atom, an alkali atom, and an ammonium group.

Description

, a 245,788 PRODUCTION OF COLOR PHOTOGRAPHIC IMAGES Jan Jaeken, Hove-Antwerp, and Robert Leopold Jansseune, Wilrijk-Antwerp, Belgium, assignors to Gevaert Photo-Broducten N. Mortsel, Belgium, a Belgian company No Drawing, Filed Apr. 3, 1961, Ser. No. 100,010 Claims priority, application Great Britain, Apr. 6, 1960,
' 12-,163/60 15 Claims. (Cl. 96-9) The present invention relates to the production of colored photographic images, more particularly to a process of color correction utilizing an integral masking procedure,
I It is known that dyes formed by color development in subtractive multicolor photographic pictures do not trans -v mit all of the light which practical considerations demand. The cyan dye which should absorb red light and transmit green and blue light usually absorbs a small amount of green and blue light, as well as a major pro- United States Patent layer containing a colorcoupler which is reactive with portion of red light. The magenta dye which should absorb green light and transmit blue and red light usually absorbs a considerable amount of blue light and a small amount of red light, as well as a major proportion of green light. The yellow dye which should absorb blue light and transmit green-and red light is usually satisfactory, Due to the above mentioned unwanted side-absorptions of the dyes formed by color development, it is practically impossible to obtain a true reproduction of the original colors on printing multicolor-photographic transparencies containing such dyes.
Correction of the colors on printing is therefor desirable, and this is usually done by masking, Since separate masks are diflicult to register with the color transparency, it is desirable that the mask be integral with the colored images.
A process for the production of a color photographic image wherein the mask is integral with the colored image is described in US. patent applications Ser. No. 705,508, now US. Patent 3,012,884, filed December 27, 1957; No. 70,914, now US. Patent 3,013,879, filed November 22, 1960, and No. 72,298, now US. Patent 3,047,385, filed November 29, 1960, by Maurice Antoine de Ramaix and Jan =Jaeken; Ser. No. 66,964, now US. Patent 3,079,256, filed November 3, 1960 by Raphael Karel Van Poucke, Arthur Henri de Cat and Marcel Hendrik Verbrugghe; vand Serial No. 71,1l7, filed November 14, 1960, by Jozef FransWillems and I an Jaeken.
According to said'pending applications a color corrected image is formed in a photographic element comprising a silver halide emulsion layer and a color coupler which is reactive withthe oxidation product of an aromatic amino developing agent to form by color development a primary dye image which absorbs a major proportion of light in one region of the visible spectrum and undesirably absorbs --ar"ninor proportion of light in at least one other region of the visible spectrum, by treating the exposed and color-developed photographic element with an oxidizing solution, such as a photographic-bleaching bath, in the presence of a compound, which after oxidation couples with the residual color coupler, whereby a secondary dye image having a gradation opposite to that of said primary dye image, and absorbing light in at least one of said unwanted minor absorption regions but transmitting substantially all the light in said major absorption region is formed.
In the last mentioned pending application a method is claimed of forming a color corrected image in .a photographic element having :atlleast .one silver halide emulsion the oxidation product of the aromatic amino developing agent to form by color development a primary dye image which absorbs a major proportion of light in one region of the visible spectrum, and undesirably absorbs a minor proportion of light in at least one other region of the visible spectrum, which method comprises treating said photographic element, after image-wise exposure and color development, with an oxidizing solution in the presence of a mask forming compound containing a grouping of the following structure:
Ra Ra wherein:
R represents a hydrogen atom or an acyl radical such as an acetyl radical,
R represents a hydrogen atom or a functional substituent which is sufliciently unstable for being split off during the oxidative coupling, such as e.g. a radical of the formula -CONH or SO X wherein X represents a hydroxyl radical, an amino radical, a substituted amino radical such as a dialkylamino radical, an heterocyclic radical, an aliphatic hydrocarbon radical, a substituted aliphatic hydrocarbon radical, an aryl radical or a substituted aryl radical;
R represents a hydrogen atom, an alkyl radical, an aralkyl radical, an aryl radical or a substituted aryl radical; and
Z represents the non-metallic atoms necessary to com: plete a heterocyclic nucleus containing 5-6 members, -at least one of Which is a nitrogen atom.
Now we have found that color corrected images can be formed by treating an imagewise exposed photographic element comprising a silver halide emulsion layer and a color coupler which is reactive with the oxidation product of an aromatic amino developing agent to form by color development a primary dye image, after the col-or forming development, with a oxidizing solution, such as a photographic bleaching bath, in the presence of a compound (called hereinafter mask forming compound) corresponding to one of the following general formulae:
as an acetyl radical;
R represents a hydrogen atom or a functional substituent which is sufliciently unstable for being split off during the oxidative coupling, such as e.g. a radical of the formula --CONH or ,SO X wherein X represents a hydroxyl radical, an amino radical, a substituted amino radical such as aidialkylarnino radical, a heterocyclic radical such as a N-rnorpholinyl radical or a N-piperidyl radical, an aliphatic hydrocarbon radical, such as an alkyl radical cg. amethyl radical or a hexadecyl radical, a substituted aliphatic hydrocarbon radical, an aryl radical, a substituted aryl radical e.g. an alkoxy substituted phenyl radical, such as a methyloxy or a hexadecyloxy radical, a carbethoxy substituted phenyl radical, an alkyl substituted phenyl radical such as a tolyl radical, a carboxy substituted a en ed 15 9 phenyl radical such as a"2,5-dichloro-phenyl radical,
and an acylarnino phenyl radical;
R represents a hydrogen atom, an alkyl radical such as a methyl radical, a her'adecyl radical or an allyl radical, an arallryl radical such as a benzyl radical, an
aryl radical such asa phenyl or a naphthyl radical or a substituted aryl radical such as a methoxy substituted phenyl radical; R represents ahy'drogen ator'n, an alkyl radical such as I a methyl radical, a hxadecyl radical, or an' allyl radical, an ar-alkyl radical such as a benzyl radical, an aryl radical such as a phenyl radical or a naphthyl radical or a substituted aryl radical such as a methoxy substituted phenyl radical;
R represents a hydrogen atom, an amino radical, a substituted amino radical such as a methylphenyl amino radical, an alkyl radical such as a methyl radical oruan ethyl radical, an aralkyl radical such as a dihalogenated phenyl radical, an hydroxy substituted phenyl radical, an alkoxysubstituted phenyl radical such as a monoor dimethoxy phenyl radical or a hexadecyc'loxy phenyl radical, an alkyl mercaptophenyl radical, an acyloxyphenyl radical such as a palrnitoyloxyphenyl radical, an acylarninophenyl radical, a dialkyl aminophenyl radical, such'as a p-(N- rnethyl-N-pentadecyl)-arninophenyl radical, an alkylsulfonylphenyl radical, or a heterocyclic radicalsuch as a furyl radical, a thienyl radical; a pyridyl radical or a 1,3-benzodioxol-5-yl radical;
L and L each represents a methine' group or a nitrogen atom, at least one of L and L being a methine group;
, Y represents the non-metallic atoms necessary to form an 'heterocyclic nucleus such-as a morpholine nucleus or a piperidine nucleus; and
n is an integer from 1 to 4.
Amidrazones which can be used as mask forming compounds in the process of the present invention and which correspond to the general Formula I are for instance the compounds listed hereinafter:
Compound R1 R, Br R4 R5 1:
1 Hm s0i -0H3 CmHaa Goon. r
coon i e a CH;
2 H- -SOQOOHS cH= -Cm u C OCH: r
a zC1s a-: CH; -cu,-C r
5 3 3 6 Q Q 7; H.-. sm-coon cu= 41mm, -c1 n s 11.-- -o0NH, 0Hi warn, Gwen: 1
9 11.- 4024210113, ciH5 0zHi ocrn 1 10 H..-. s'0l-C 000H 0H; -016Hfl Goon,
dour
OCHs 11 H S02 'CH: CioHu OOCHQ L bin-s0 SOzOH benzyl radical, a substituted benzyl radical such as a methoxy substituted benzyl radical, an alkylene radical such as a methoxy styryl radical, an arylradi- Amidrazones which can be used as mask forming compounds in the process of the present invention and which correspond to the general Formula II are for in cal, a substituted aryl radical such as a monoor stance the compounds listed hereinafter:
9 .Mask' formingv compounds having two. groups which can be split off during the oxidative coupling are e.g.:
use? CzHs The amidrazone compounds having the general For-- mulae I and II- can: be synthetized according to H. Bredereck, Ber. 92, 837-849 (1959), according to the reaction. scheme 10 carbazide. or thiosemicarbazide in alkaline medium. The reaction: scheme is the following:
wherein: R R and'R have the same significance as indicated in the general Formulae I and II.
On carrying out the second step of. the latter reaction with hexadecyl sulfonyl hydrazide instead of semicarbazide a non-migratory mask compound is obtained. As starting materials thioamides can be used which are prepared accordingtosuificiently known. methods. Examples ofthese methods are e.g. the method indicated as the Wilgerodt-Kindler' reaction described by M. Carmack in Org. Reactions, vol. 3, p; 83/107, edited by R. Adams, John Wiley and Sons, New York (1946), and the transformation of amides into thioamides in pyridine by means of phosphorus pentasulfide described by E. Klingsberg,
J.A.'C.S. 73, p'. 4988 (1951).
Byway ofexample the preparations of some mask compounds of the present invention are given hereinafter.
PREPARATION l N-phenyl-Z,6-dimethyl pyridone- (4 )-hydi'az0r te-dihydr0- chloride This compoundcan be-prepared according, to S. Hiinig. andG. Kobrich, Ann. 617, p. 194 (1958)..
. PREPARATION .2. N ;N dz'nrethyl N '-n-hexadecylsul fonyl formamidrazone HCN(CH N-NH-Soz onz wcn A solution of26g. (0.75 mol) of n-hexadecyl'sulfonyl chloride in 280 cm. of ether is added dropwise to a solution of an exoess of hydrazine hydrate (40 cm?) in 200 em. of ethanol at temperature of 25 C; After stirring for min, 120 cm. of water are added to this solution. Then-hexadecyl sulfonyl' hydrazide crystals thus obtained are suckedoff: and washed with a? mixture of water and ethanol (1:3 by weight).
After drying an recrystallizat-ionafromacetonitrile, 24 g. of n-hexadecyl sulfonyl hydrazide melting at.89 C. are obtained.
A, solution of 2.31: gof phosphorus oxychloride (0.0050 mol) in 4 cm. of anhydrous benzene is added? to a solution of 3.65 g. (0.0050 mol) of dimethylformamide in 4 =cm. of anhydrous benzene at a temperature: of C. This mixture is kept overnightatroom temperature. Next, asuspension of 4 g. (0.0125 mol) of n-hexadecylsulfonylhydrazide in cm. of anhydrous benzene, prepared as described hereinbefore, is admixed at 2025 C. After stirring for 5 h. and storing for 12 h., the resulting hydrochloride is precipitated with ether, sucked off and Washed'with ether. 5.8 g. of a hydrochloride melting at 150 C. (with decomposition). is obtained: The base is set free by introducing said hydrochlorideinto water, neutralizing with sodium bicarbonate and extracting. with benzene. Next, this benzene solution is evaporated under reduced pressure at 40 C., and the resulting residue is washed with ethanol. 1.4" g. of N ,N dimethyl N -n hexadecylsulfonyl formamidrazone melting at 89 C. are Obtained. This melting point does not rise after recrystallization from methanol or free acetonitrile.
PREPARATION 3 N ,N -cyclodiethylene oxide-N -n-hexadecylsulfonylthieneamidrazone H O G H OHz-CE:
CHrCHa NNHSO 2-(0 H2) -43133 5.6 g. (0.050 mol) of 2-thiopheno aldehyde, 2.4 g. (0.075 mol) of sulfur and 6.5 g. (0.075 mol) of morpholine are heated .for 3 h. on a water-bath. After pouring the reaction mixture into 100 cm. of water, sucking off, ,washing with water and drying, 11.5 g. of 'a product melting at 72 C. are obtained. After recrystal-- lization from isopropanol, 7.8 g. of thiothieno morpholide melting constantly at 77 C. are obtained.
A solution of 2.13 g. (0.010 mol) of this compound in 15 cm. of acetone is refluxed for 1 h. with 2 cm. (0.030 mol) of methyliodide. The resulting 'precipi-- tate is sucked off and washed with acetone. 3.8 g. of 4-(alpha-methylthiothienylidene) morpholinium iodide melting at 163 C. (with decomposition) are obtained.
1.95 g. (0.0055 mol) of this morpholinium iodide and 1.6 g. (0.005 mol) of n-hexadecylsulfonyl hydrazide, prepared as described in Preparation 2, are allowed to react for 24 h. at room temperature in 18 cm. of pyridine. After pouring this reactionmixture into 100 cm. of water, sucking ofi, washing with water and drying, 2 g. of a product melting at 60 C. are obtained. After re-- crystallization from methanol 1 g. of N ,N -cyclodiethylene oxide-N -n-hexadecylsulfonyl thienamidrazone -melt-' ing at 78 C. is obtained.
PREPARATION 4 N ,N -cyclodiethylene oxide-N -hexadecylsulfonyf benzamidrazone 9.65 g. (0.0275 mol) of 4-(alpha-methylthiobenzylidene)-morpholinium iodide prepared according to D. Peak, J. Chem. Soc. (1952), 4067-75, and 8 g. (0.025 mol) of n-hexa-decylsulfonylhydrazide prepared according to Preparation 1, are heated for 2 h. at C. in a mix-. ture of 95 cmfiof pyridine and 5 cm. of piperidine. Next the reaction mixture is poured out into 500 cm. of water. The precipitate formed is sucked off, washed with water and dried. 11.7 g. of product melting on sharply at 80 C. are obtained. After recrystallization from methanol 8 g. of N ,N -cyclodiethylene oxide-N, -n-: hexadecylsulfonyl benzamidrazone melting at 94? C. for obtained.
PREPARATION 5 N ,N -cycl0diethyleneoxide-N -n-hexadecylsulfanyl phenyl acetamidrazone /CH2-CE: H CHz-CH: N-NH-SOr-(CHzha-CHa 1 g. (0.0027 mol) of 4-(l-methylthio-2-phenyl ethyl-3 idene)-n1orpholinium iodide, prepared according to Dr. Peak, J. Chem. Soc. (1952), 4071, and 0.8 g. (0.0025 mol) of n-hexadecylsulfonyl hydrazide .are allowed to re-- act for 24 h. at room temperature in 20 cm. of pyridine. After pouring this solution-into water and recrystallization from methanol 0.5g. of amidrazone-melting at 79 C. is obtained.
PREPARATION 6' N ZN -cyclopentyl-N (4-carboxyphenylsulfonyl -3- meth0xy-4-n-hexadecylbenzamidrazone /CHz-Cgz I N-NHSOr- OCH3.
7.5 g. (0.33 mol) of sodium are dissolved in 750 cm. of methyl Cellosolve (trade name for ethylene glycol monomethylether). After adding 50 g. (0.33 mol) of 3-methoxy-4-hydroxybenzaldehyde and refluxing the reaction mixture until complete dissolution of the reactants g. (0.3 mol) of n-hexadecylbromide are dropwise added. After further. heating for 1.5 h., the reaction mixture is cooled and 'suckedotf. The filtered crystals are then recrystallized from methanol yielding 86 g. of 3 methoxy 4 n hexadecyloxybenzaldehyde. Melting point: 69 C.
A mixture consisting of 9.4 g. (0.025 mol) of this aldehyde, 1.2 g. of flowers of sulfur and 3.7 cm'. (0.038 mol) of piperidine is heated for 6 h. on a water-bath. After .cooling, the product obtained is ground under water, sucked off, washed with water and recrystallized from ethanol yielding 9.7 g. of 3-methoxy-4-n-hexadecyloxybenzothiopiperidine. Melting point: 67 C.
A mixture consisting of 38 g. (0.08 mol) of this compound, 16 cm. (0.24 mol) of methyl iodide and 160 cm. of anhydrous acetone are refluxed for 1 h. After sucking off and washing with ether 41.5 g. of l-alpha-methylthio 3-methoxy-4-r1-hexadecyloxy benzylidene-piperidinium iodide are obtained. Melting point: 90 C. (with decomposition). On recrystallization the product is unstable.
6.17 g.. (0.01 mol) of this compound dissolved in 50 cm. of pyridine are allowed to react for 12 h. at room temperature with 2.16 g. (0.01 mol) of 4-carboxyphenyl sulfonyl hydrazide. After. pouring into ice, sucking off, washing with water and recrystallization from acetonitrile, 3 g. of 'N ,N -cyclopentyl-N -(4-carboxyphenylsulfonyl)- 3 methoxy 4-N-hexadecyloxybenzamidrazone are obtained. Melting point; 108 C.
The 4-carboxyphenyl sulfonyl hydrazide used in the above preparation is obtained by first dissolving 11 g. (0.05 mol) of 4-carboxyphenylsulfonyl chloride in 650 COOH ' cm. of anhydrous ether and by adding thereto at -5 C.
N ,N -cyclopentyl-N -n-hexadecylsulfonyl-3-methoxy-4- hydroxybenzamidrazone CHz-CHz N HOO \CH2-C2 (I) 0 H3 N-NHS O r( 2)1s z 8.75 g..(0.0575 mol) of 3-metl1oxy-4-hydroxybenzaldehyde and-5 0111.3 (0.050 mol) of piperidine are reacted for 8 h. at C. with 2.4 g. (0.075 mol) of sulfur. The
' sticky mass is cooled and transformed into a powdery substance by adding water thereto. This powder is sucked oii and washed with water until neutral. The crude product obtained is recrystallized. from petroleum naphtha (boiling range. 90-120) yielding 7 g. of 3-methoxy-4- hydroxybenzothiopiperidide. Melting point: 118 C. Re-
1.3 crystallization from ethylaeetate raises the melting point to 119 C. p 15 g. (0.06 mol) of the foregoing thioamide are refiuxed for 1 h. with 17 cm. (0.28 mol) of methyliodide in 177 cm. of anhydrous acetone.
After cooling the reaction product is sucked off and washed with ether yielding 23 g. of 1-(alpha-methylthio- 3 methoxy-4-hydroxy-benzylidene)-piperidinium iodide. Melting point: 176 C. (with decomposition). The prodnot is unstable on recrystallization.
23 g. (0.06 mol) of the foregoing iodide salt are reacted at room temperature for 12 h. with 18.4 g. (0.06 mol) of n-hexadecyl sulfonyl hydrazide dissolved in 230 cm. of pyridine.
After pouring out the reaction mixture on ice, the solidified product is Washed with water and recrystallized from ethanol. 25 g. of N ,N -cyclopentyl-N -n-hexadecyl sulfonyl 3 methoxy-4-hydroxybenzamidrazone are obtained. Melting pointi 93 C.
PREPARATION 8 A mixture consisting of 13.6 g. (0.1 mol) of p-methoxybenz'ald'ehyde, 4.8 g. (0.15 mol) of flowers of sulfur and 13 cm. (0.15 mol) of morphoiine is refluxed for 3 h. on a water-bath. After cooling, sucking off, washing with water and recrystallization from ethanol, 20.5 g. of 4- methoxybenzothiomorpholide are obtained. Melting point: 109 C. A further recrystallization does not alter the melting point.
A mixture consisting of 11.8 g. (0.05 mol) of this thiomorpholide, 50 cm. of anhydrous acetone and 5 cm. (0.05 .mol) of methyl iodide is refluxed for 1 h. The precipitate formed is sucked ofi and Washed with ether to yield 18.5 g. of 4-(alpha-methylthio-4-n1ethoxybenzylidene)-morpholiniurn iodide. Melting point: 152 C. (with decomposition). On recrystallization this product is not stable.
1.04 g. (0.00275 mol) of this morpholinium iodide is reacted for 12 h, at room temperature in a mixture of 35 cm. of pyridine and 0.8 g. (0.0025 mol) of n-hexadecylsulfonyl hydrazide. The reaction mixture is poured into ice. The formed crystals are sucked off, washed with water and recrystallized from ethanol to yield 1 g. of N N cyclodiethylene oxide N -n-hexadecylsulfonyl-4-me thoxybenzarnidrazone. Melting point: 69 C.
PREPARATION 9 N ,N -cycldiethylene oxid-N -n-lzexadecylsulf0nyl-2,4- dichlorobenzamidrazbne To a chilled solution of 6 g. (0.15 mol) of sodium hydroxide in 50 crn. of Water are first added at 0 C. 11 g. (0.125 mol) of morpholine, and then at 0 to C. 26.2 g. (0.125 mol) of 2,4-dichlorobenz'oylchloride. After adding the reactants the reaction mixture is stirred for another hour at the same temperature. After sucking off, washing until neutral with water and recrystallization from petroleumnaphtha, 24 g. of 2,4-dichloro-benzomorpholide are obtained. Melting point: 94 C.
5.2 g. (0.02 mol) of this morpholide in a mixture of 25 cm. of pyridine and 1.8 g. (0.008 mol) of phosphorus pentasulfide are refluxed for 40 min. After pouring the reaction mixture into ice the formed precipitate is sucked off, washed with water and recrystallized from ethanol to yield 4.5 g. of 2,4-dichlorobenzothiomorpholide. Melting point: 148 C.
34.5 g. (0.125 mol) of this thiomorpholide dissolved in 22.5 cm. (0.375 mol) of methyliodide are refluxed for 1 h. After sucking oil, 20 g. of 4-(alpha-methylthio-2,4- dichlorobenzylidene)-morpholinium iodide are obtained. Melting point: C. (with decomposition). This product i unstable on recrystallization.
55 g. (0. 13 mol) of this product dissolved in 750 cm. of pyridine are reacted at room temperature for 48 h. with 39 g. (0.12 mol) of n-hexadecylsulfonylhydrazide. After pouring this reaction mixture into ice, sucking otf, washing with water and recrystallization, 54 g. of N ,N cyclodiethylene oxide-N -n-hexadecylsu-lfonyl-2,4-dichlorobenzamidrazone are obtained. Melting point: 70 C.
PREPARATION 10 w N -methyl-N -pl ienyl-N -n-hexadecylsulfohyb b'enzamidrazone PREPARATION 11 N ,N -cycl0diethyleneoxide-N -n-hexadecylsulf0nylz-chlorob'enzamidrazone To a chilled solution of 6 g. (0.15 mol) of sodium hydroxide in 50 cm. of water are first added at 0 C. 11 g. (0.125 mol) of morpholine and then at 0 to 5 C. 22 g. (0.125 mol) of o-chlorobenzoylchloride. After the addition of the reactants stirring is continued for /2 h. at the same temperature. The product formed is filtered off and washed with water until neutral. Recrystallization from petroleum naphtha yields 20 g. of 2-chlorobenzomorpholide. Melting point: 73 C.
14.5 g. (0.065 mol) of the preceding amide are reacted at reflux temperature for 40 with 5.8 g. (0.026 mol) of phosphorus pent-asulfide in 65 cm. of pyridine. After pouring out the reaction mixture in ice, sucking off, washing with water and :recrystallizing from ethanol 11 g. of 2chlorobe-nzothiornorpholide are obtained. Melting point: 124 C.
11 g. (0.045 rnol) of the preceding thioamide are refiuxed for 1 h. with 8.8 cm. (0.15 mol) of methyliodid'e in 40 cm. of anhydrous acetone. After cooling, the formed reaction product is sucked off and washed with ether to yield 16 "g. of 4--(alpha-methyl-thio-2-chlorobenzylidene)-morp holini urn iodide. Melting point: 152 C. (with decomposition). The product cannot be recrystallized because it is not stable enough.
16 g. (0.04 mol) of the preceding morpholinium iodide are reacted at room temperature for 48 11. with 11.5 g.
(0.036 mol) of nhexadecylsulfonylhydraziide in 220 cm. of pyridine. The reaction mixture is poured into ice and the precipitate formed is sucked otf, washed with water and recrystallized from nhexane to yield 17 g. of N ,N
PREPARATION 12 N -methyl-N -n-hexadecyl-N (4'-carboxyphenylsul fonyl -3 ,4 -dim'etl txy benzamidrazone C H;
z C a0--- 915- 3 To a solution of 25.5 g. (0.1 mol) of methyl-n-hexadecylamine in a mixture of 250cm. of diox-ane and 22.5
cm. (0.11 mol) of N sodium hydroxide is added drop-- wise at 20 C. a solution of 20.5 g. (0.1 mol) of 3,4- dimethoxybenzoylchloride in 50 cm. of dioxane. After stiring this mixture for 1 h. 125 cm. of water are added. The formed oily layer is dried on sodium sulfate and d stilled under reduced pressure. Boiling point: 236- 240 C., 0.4 mm. of Hg pressure. Yield: 34- g. of 3,4- dimethoxy-benzoic acid-methyl-n-hexadecylamide.
45 g. (0.1 mol) of the preceding amide are refluxed for 2 h. with 24 g. (0.1 mol) of phosphorus pentasulfide in 100 0111. of pyridine. ing sodium chloride, the coagulated product .is sucked off, washed with water and recrystallized from acetonitrile to yield 34 g. of 3,4-dimethoxyabenzothio-methyl nhexadecylarnide. Melting point: 63 C.
g. (0.023 mol) of the preceding thioamide are dissolved at room temperature in 10 cm. of methyliodide. Immediately after complete dissolution ether is added and the solution is left for 12 h. in a refrigerator. 6.1 g. of
alpha-methylthio 3,4 di-methoxy-henzylidene-methyl-nhexadecylammonium iodide are obtained. Melting point: 100 C. (with decomposition). The product is unstable and cannot be purified by recrystallization.
13.5 g. (0.0234 mol) of the preceding compound are allowed to react for 72 h. .at room temperature in 50 cm. of pyridine with 5.05 g. (0.0234 mol) of 4-carboxyphenylsulfonylhydrazide. The solvent is distilled off and the residue is left under Water to solidify. The solidified product is freed from water by sucking cit and recrystalg l-ized from ethanol to yield 8 g. of N methyl-N -n-hexadecyl-N -(4 carboxyphenylsulfonyl)3,4 dimethoxybenzaimidrazone. Melting point: 142 C.
, PREPARATION 13 N -methyl-N -n-hexadecyl-N (4'tolusulfonyl) -4- methoxy benzamidrazone yields 70 g. of p-n1ethoxybenzoyl-N-methyl-N-n-hexadecylarnide. Melting point: 50 C.
15 g. (0.04 mol) of this amide are refluxed for 40 min. with 4 g. (0.016 mol) of phosphorus pentasulfide in 150 cm. of pyridine. The reaction mixture is poured on ice and the solidified material formedis sucked off, washed with water and recrystallized from ethanol to yield 13.5
After pouring into ice and add-' Whilst stirring at 10 C., 41 g. (0.24 mol) of 16 g. of 4-methoxybenzothio-N-methyl N n=hexadeeylamide. Melting point: 63 C.
13.5 g. (0.033 mol) of this thioam-ide are refluxed for 1 hf. with 13.5 cm. (0.02-2'mol) of methyliodide in ctn. of acetone. After distilling off the'solvent and washing the residue with the ether, 17 g. of valpha-methylthio- 4-methoxybenzylideneamethyl-n-hexadecyl ammonium iodide are obtained. Melting point: C. (with decomposition). This'product is not stable enough for being purified by recrystallization.
11 g. (0.02 mol) of this compound are reacted for 12 h. at room temperature with 3.7 g. (0.02 mol) of p-tolusulfonylhydrazide in 70 cm. of pyridine. The reaction mixture is poured on ice; The precipitatezformed is Washed'with water :and recrystallized fromxmethanol to yield 8 g. of N methyl N n hexadecyl N (4- tolusulfonyl) 4 methoxybenzamidrazone. Melting point: 66 C.
PREPARATION 14 N -phenyI-N -allyI-N -(4'-t0lusulfonyl)-benzamidrazone MHSOP CH.
To a boiling solution of 13.3 g. (0.1 mol) of N-allylaniline in toluene is dropwise added a solution of 14 g. (0.1 mol) of 'benzoylchloride in 50 crn. of toluene insuch a rate that. the toluene on being distilled over carries off the formed :hydrogen'chloride. This. reaction is com tin-ued for 8 h., during which period toluene is added for maintaining the liquid volume constant. After distilling oil the solvent the residue is distilled under reduced pressure to yield 15 g. of -N-allylbenzanilide. Boiling range: 134138 C./0.6 mm. of Hg pressure.
76g. (0.32 mol) of this anilide are allowed to react for 40 min. with 44.5 g. (0.2 mol) of phosphorus pentasulfide in 450 crn. of pyridine. The reaction mixture is poured on ice, washed with a sodium sulfide solution and with water. Recrystallization from n-hexane yields 57 g. of N-allyllbenzothioanilide. Melting point: 69 C.
5 g. (0.02 mol) of this thioanilide are reacted for 12 h. at room temperature With 15 cm. of methyliodide. After sucking oil the solid product and washing with acetone, 7.2 g. of alpha-methylthiobenzylidene N-allylanilinium iodide are obtained. Melting point: 180 C. (with decomposition). -For the product is not stable enough it cannot be purified by recrystallization.
4 g. (0.01 mol) of the preceding compound and 1.7 g. (0.03 mol) of potassium hydroxide dissolved in 40 cm. of anhydrous ethanol are reacted for 24 h. at roorntemperature with 1.86 g. (0.01 mol) of p-tolusulfonylhydrazide. After evaporating under reduced pressure at 30 C., the residue is first Washed with water and next with ethanol in order to obtain a solid product. After recrystallization from methanol 1.3 g. of N -phenyl-N allyl-N (4'-tolusulfonyl)'-'benzamidrazone are obtained. Melting point: C.
PREPARATION 15 88.2 g. (0.3 mol) of dibenzoylpiperazine prepared according to vA. V. Hofrnann, Ber. 23, 3301 (1890), are-re fi-uxed for 2 h. with 80 g. (0.36 mol) of phosphorus pentasulphide in 200 cm. of pyridine. The reaction mixture is poured on ice, sucked ofi, washed with an aqueous sodium sulphide solution and with water. By boiling the washed precipitate in carbon disulphide and by recrystallizing from dichloroethane 6 g. of dibenzothiopiperazide are obtained. Melting point: 275 C. (unsharp).
1.83 g. (0.005 mol) of this product is refluxed for l h. with 3.6 cm. (0.06 mol) of methyliodide in 40 cm. of dichloroethane. The reaction mixture is sucked off and the solid product obtained is washed with dichloroethane to yield 3.1 g. of 1,4-di(Q-methylthio benzylidene)-piperazonium iodide. Melting point: 190 C. (with decomposition). This product is unstable and cannot be purified by recrystallization.
7.2 g. (0.12 mol) of the foregoing compound are allowed to react for 24 h. at room temperature with 7.5 g. (0.24 mol) of n-hexadecylsulfonyhhydrazide in 150 cm. of pyridine. The reaction mixture is poured on ice, the solid product formed is sucked off, washed With water and next with methanol. Recrystallization from methyl-ethyletone yields 7 g. of N N N N diethylene di (N n hexadecylsulfonylbenzamidrazone). Melting point: 141 C.
' @nt r A solution in cm? of Warm ethanol of 1.99 g. (0.005 mol) of N,N'-dimethyl-N,Ndiphenyl-S-methylisothiouronium iodide, prepared according to D. Peak, J. Chem. Soc., 4072 (1952), is dropwise added to 0.25 cm. (0.005 mol) of hydrazine hydrate whilst heating on a water-bath. Heating is continued for 2 h. and air is bubbled through the reaction mixture until no more methylmercaptane is formed. After evaporation to dryness, the residue is washed with ether and recrystallized from isopropanol. 1 g. of N,N-dimethyl-N,N-diphenyl- N"-amino-guanidine is obtained. Melting point: 182 C.
According to a preferred embodiment of the present invention, the mask forming compound is incorporated in one of the layers present in the light sensitive photographic material, preferably in the silver halide emulsion layer whereinthe mask image is to be formed by oxidative coupling of the residual color coupler, present in that layer, with the mask forming substance; in order to prevent the diffusion of the mask forming compound out of the silver halide emulsion layer wherein this compound originally Was incorporated, preferably mask forming compounds are used containing a radical (e.g. the radical X and/or R in the above formulae) com prising a linear chain of 5 to carbon atoms.
The process of color correction of the present invention may be practised i.e. by using a color photographic material containing a coupler for magenta belonging to the class of the pyrazolone or indazolone color couplers and/or a coupler for cyan belonging to the class of the phenol or naphthol color couplers. Depending upon the structure of the color coupler used in combinationwith the mask-forming compound according to the present invention, yellow to magenta colored mask images are obtained on treating the photographic material with an oxidizing substance such as present in a potassium ferricyanide bleaching bath.
It has been found that by oxidative coupling of the mask-forming compounds of the Formula II above with a pyrazolone or indazolone color coupler for magenta, a yellow colored mask image is obtained which compensates the undesirable side-absorption in the blue part of the spectrum of the magenta dye image obtained by 18' color development of the exposed areas of the layer containing said coupler for magenta.
It has further been found that by oxidative coupling of the mask-forming compounds of the Formula I or II above with naphthol color couplers for cyan, a yellow to magenta colored mask image is obtained which compensates the undesirable side-absorption in the blue and green part of the spectrum of the cyan image obtained by color development of the exposed areas of the layer containing said cyan coupler. Naphthol color couplers which are especially useful for obtaining a mask image by reaction with the mask forming substances according to the present invention are e.g. those represented by the general formula:
(.FH ill-D o O-NII- i SOaM Z wherein:
X represents a member selected from the group consisting of an oxygen atom, a sulfur atom, a NHCO group, a CONH group, a SO NH- group, a NH-SO group, a -N-alkyl group and asulfonyl group;
Z represents a member selected from the group consisting of a hydrogen atom and a halogen atom;
D represents an aliphatic radical comprising a linear chain of at least 5 and at most 20 carbon atoms, preferably 14, 16 or 18 carbon atoms;
M represents a member selected from the group consisting of a hydrogen atom, an alkali metal atom and an ammonium group.
Suitable color couplers of the above general formula are for instance:
N-(2-n-hexadecyloxy-5-sulfo)' phenyl 1 hydroxy-2- naphthoic acid amide sodium salt, N(2-n-hexadecyloxy 5 sulfo) phenyl-1-hydroxy-4- chloro-Z-naphthoic acid amide sodium salt, N-(2-n-hexadecylmercapto 5sulfo) phenyl-l-hydroxy- 2-naphthoic acid amide sodium salt, N-(2'-n-hexadecylmercapto-5-sulfo) phenyl-l-hydroxy- 4-bromo-2-naphthoic acid amide sodium salt, N-(2-n-hexadecylmercapto-5'-sulfo) phenyl-l-hydroxy- 4-chloro-2-naphthoic acid amide sodium salt, N-(2-palmitoylarnino 4' sulfo) phenyl-l-hydroxy-Z- naphthoic acid amide sodium salt, N-(2-methyl cetylamino-5'-sulfo )-phenyl 1 hydroxy-4- chloro-Z-naphthoic acid amide sodium salt, N-('6'-n-hexadecylsulfonylphenyl)-1-hydroxy 2 naphthoic acid amide-3-sodium sulfonate, N-(6-n-hexadecylsulfonylphenyl') 1 hydroxy-4-chloro- Z-naphthoic acid amide-3-sodium sulfonate, N-(4-n hexadecylsulfonyl)-1-hydroXy-2-naphthoic acid amide-3-sodium sulfonate.
These col'or couplers for cyan can be prepared eg by condensation of l-hydroxy-Z-naphthoic acid or its derivatives with the suitable aromatic amines according to US. patent application Serial No. 66,289, filed' October 31, 1960, by Arthur Henri de Cat, Raphael Karel Van Poucke and Hector Alfons Vanden Eynde.
It is to be noted that by oxidative coupling of some of the amidrazone mask forming compounds of the Formula I or 11 above with color couplers for cyan of the formula given above, a yellow to orange colored mask image is obtained which compensates the undesirable side-absorption in the blue as Well as in the green part of the spectrum.
For carrying out the process according to the present invention, the color couplers and mask compounds can be incorporated into a photographic silver halide emulsion prepared by means of the colloids usually employed therefor, such as for instance gelatin, polyvinyl alcohol, cl-' lodion or other natural or synthetic colloids. The silver halide emulsion can be coated on a support consisting of paper, glass, nitrocellulose, cellulose esters such as cellulose triacetate, polyester, polystyrene or another natural or synthetic resin, and forms part of a photographic material with one or more emulsion layers. The multilayer material usually comprises the following elements: a support, a red-sensitive emulsion layer having a color coupler for cyan, a green-sensitive emulsion layer having a color coupler for magenta and a blue-sensitive emulsion layer having a color coupler for yellow. There is a yellow filter composed in most of the cases of a gelatin layer containing dispersed colloidal silver, located between the blue-sensitive emulsion layer and the green-sensitive emulsion layer. It is not only possible to incorporate the color couplers into the light-sensitive silver halide emulsion layer itself but they can also be incorporated into an adjacent non-light-sensitive colloid layer or into a nonlight-sensitive layer which is separated from the lightsensitive emulsion layer by a water-permeable colloid layer.
The process according to the invention proceeds as follows: silver halide is reduced to silver at the exposed areas in a color developing bath containing a primary amine aromatic developing agent which is at thesame time oxidized. The oxidized developing agent reacts with the color coupler and forms a dyestuff, the. mask forming compound according to the invention not being affected. After the color development, the material comes into the bleaching bath wherein the oxidation of the mask forming compound takes place. The remaining color coupler still available at the non-exposed areas of the material couples oxidatively with the oxidation product of the compound thus formed whereby the colored mask is formed. Subsequently, the photographic color material is washed with water, fixed and dried.
The following aromatic amino-compounds can be used as developers for such material: mono-, diand triamino-aryl compounds, more especially N,N-dialkyl-pphenylenediamines, such as N,N diethyl p phenylenediamine and N,N-diethyl-2-methyl p-phenylene diamine,-
and derivatives thereof such as N,N-dialkyl-N-sulfomethylor carboxymethyl-p-phenylenediamine. As useful monoamino-developers should be cited: aminophenols and aminocresols or their halogen derivatives and also the amino-naphthols.
The bleaching bath generally contains potassium bro- EXAMPLE I To /2 kg. of a red-sensitive silver bromo-iodide (2% iodide) emulsion containing /6 mol of silver halide are added: (1) a 10% aqueous solution containing as a color coupler for cyan 7 g. of 1,2-hydroxy-naphthoic acid-4- sulfo-2-n-hexadecylsulfonyl anilide, prepared according to a method described in our Belgian patent specification No. 584,846, and cm. of 2 N sodium hydroxide, and (2) 2 g. of N ,N .-cyclodiethylene oxide-N -n-hexa decylsulfonyl benzamidrazone prepared as described in Preparation 4, dissolved in 10 cm. of ethylene glycol monomethylether. Next, the emulsion is acidified with N acetic acid to pH=5.8 and brought to a volume of 1 litre by admixing water. After coating this emulsion onto a film support, the light-sensitive material thus obtained is.
exposed through a grey-wedge with a constant 0.15, and
then developed for 9 minutes at 20 C. in a color developing bath of the following composition:
Water to 1000 cm. (pH:
This material is rinsed for 30 minutes at 18 to 20 C. and fixed for 5 minutes at 20. C. in a fixing bath of the following composition:
G. Sodium thiosulfate 200 Sodium bisulfite 25 Potassium alum 20 Sodium biacetate 20 Boric acid 7.5
Water to 1000 cm. (pH: 4).
Next, the material is rinsed again for 10 minutes at 18 to 20 C. and treated for 5 minutes in a bleaching bath of the following composition:
G. Potassium ferricyanide 100 Potassium bromide 15 Borax 2O Magnesium sulfate 50 Water to 1000 cm. (pH: 8.6).
Rinsing is continued for another 10 minutes at 18 to 20 C. and then the material is fixed again for 5 minutes at 20 C. in a bath of the following composition:
G. Sodium thiosulfate Borax 20 Magnesium sulfate 50 Water to 1000 cm. (pH: 8.9)..
Finally, rinsing is-continued for 10 minutes at 18 to 20 C. and the material is dried. The strip of finished light-sensitive color material shows in addition to a cyan wedge 21 redmasking wedge of opposite gradation, by whichthe side-absorptions of the cyan image are compensated.
EXAMPLE 2 To /2 kg. of a green-sensitive silver'bromo-iodide (2% iodide) emulsion containing mol ofsilverhalide is added an alcoholic solution of 6 g. of 1-(4-sulfophenyl)- 3-pentadecyl-pyrazolone-(5), prepared analogously to the method of Example 2 of British specification 502,665, and 2 g. of N ,N -cyclodiethylene oxide-N -hexadecyb sulfonyl benzamidrazone prepared according to Preparation 4. After-adding the usual additives the emulsion is coated, exposed, developed and further treated as indicated in Example 1. The finished strip shows in addition to a magenta wedge a yellow masking wedge of opposite gradation reducing the disturbing influence of the side adsorption in the formed magenta image.
EXAMPLE 3 To /2 kg. of a red-sensitive bromo-iodide emulsion (3% iodide) containing /6 mol of silver halide are added: (1) 9 g. of N (6' -cetylsu1fonyplheny) l hydroxy 2- naphthoic acid amide-3'-sodium sulfonate dissolved in a mixture of 193 cm. of water and 7 cm. of aqueous 2 N sodium hydroxide, and (2) 6 g. of the mask compound prepared according to Preparation 11, dissolved in a mixture of 6 cm. of 2 N sodium hydroxide,.6 cm. of ethanol and 18 cm. of distilled water. After acidification to pH 6, the usual additives such as hardeners, wetting agents and stabilizers and the necessary quantity of distilled water are addedto the emulsion in order to obtain 1 kg. of flowable emulsion. The emulsion is coated on a suit- 21 ablesupport and-dried. After exposure through a greywedge with a constant 0.15, the photographic material composed in this way is developed and further treated as in Example 1. In the exposed and processed strip, in addition to a cyan image also an orange to yellow mask image is formed, with a gradation opposed to that of the cyan image, and which compensates the side-absorptions of the cyan image in the blue as well as in the green region of the spectrum.
EXAMPLE 4.
To /2 kg. of .a red-sensitive bromo-iodide emulsion (3% iodide) containing mol of silver halide are added: (1) 9 g. of N-(6-n-hexadecylsulfonylphenyl)-1-hydroxy- Z-naphthoic acid amide-3-sodium sulfonate dissolved in a mixture of 193 cm. of water and 7 cm. of aqueous 2 N sodium hydroxide, and (2) 6. g. of the mask compound prepared according to Preparation 4, dissolved in a mixture of 12 cm. of 2 N sodium hydroxide and 18 cm. of ethanol. After acidification to pH 6, the usual additives such as hardeners, wetting agents and stabilizers, and the necessary quantity of distilled water are added to the emulsion in order to obtain 1 kg. of flowable emulsion. The emulsion is coated on a suitable support and dried. After exposure through a grey-wedge with a constant 0.15, the photographic material composed in this way is developed and further treated as in Example 1. In the exposed .and processed strip, in addition to a cyan image also an orange to yellow mask image is formed, with a gradation opposed to that of the cyan image, and which compensates the side-absorptions of the cyan image chiefly in the blue region of the spectrum.
EXAMPLE 5 To /2 kg. of a red-sensitive =bromo-iodide emulsion (3% iodide) containing mol of silver halide .are added: (1) 9 g. of N-(6f-n hexadecylsulfonyphenyl)-1-hydr.oxy- Z-naphthoic acid amide-3-sodium sulfonate dissolved in a mixture of 193 cm. of water and 7 cm. of aqueous 2 N sodium hydroxide, and (2) 6 g. of the mask compound prepared according to Preparation 9, dissolved in a mixture of 6 cm. of 2 -N sodium hydroxide, 6 cm. of ethanol and 18 cm? of distilled water. After acidification to pH 6, the usual additives such as hardeners, wetting agents and stabilizers and the necessary quantity of distilled water are added to the emulsion in order to obtain 1 kg. of flowable emulsion. The emulsion is coated on a suitable support and dried. After exposure through a greywedge with a constant 0.15, the photographic material composed in this way is developed and further treated as in Example 1. In the exposed and processed strip, in addition to a cyan image also an orange to yellow mask image is. formed, with a. gradation opposed to that of the cyan image, and which compensates the side-absorption of the cyan image in the blue as well as in the green region of the. spectrum.
EXAMPLE 6 To /2 kg. of .a red-sensitive bromo-iodide emulsion (3% iodide) containing Amol of silver halide are added: (1) 9' g. of N-(6-n-hexadecylsulfonylphenyl-1-hydroxy-2- naphthoic acid amide-3-sodium sulfonates dissolved in a mixture of 193 cm. of water and 7 cm. of aqueous 2 N sodium hydroxide, and (2) 2 g. of the mask compound prepared according -to Preparation 7, dissolved in a mixture of 17.5 cm. of diacetone alcohol and 2.5 cm. of alcoholic N/2 sodium hydroxide. After acidification to pH 6, the usual additives such as hardeners, wetting agents and stabilizers and the necessary quantity of distilled water are added to the emulsion in order to obtain 1 kg. of flowable emulsion. The emulsion is coated on a suitable support and dried. After exposure through a grey-wedge With a constant 0.15, the photographic material composed this way is developed. and further treated as in Example 1. Inthe exposed and processed strip, in addition to a cyan image also an orange one is formed, with a gradation opposed to that of the cyan image, and which compensates the side-absorptions of the cyan image in the blue as well as in the green region of the spectrum.
EXAMPLE 7 To /2 kg. of a red-sensitive bromo-iodide emulsion (3% iodide) containing /6 mol of silver halide are added: (1) 9 g. of N-(6-n-hexadecylsulfonylphenyl)-1- hydroxy-2rnaphthoic acid amide-3'-sodium sulfonate dissolved in a mixture of 193 cm. of Water and 7 cm. of aqueous 2 N sodium hydroxide, and (2) 6 g. of the mask compound prepared according to Preparation 8, dissolved in a mixture of 6 cm. of 2 N sodium hydroxide and 24 cm. of ethanol. After acidification to pH 6 the usual additives such as hardeners, wetting agents and stabilizers and the necessary quantity of distilled water are added to the emulsion in order to obtain 1 kg. of flowable emulsion. The emulsion is coated on a suitable support and dried. After exposure through a greyawedge with a constant 0.15, the photographic material composed in this way is developed and further treated as in Example 1. In the exposed and processed strip, in addition to a cyan image also an orange to magenta mask image is formed, with a gradation opposed to that of the cyan image, and which compensates the side-absorptions of the cyan image in the blue and the green region of the spectrum.
EXAMPLE 8 To /2 kg. of a red-sensitive bromo-iodide emulsion (3% iodide) containing /6 mol of silver halide are added: (1) 9 g. of N-(6'-n-hexadecylsulfonylphenyl)-1-hydroxy- 2-naphthoic acid amide-3'-sodium sulfonate dissolved in a mixture of 193 cm. of Water and 7 cm. of aqueous 2 N sodium hydroxide, and (2) 3 g. of the mask compound prepared according to Preparation 6, dissolved in a mixture of 3 cm. of 2 N sodium hydroxide, 3 cm. of ethanol, and 9 cm? of distilled water. After acidification to pH 6, the usual additives such as hardeners, wetting agents and stabilizers, and the necessary quantity of distilled water are added to the emulsion in order to obtain 1 kg. of flowable emulsion. The emulsion is coated on a suitable support and dried. After exposure through a grey-wedge With a constant 0.15, the photographic material composed in this way is developed and further treated as in Example 1. In the exposed and processed strip, in addition to a cyan image also an orange to magenta mask image is formed, with a gradation opposed to that of the cyan image, and which compensates the side-absorptions of the cyan image in the blue and the green regions of the spectrum.
EXAMPLE 9 To a /2 kg. of red-sensitive silver bromo-iodide emulsion (2% iodide) containing /6 mol of silver halide are added: (1) 10 g. of N-(6-n-hexadecylsulfonylphenyl)-lhydroxy-Z-naphthoic acid amide-3-sodium sulfonate dissolved in a mixture of 193 cm. of Water and 7 cm. of aqueous 2 N sodium hydroxide, and (2) 6 g. of the mask compound prepared according to Preparation 11, dissolved in a mixture of 6 cm. of 2 N. sodium hydroxide, 6 cm. of ethanol and 18 cm. of distilled Water. After acidification to pH 6, the usual additives such as hardeners, wetting agents and stabilizers, and the necessary quantity of distilled water are added to the emulsion in order to obtain 1 kg. of flowable emulsion. After coating this emulsion forms part of a multilayer photographic material consisting of the following superposed layers in the indicated sequence: a support, an anti-halation layer, a gelatin insulating layer, the above-mentioned red-sensitive emulsion.
layer containing a color coupler for cyan, a gelatin. interlayer, a green sensitive emulsion layer containing a color coupler for magenta, a yellow filter layer, a blue-sensitive emulsion layer containing a color coupler for yellow and at last a gelatin overcoat as antistres layer. After exposure through a grey-Wedge the photographic material is developed and further treated as in Eaxmple 1. A
23 mainly cyan-colored image is obtained together with an orange to yellow dye image in the red-sensitive layer, said orange to yellow dye image being of opposite gradation in respect of the cyan dye image and compensating the side-absorption of the cyan image in the blue as well as in the green region of the spectrum.
EXAMPLE A photographic multilayer material consisting of the following superposed layers in the indicated sequence: a support, an anti-halation layer, a gelatin insulating layer, a red-sensitive emulsion layer containing a color coupler for cyan, a gelatin interlayer, a green-sensitive emulsion layer containing a color coupler for magenta, a yellow filter layer, a blue-sensitive emulsion layer containing a color coupler for yellow and at last a gelatin overcoat as antistress layer. The red-sensitive emulsion layer is coated starting from a red-sensitized gelatino silver bromo-iodide emulsion. This emulsion is prepared as follows: to /2 kg. of a gelatino silver bromo-iodide emulsion (2% iodide) containing mol of silver halide are added: (1) 9 g. of N-(6-n-hexadecylsulfonylphenyl)-lhydroxy-Z-naphthoic acid amide-3'-sodium sulfonate dissolved in a mixture of 175 cm. of water and 6.3 cm. of aqueous 2 N sodium hydroxide, and (2) 6 g. of the mask compound prepared according to Preparation 11, dissolved in a mixture of 6 cm. of 2 N sodium hydroxide, 6 cm. of ethanol and 18 cm. of distilled water. Next, this emulsion is acidified with acetic acid to pH 6, and after adding the usual additives such as hardeners, wetting agents, stabilizers and the necessary quantity of distilled water, 1 kg. of fiowable emulsion is obtained. The greensensitive emulsion layer is coated starting from a greensensitized gelatino silver bromo-iodide emulsion. This emulsion is prepared by adding to /2 kg. of gelatino silver bromo-iodide emulsion (2% iodide) containing /6 mol of silver halide, 9 g. of a slightly alkaline alcoholic solution of 2-(l-phenyl-5-oxo-3-pyrazolinylimino)-3-carbethoxyr 4-p-(1-nhexadecyloxy)-phenyl-thiazoline, 6- g. of the mask compound 3-ethyl-2-benzothiazolone-B-n-hexadecylsulfonyl hydrazone prepared according to our British patent specification No. 975,932 and having the following formula:
and dissolved by heating in a mixture of alcohol and water (1:3) with a little sodium hydroxide, acidifying with acetic acid to pH 6, and adding the usual additives such as hardeners, wetting agents, stabilizers and the necessary quantity of distilled water to obtain 1 kg. of flowable emulsion. The light sensitive multilayer photographic material is exposed through a grey-wedge, de-v veloped and further treated as described in Example 1.
In the red-sensitive emulsion layer in addition to a cyan To /2 kg. of a red-sensitive broino-iodide emulsion (3% of iodide) containing /6 mol of silver halide are added: (1) 10 g. of N-(6'-n-hexadecylsulfonyl-phenyl)- 1-hydroxy-2-naphthoic acid amide-3-sodium sultonate dissolved in a mixture of 193 cm. of water and 7 cm.
of aqueous 2 N sodium hydroxide, and. (2) '5 g. of the mask compound prepared according to Preparation 12, dissolved in a mixture of 37.5 cm. of water and 12.5 cm. N sodium hydroxide. After acidification with acetic acid to pH 6, the usual additives such as hardeners, wetting agents and stabilizers and the necessary quantity of distilled water are added to the emulsion in order to obtain 1 kg. of fiowable emulsion. The emulsion is coated on a suitable support and dried. After exposure through-a grey-wedge with a constant. 0.15, the photographic material composed in this way is developed and further treated as in Example 1. In the exposedand processed strip, in addition toa cyan image .also an orange mask image is formed, with a gradation opposed to that of the cyan image, and which compensates the side-absorptions of the cyan image in the blue as well as in the green region of the spectrum.
We claim:
1. In a method of forming a color corrected image in a photographic element having at least one silver halide emulsion layer containing a color coupler for magenta which is reactive with the oxidation product. of an aromatic amino developing agent-to form by color development a magenta primary dye image which absorbs a major proportion of light in one region of the visible spectrum, and undesirably absorbs a minor proportion of light in at least one other region of the visible spectrum, in which method said element is exposed to said image to be photographed, developed with'said developing agent and thereafter treated with an oxidizing solution, the improvement wherein said element has present therein a mask-forming compound having the formula:
wherein R is a member of the group consisting of a hydrogen atom and an acyl radical,
R is a member of the group consistingof a hydrogen atom, an'amino radical, an alkyl radical, an alkylene radical, an aryl radical, and a heterocyclic radical,
Y represents the non-metallic atoms necessary to complete a nitrogen-containing heterocyclic nucleus, and
X is a member of the group consisting of an hydroxyl radical, an amino radica1,=an aliphatic hydrocarbon radical, an aryl radical, and a heterocyclic radical; whereby the residual color coupler oxidatively couples with said mask-forming compound to form a secondary dye image having a gradation opposite to that of said magenta primary dye image, said secondary .image absorbing regions but transmitting substantially all the light in said-major absorption region.
2. The method of claim 1 wherein said color coupler for magenta is a member of the group consisting of the indazolone and pyrazolone color couplers.
3. The method of claim 1 wherein said oxidizing solution is a photographic bleaching bath.
4. The method of claim 1 wherein said mask-forming compound ispresent in at least said one emulsion layer.
5. The method of claim 2 wherein said mask-forming compound forms a yellow secondary dye image.
6. A color photographic element useful in the method of claim 1, said element having superposed silver halide emulsion layers sensitive to diiferent regions of the visible spectrum, at least one of said layers containing a color coupler for magenta which is reactive with the oxidation product of an aromatic amino developing agent to form by color development a magenta primary dye image which absorbs a major proportion of light in' one region of the spectrum, and undmirably absorbs a minor pro portion of light in at least one other region of the 25' visible spectrum, such layer also containing a mask-forming compound-of the formula:
I" Il a I'M t t t sozx wherein R is a member of the group consisting of a hydrogen atom and an acyl radical,
Y represents the non-metallic atoms necessary to complete a nitrogen-containing heterocyclic nucleus,
R is a member of the group consisting of a hydrogen atom; an amino radical, an alkyl radical, an alkylene radical, an aryl radical, and a heterocyclic radical, and
X is a member of the group consisting of an hydroxyl radical, an amino radical, an aliphatic hydrocarbon radical, an aryl radical, and a heterocyclic radical;
said color coupler for magenta also being reactive with the oxidation product of said mask-forming compound to form a secondary dye image having a gradation opposite to that of said magenta primary dye image, and absorbing light in at least one of said unwanted minor absorption regions but transmitting substantially all the light in said major absorption region.
7. The element of claim 6 wherein said color coupler for magenta is a member of the group consisting of the indazolone and pyrazolone color couplers.
8. In a method of forming a color corrected image in a photographic element having at least one silver halide emulsion layer containing a color coupler for cyan which is reactive with the oxidation product of an aromatic amino developing agent to form by color development a cyan primary dye image which absorbs a major proportion of light in one region of the visible spectrum, and undesirably absorbs a minor proportion of light in at least one other region of the visible spectrum, in which method said element is exposed to said image to be photographed, developed with said developing agent and thereafter treated with an oxidizing solution, the improvement wherein said element has present therein a masktorming compound having a formula selected from the group consisting of:
R is a member of the group consisting of a hydrogen atom and an acyl radical,
R is a member of the group consisting of a hydrogen atom, an amino radical, an alkyl radical, an alkylene radical, an aryl radical, and a heterocyclic radical,
R and R are each a member of the group consisting of a hydrogen atom, an alkyl radical, and an aryl radical,
Y represents the non-metallic atoms necessary to complete a nitrogen-containing heterocyclic nucleus, and
X is a member of the group consisting of an hydroxyl radical, an amino radical, an aliphatic hydrogen radical, an aryl radical, and a hetercyclic radical;
whereby the residual color coupler oxidatively couples with said mask-forming compound to form a secondary dye image having a gradation opposite to that of said cyan primary dye image, said secondary image absorbing light in at least one of said undesirable minor absorption regions but transmitting substantially all the light in said major absorption region.
9. The method of claim 8 wherein said color coupler 26 for cyan is a member of the group consisting o-tthe phenol and naphthol color couplers.
19. The method of claim 9' wherein said, color coupler has the formula:
({)II IIQD wherein:
X is a radical of the group consisting of O', -S-,
and SO Z is a member of the group consisting of a hydrogen atom and a halogen atom,
D is an aliphatic radical comprising a linear chain-of 5-20 carbon atoms, and
M is a member of the group consisting of a hydrogen atom, an alkali atom, and an ammonium group.
1 1. The method of claim 8 wherein said oxidizing bath is a photographic bleaching bath.
12. The method of claim 8 wherein said mask-forming compound is present in the same emulsion layer containing said colo-r coupler.
13. The method of claim 9 wherein said mask-forming compound forms .a yellow-to-magenta secondary dye image.
'14. A color photographic element useful in the method of claim 8, said element having superposed silver halide emulsion layers sensitive to diiferent regions of the visible spectrum, at least one of said layers containing a color coupler for cyan which is reactive with the oxidation product of an aromatic amino developing agent to form by color development a cyan primary dye image which absorbs a major proportion of light in one region of the spectrum, and undesirably absorbs a minor proportion of light in at least one other region of the visible spectrum, such layer also containing a mask-forming compound of a formula selected from the group consisting of:
wherein:
R is a member of the group consisting of a hydrogen atom and an acyl radical,
Y represents the non-metallic atoms necessary to complete a nitrogen-containing hetero-cyclic nucleus,
R is a member of the group consisting of a hydrogenation, an amino radical, an alkyl radical, an alkylene radical, an aryl radical, and a heterocyclic radical,
R and R are each selected :from the group consisting of a hydrogen atom, an alkyl radical, and an aryl radical, and
X is a member of the group consisting of an hydroxyl radical, an amino radical, an aliphatic hydrogen radical, an aryl radical, and a heterocyclic radical;
said color coupler for magenta also being reactive with the oxidation product of said mask-forming compound to form a secondary dye image having a gradation opposite to that of said cyan primary dye image, and absorbing light in at least one of said unwanted minor absorption wherein:
X is a radical of the group consisting of O,
Z is a member of the group consisting of a hydrogen atom and a halogen atom,
D is an aliphatic radical comprising a linear chain of 520 carbon atoms, and
M is a member of the group consisting of a hydrogen atom, an alkali atom, and an ammonium group.
References Cited by the Examiner UNITED STATES PATENTS 2/1950 Hanford 96 55 8/1950 Young 96-55 2/ 1958 Jennen 96-10() 8/1961 Lofiler etal. 969 12/1-961 De 'Ramaix et al. 96-9 12/1961 De Ramaix 9655 X 7/ 1962 De Ra'rnaix et a1. 969
FOREIGN PATENTS 12/1-952 Great Britain. 2/1958 Great Britain.
NORMAN G. TORCHIN, Primary Examiner.
20 HAROLD N. BU'RSTEI-N, Examiner.
R. A. BURROUGHS, J. T. BROWN,
Assistant Examiners.

Claims (1)

1. IN A METHOD OF FORMING A COLOR CORRECTED IMAGE IN A PHOTOGRAPHIC ELEMENT HAVING AT LEAST ONE SILVER HALIDE EMULSION LAYER CONTAINING A COLOR COUPLER FOR MAGENTA WHICH IS REACTIVE WITH THE OXIDATION PRODUCT OF AN AROMATIC AMINO DEVELOPING AGENT TO FORM BY COLOR DEVEOP MENT A MAGENTA PRIMARY DYE IMAGE WHICH ABSORBS A MAJOR PROPORTION OF LIGHT IN ONE REGION OF THE VISIBLE SPECTRUM, AND UNDESIRABLY ABSORBS A MINOR PROPORTION OF LIGHT IN AT LEAST ONE OTHER REGION OF THE VISIBLE SPECTRUM, IN WHICH METHOD SAID ELEMENT IS EXPOSED TO SAID IMAGE TO BE PHOTOGRAPHED, DEVELOPED WITH SAID DEVELOPING AGENT AND THEREAFTER TREATED WITH AN OXIDIZING SOLUTION, THE IMPROVEMENT WHEREIN SAID ELEMENT HAS PRESENT THEREIN A MASK-FORMING COMPOUND HAVING THE FORMULA:
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3457077A (en) * 1965-05-26 1969-07-22 Agfa Gevaert Ag Photographic couplers
US3467520A (en) * 1964-03-20 1969-09-16 Agfa Ag Production of colored direct positive photographic images
US3525614A (en) * 1966-09-19 1970-08-25 Agfa Gevaert Nv Photographic processes and elements comprising integral color correction mask-forming compounds
US4115121A (en) * 1976-04-14 1978-09-19 Ciba-Geigy Ag Silver halide color photographic material containing yellow coupler

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1175072B (en) * 1963-04-11 1964-07-30 Agfa Ag Photographic light-sensitive material comprising at least one halide silver emulsion layer
GB1044959A (en) * 1963-10-10 1966-10-05 Gevaert Photo Prod Nv Method and material for producing photographic colour images
GB1246114A (en) * 1968-01-05 1971-09-15 Agfa Gevaert Benzoylacetamide derivatives and their use as colour couplers
GB1498954A (en) * 1974-04-02 1978-01-25 Agfa Gevaert Colour photographic silver halide development
EP0109118B1 (en) * 1982-11-12 1986-06-04 Agfa-Gevaert N.V. Photographic colour material incorporating developing agents for colour development
DE4124587A1 (en) * 1991-07-24 1993-01-28 Luitpold Werk Chem Pharm DIMETHYLACETETIC ACID AMIDE, PROCESS FOR THEIR PREPARATION AND MEDICAMENTS
DE4218159C2 (en) * 1992-06-02 1997-07-31 Luitpold Pharma Gmbh 4,4,4-trifluoroacetoacetic acid amides, process for their preparation and pharmaceuticals
US6124242A (en) * 1998-06-26 2000-09-26 Basf Aktiengesellschaft Herbicidal compositions and processes based on ferrodoxin:NADP reductase inhibitors

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2498418A (en) * 1948-05-18 1950-02-21 Gen Aniline & Film Corp Production of azo dyestuff images from n-acyl-n-aryl hydrazine developers
US2518739A (en) * 1947-07-03 1950-08-15 Eastman Kodak Co Method of masking photographic color images
GB685061A (en) * 1949-12-13 1952-12-31 Gevaert Photo Prod Nv Improvements in or relating to the manufacture of photographic multi-colour images
GB790327A (en) * 1954-07-13 1958-02-05 C Schleussner Fotowerke G M B Improvements in or relating to colour photography
US2994607A (en) * 1956-11-20 1961-08-01 Agfa Ag Process for the production of color-corrected color photographic images
US3012884A (en) * 1956-12-31 1961-12-12 Gevaert Photo Prod Nv Production of colored photographic images
US3047385A (en) * 1959-11-30 1962-07-31 Gevaert Photo Prod Nv Production of color photographic images

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE523247A (en) *
BE444782A (en) * 1941-03-17 1942-04-30
GB562960A (en) * 1942-11-25 1944-07-24 Douglas William Stammers Production of coloured photographic images
BE491102A (en) * 1948-09-15
US2895825A (en) * 1954-03-18 1959-07-21 Agfa Ag Production of photographic colour images with heterocyclic developers
DE963297C (en) * 1954-07-13 1957-05-02 C Schleussner Fotowerke G M B Process for producing color photographic images by chromogenic development
BE544737A (en) * 1955-01-28
BE567154A (en) * 1957-04-26

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2518739A (en) * 1947-07-03 1950-08-15 Eastman Kodak Co Method of masking photographic color images
US2498418A (en) * 1948-05-18 1950-02-21 Gen Aniline & Film Corp Production of azo dyestuff images from n-acyl-n-aryl hydrazine developers
GB685061A (en) * 1949-12-13 1952-12-31 Gevaert Photo Prod Nv Improvements in or relating to the manufacture of photographic multi-colour images
US2823998A (en) * 1949-12-13 1958-02-18 Gevaert Photo Prod Nv Process and material for producing photographic multi-color images
GB790327A (en) * 1954-07-13 1958-02-05 C Schleussner Fotowerke G M B Improvements in or relating to colour photography
US2994607A (en) * 1956-11-20 1961-08-01 Agfa Ag Process for the production of color-corrected color photographic images
US3012884A (en) * 1956-12-31 1961-12-12 Gevaert Photo Prod Nv Production of colored photographic images
US3013879A (en) * 1956-12-31 1961-12-19 Gevaert Photo Prod Nv Production of color photographic images
US3047385A (en) * 1959-11-30 1962-07-31 Gevaert Photo Prod Nv Production of color photographic images

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3467520A (en) * 1964-03-20 1969-09-16 Agfa Ag Production of colored direct positive photographic images
US3457077A (en) * 1965-05-26 1969-07-22 Agfa Gevaert Ag Photographic couplers
US3525614A (en) * 1966-09-19 1970-08-25 Agfa Gevaert Nv Photographic processes and elements comprising integral color correction mask-forming compounds
US4115121A (en) * 1976-04-14 1978-09-19 Ciba-Geigy Ag Silver halide color photographic material containing yellow coupler
US4229577A (en) * 1976-04-14 1980-10-21 Ciba-Geigy Ag Yellow photographic color couplers containing 3-imino-1,3,4-thiadiazolyl-4 groups

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