US3293032A - Process for the preparation of colour images - Google Patents

Process for the preparation of colour images Download PDF

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US3293032A
US3293032A US342305A US34230564A US3293032A US 3293032 A US3293032 A US 3293032A US 342305 A US342305 A US 342305A US 34230564 A US34230564 A US 34230564A US 3293032 A US3293032 A US 3293032A
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colour
silver halide
colourless
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emulsion layer
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Jaeken Jan
Ramaix Maurice Antoine De
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Gevaert Photo Producten NV
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    • 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
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials

Definitions

  • PROCESS FOR THE PREPARATION OF COLOUR IMAGES Filed Feb. 5, 1964 3 Sheets-Sheet s 350 400 60 500 20 40 0 flfl 20 40 60 700 WI 'M/VGH/ m 0; IN VEN TOR5 17% Jae/762a BY Maw/ca Amw/ze de Pal/mix United States l atent C) 3,293,032 PROCESS FOR THE PREPARATION OF COLOUR IMAGES Jan Jaeken and Maurice Antoine de Ramaix, Hove, Belgium, assignors to Gevaert Photo-Producten, N.V., Mortsel-Antwerpen, Belgium, a Belgian company Filed Feb. 3, 1964, Ser. No. 342,305 Claims priority, application Great Britain, Aug. 2, 1961,
  • This invention refers to a process and a material for the Preparation of photographic reversal colour images.
  • a photographic colour material is usually composed of three silver halide emulsion layers which can be colour-developed and wherein on development are formed respectively according to the type of colour coupler, a yellow, a magenta and a cyan dye image.
  • Each of the three silver halide emulsion layers is differently spectrally sensitized according to the absorption range of the dye to be formed.
  • a masking process is transformed in a process for preparing direct positive colour images.
  • the oxidative coupling is normally carried out in an alkaline oxidative bleaching bath e.g., a potassium ferriice cyanide bleaching bath wherein the reduced silver metal is simultaneously dissolved.
  • an alkaline oxidative bleaching bath e.g., a potassium ferriice cyanide bleaching bath wherein the reduced silver metal is simultaneously dissolved.
  • the quinone-imine dyes and azomethine dyes formed by coupling of the usual colourless couplers with an aromatic primary amino developing agent oxidized on development can be destroyed by treatment with a strong acid.
  • the dyes formed with these colour couplers by oxidative coupling with the oxidative coupling compounds mentioned in the above cited patents for an integral masking method are strongly acidresistant.
  • a photographic material which contains at least one water-permeable colloid layer wherein light-sensitive silver halide grains are present and wherein said waterpermeable colloid layer or water-permeable colloid layer adjacent thereto contains at least one compound which on development in the exposed areas couples with an oxidation product of a developing agent to form on these areas a dye which can be destroyed or transformed in colourless product by a chemical treatment, and wherein the said water-permeable colloid layer containing the silver halide or a water-permeable colloid layer adjacent thereto also contains a compound which on treatment of the colour developed photographic element in an oxidizing solution oxidatively couples with said colourless compound to form in the non-developed areas a secondary dye which cannot be destroyed or transformed to colourless produots by the said chemical treatment for destruction or transformation of the primary dye.
  • a photographic element comprising (a) at least one water-permeable layer which contains light-sensitive silver halide grains,
  • the oxidatively coupling compound can oxidatively couple with the colour coupler in the colloid layer wherein the latter is present during the treatment in the oxidative bleaching solution.
  • this process comprises the steps of exposing to an object a photographic element containing a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsi-on layer and a blue-sensitive silver halide emulsion layer, each of said layers containing a colour coupler capable of forming on deveolprncnt a dye which by treatment with a strong acidic solution can be transformed in colourless products, the red-sensitive emulsion layer also containing a compound which is capable of forming an acid-resistant cyan dye by oxidative coupling with the colour coupler present in that emulsion layer, the greensensitive emulsion layer also containing a compound which is capable of forming an acid-resistant magenta dye by oxidative coupling with the colour coupler present in that emulsion layer, the blue-sensitive emulsion layer also containing a compound which is capable of forming an acid-resistant yellow dye, by
  • the class of the cyan colour couplers mainly consists of phenol and a-naphthol compounds which in the usual colour development with aromatic primary amino developing agents, eg N,N-d:iethyl-pphenylene diamine, form indo-phenol or quinone-imine dyes which are not completely acid-resistant.
  • aromatic primary amino developing agents eg N,N-d:iethyl-pphenylene diamine
  • naphthol colour couplers are preferably used.
  • Suitable colour couplers for cyan to be applied in the process according to the present invention are described in the Belgian patent specifications Nos. 584,152, 584,846, 587,525, 590,934 and 595,694.
  • Naphthol colour couplers which are more particularly preferred correspond to the following general formula:
  • i l w Q son/r Y X represents an oxygen atom, a sulfur atom, a -NHCO group, a CONH group, a -SO NH group, a -NHSO group, a
  • Y represents a hydrogen atom or 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, and
  • M represents a hydrogen atom, an alkali metal atom or an ammonium group.
  • Suitable colour couplers of the above general formula are e.g.:
  • colour couplers for cyan can be prepared e.g. by condensation of l-hydroxy-Z-naphthoic acid or one of its derivatives with one of the suitable aromatic amines according to German patent specification No. 1,121,061.
  • Suitable pyrazolone colour couplers to be applied in the process according to the present invention are described in the British patent specifications Nos. 502,665 and 636,988 and the US. patent application Ser. No. 314,806.
  • Ar represents a phenyl radical or a phenyl radical containing a solubilizing group such as a sulphonic acid group, and
  • D represents an aliphatic radical comprising a linear chain of at least 5 and at most 20 carbon atoms.
  • pyrazolone colour couplers of the 3-acylamino-Spyrazolone type which are preferably used in a form fast to diffusion, such as the colour couplers according to the general formula described in the US. patent application Ser. No. 314,806.
  • the class of the usual colour couplers for yellow comprises compounds containing an active methylene group in an open chain structure.
  • dyes are formed absorbing too much in the short wavelength range of the visible spectrum and also in the UV, range.
  • the colour couplers used in the present invention are preferably used fast to diffusion in a colloid layer such as a gelatino silver halide emulsion layer.
  • colour couplers for yellow, magenta and cyan only refer to the colour formed during the primary colour development and do not apply to the colour obtained with these colour couplers after the oxidative coupling.
  • R represents a lower alkyl group e.g. a methyl group
  • R represents a member selected from the group consisting of a lower alkyl group, e.g. a methyl group, and an aryl group, e.g. a phenyl group and a substituted phenyl p,
  • R represents an aliphatic radical rendering the molecule non-migratory and having more than 5 and less than 20 carbon atoms e.g. a member from the group consisting of a nonyl, an undecyl, a tridecyl and a pentadecyl group.
  • amidrazone compounds More particularly as amidrazone compounds are cited the compounds corresponding to the following general formulae:
  • R is a member selected from the group consisting of a hydrogen atom and an acyl radical
  • R is a functional substituent of suflicient instability as to be capable of splitting off during oxidative coupling, said substituent being selected from the group consist- 6 ing of CONH and -SO X, wherein X is a member selected from the group consisting of a hydroxyl radi- I cal, an amino radical, a heterocyclic radical, an aliphatic hydrocarbon radical and an aryl radical, R is a member selected from the group consisting of a hydrogen atom, an alkyl radical and an aryl radical, R is a member selected from the group consisting of a hydrogen atom, an alkyl radical and an aryl radical, R is a member selected from the group consisting of a hydrogen atom, an amino radical, a heterocyclic radical, a hydrocarbon radical such as e.g. an alkyl radical, and an aryl radical, and Y represents the non-metallic atoms necessary to close a nitrogen-containing heterocyclic nucleus. More particularly as hydrazone compounds are
  • R represents a member selected from the group consisting of a hydrogen atom and an acetyl group
  • R represents an unstable function-a1 substituent remaining intact during colour development but splitting off in the presence of said oxidizing solution, preferably a SO X radical, wherein X represents an organic radical comprising a linear chain of 5 to 20 carbon atoms,
  • R represents a member selected from the group consisting of an alkyl radical and an aryl radical
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing 5-6 members, at least one of which is a nitrogen atom.
  • R' represents an unstable functional substituent remaining intact during colour development but splitting off in the presence of said oxidizing solution preferably a CONH or SO X radical wherein X represents a member selected from the group consisting of an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group and a substituted aralkyl group,
  • each of R' and R' represents a member selected from the group consisting of an alkyl radical, a substituted alkyl radical, an aryl radical, a substituted aryl radical, an aralkyl radical and substituted ralkyl radical, and
  • Z represents the necessary atoms to close a 6-membered aromatic nucleus or a substituted 6-membered aromatic nucleus e.g. a halogen substituted nucleus, an alkyl substituted nucleus, an arylamino substituted nucleus and an alkoxy substituted nucleus.
  • R' represents an unstable functional substituent remaining intact during colour development but splitting off in the presence of said oxidizing solution, preferably a NH CO radical or a XSO radical wherein X represents a member selected from the group consisting of an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group and a substituted aralkyl group,
  • R" represents a member selected from the group consisting of an aryl group, a substituted aryl group, a heterocyclic radical, and a substituted heterocyclic radical,
  • R" represents a member selected from the group consisting of an alkyl group and a substituted alkyl group
  • Z" represents the necessary atoms to close a member selected from the group consisting of an aromatic nucleus or a substituted aromatic nucleus e.g. a halogen substituted nucleus, an alkyl substituted nucleus, an acylamino substituted nucleus, an alkoxy substituted nucleus, a sulfamyl substituted nucleus and an arylsulfonyl substituted nucleus.
  • an aromatic nucleus or a substituted aromatic nucleus e.g. a halogen substituted nucleus, an alkyl substituted nucleus, an acylamino substituted nucleus, an alkoxy substituted nucleus, a sulfamyl substituted nucleus and an arylsulfonyl substituted nucleus.
  • the 4-oarboxybenzene sulfonylhydrazi'de used in the latter preparation step is obtained by first dissolving 11 g. (0:05 mol) of 4-carboxybenzenesulfonyl chloride in 650 0111. of anhydrous ether and by adding thereto at 5 C. 6.5 can? of hydrazine. After washing the precipitate With cold ethanol, the obtained salt is boiled in ethanol and then ground under 5 N hydrochloric acid in order to set free the carboxylic acid from the hydrazinium salt. After recrystallization of this canboxylic acid from Water, 6 g. of 4-carboxybenzene sul-fionyl-hydnazide is obtained. Melting point: 235 C. with decomposition.
  • PREPARATION 3 (ix-morp'holino-o-chlorobenzaldehyde) -nhexadecylsulfonyl hydrazone OHr-CHz
  • a chilled solution of 6 g. (0.15 mol) of sodium hydroxide in 50 cm. of Water are firs-t added at 0 C. 11g. (0.125 mol) of morpholine and then at 0 to 5 C. 22 g. (0.125 mol) of o-chlorobenzoyl ch'lori'de. After the addition of the reactants, stirring is continued for /2 h. at the same temperature.
  • the product formed is filtered 011 and washed with Water until neutnal. Recrystalliza- 1 1 tion from petroleum naphtha (boiling range: 90120 C.) yields 20 g. of 2-chloro-benzoylmorpholide. Melting point: 73 C.
  • PREPARATION 6 10-methyZ-9-acridan0ne-(2'-n-hexadecyloxy-5-carb0xyphenyD-sulfonyl hydrazone OOOH
  • a mixture of 15.5 g. (0.074 mol) of N-methylacridone, prepared according to Gilman, J. Org. Chem. 17 (1952) 860, 465 cm. of pyridine and 10.3 g. (0.044 mol) of phosphorus pentasulfide is boiled for l h. After cooling, the reaction mixture is poured onto ice. The formed precipitate is sucked off, Washed with Water and recystallized from methyl Cellosolve yielding 12.5 g. of N-methylthioacndone. Melting point: above 260 C.
  • the precipitate is recrystallized successively from ethanol and acetonitrile yielding 8.5 g. of 2-hexadecyloXy-5- carboxyphenyl sulfonyl hydrazide. Melting point: 141 C.
  • PREPARATION 7 1-metlzyl-2-o-chlorophenyZ-4-quinol0ne-n-hexade'cylsulfonyl hydrazone hydrochloride 11.3 g. (0.05 mol) of the ethyl ester of o-chlorobenzoyl acetic acid, 4.7 ccs. (0.05 mol) of aniline and 2 drops of concentrated hydrochloric acid are allowed to react for 6 days at 20 C. under vacuum in a desiccator containing sulfuric acid as desiccant. The reaction mixture is taken up into ether, washed with N hydrochloric acid and then with water and after drying over sodium sulphate evaporated till dry.
  • PREPARATION 8 I-methyI-2-phenyl-4-quin0l0ne-(2'-n-hexadecyl0xy-5'- carboxyphenyD-sulfonyl hydrazone COOH 87 cm. (0.5 mol) of the ethylester of benzoyl acetic acid, 47.6 cm. (0.5 mol) of aniline and 1 cm. of concentrated hydrochloric acid are allowed to react for 10 days at 20 C. under vacuum in a desiccator containing sulfuric acid as desiccant. The solid substance obtained is washed with a little methanol and recrystallized from methanol yielding g. of the ethylester of ,B-anilino-cinnamic acid. Melting point: 71 C.
  • the nitro compound is converted into the corresponding amino compound by reduction in dioxan medium with Raney nickel as catalyst and under hydrogen pres sure. Thereupon an aquimolar mixture of the amino compound and succinic anhydride in aceto nitrile are refluxed for 1 hour yielding the desired compounds.
  • a secondary acid-resisting yellow, magenta or cyan dye-image which is by that very fact of opposite gradation to that of the primary dye image formed on colour development and which is non acid-resistant, so that after the after-treatment with an acid, a positive dye image is left.
  • the yellow dyestuff of the positive image has preferably an absorption maximum between 430 and 480 mg.
  • the magenta dyestuff of the positive image has preferably an absorption maximum between 520 and 550 mg.
  • the cyan dyestufi of the positive image has preferably an absorption maximum between 610 and 680 mu.
  • the 4-aminopyrazolone-3 derivatives described in the present invention are preferably used for oxidatively cou pling with colourless colour couplers of the phenol and naphthol type to form a magenta dyestuff.
  • cyan With hydrazone compounds described in the present invention cyan,
  • 18 magenta as well as yellow dyestuffs can be formed depending onthe type of the heterocyclic ring closed by Z and the type of the colour coupler used on oxidatively coupling viz. a colour coupler of the phenol or naphthol 5 type, a colour coupler with active methylene group such .as a pyrazolone colour coupler or a ketomethylene colour coupler for yellow.
  • amidrazone compounds described in the present inlvention are preferably used for oxidatively coupling with colour couplers of the phenol or naphthol type to form from yellow to magenta dyestufis.
  • FIGURES 1, 2 and 3 represent the absorption curves of a cyan dye, a magenta dye and a yellow dye respectively obtained according to the process described in Examples 8, 4 and 11 respectively.
  • the colour couplers as well as the oxidatively coupling compounds are preferably of the nondiffusing type.
  • the ratio in mols of light-sensitive silver halide to colour coupler is preferably comprised between 6:1 and 15:1 and the ratio of colour coupler to oxidatively coupling compound preferably varies from 1:1 to 1:3.
  • a photographic multilayer material preferably contains the following elements: (1) a support, (2) a red-sensitized silver halide emulsion layer containing a colour coupler capable of forming on development a quinone-imine or azomethine dye and an oxidatively coupling compound which, after the development, on treatment with an oxidative bleaching bath, reacts with the residual colour coupler so as to form an acid-resisting cyan dye, (3) a green-sensitized silver halide emulsion layer containing a colour coupler capable of forming on development a quinone-imine or azomethine dye and an oxidatively coupling compound which, after the development, on treatment with an oxidative bleaching bath, reacts with the residual colour coupler so as to form an acid-resistant magenta dye, (4) a yellow filter layer consisting of a gelatin layer containing colloidal silver, and adjacent thereto, (5) a blue-sensitive silver halide emulsion layer
  • the colour couplers and the corresponding oxidatively coupling compounds can be present not only in their respective light-sensitive silver halide emulsion layers, but also in adjacent non light-sensitive colloid layers.
  • the process of forming direct positive colour images according to this invention preferably is carried out using a photographic colour material containing differently sensitized silver halide emulsion layers each containing a colour coupler and the corresponding oxidatively coupling compound
  • the process according to this invention can be applied with photographic materials containing mixed packet photographic silver halide emulsions such as described in the British patent specification No. 810,780, the French patent specification No. 1,258,509, the Canadian patent specification No. 518,723, the British patent specifications Nos. 786,274, 524,154, 524,555, 777,587, 755,987, 766,895, 718,404 and 793,570, the U.S. patent specifications Nos.
  • a light-sensitive element for colour photography comprising a support and a plurality of differently sensitized emulsions colour couplers fast to diffusion and capable of forming dyes selected from the group consisting of quinone-imine and azomethine dyes with the oxidation products of a developer, at least one of said silver halide emulsions being applied in the form of a layer and at least one other of said emulsions being applied in the form of finely distributed hardened particles.
  • two differently sensitized emulsions each of these containing respectively greenand red-sensitized silver halide, a colour coupler and an oxidatively coupling compound forming on oxidative coupling with containing said colour coupler respectively a cyan and a magenta dye, have been dispersed in the form of emulsion particles in a colloid layer onto which a yellow filter layer is coated whereon a blue-sensitive silver halide emulsion layer is coated containing a colour coupler and an oxidatively coupling compound forming a yellow dye with said colour coupler during treatment with an oxidizing solution.
  • the silver halide emulsions wherein the non-dilfusing colour couplers and the non-diffusing oxidatively coupling compounds are incorporated contain the usual col- Ioids e.g. gelatin, polyvinyl alcohol, collodion or other natural colloids.
  • col- Ioids e.g. gelatin, polyvinyl alcohol, collodion or other natural colloids.
  • the silver halide emulsion layers can be coated onto a support of paper, glass, cellulose nitrate, organic cellulose esters e.g. cellulose triacetate, polyesters e.g. poly-' ethylene glycol terephthaliate, polymers e.g. polystyrene, or any other natural or synthetic plastic material.
  • the used developing agents in principle should form with the colour couplers a non acid-resisting dye which can be destroyed in an acid containing bath.
  • a non acid-resisting dye which can be destroyed in an acid containing bath.
  • quinone-imine and azo-rnethine dyes are formed which as known are not very acid-resistant.
  • Developing agents which come into consideration therefore are aromatic amino compounds e.g. mono-, diand triaminoaryl compounds, more especially N,N-dialkyl-pphenylenediamine and derivatives such as N,N-dialkyl- N'-sulphomethyl-p-phenylenediamine or N,N-dia1kyl-N- carboxymethyl-p-phenylenediamine.
  • monoamine developing agents aminophenols and aminocresols, or their halogen derivatives, and also amin-onaphth-ols come into consideration.
  • the photographic bleaching bath wherein the oxidative coupling preferably takes place and wherein the metallic silver is reoxidized is an alkaline bleaching bath. It has preferably a pH of at least 8 and preferably contains as oxidizing compound potassium ferricyanide, and further salts e.g. borax, potassium bromide and magnesium sulphate.
  • the acid treatment which causes the destruction of the non acid-resistant quinone-imine and azomethine dyes which are formed on the exposed areas during the development step is carried out in an acid solution having preferably a pH at least 1.
  • the acid solution contains preferably a strong acid such as hydrochloric and/or sulfuric acid. It has been stated that the destruction of the primary dyes can be accelerated if an oxidizing agent such as potassium dichromate is also present in the acid solution. It has also been stated that the destruction of the primary quinone-imine or azomethine dyes is complete, even after short treatment if a combination is used of a strong acid and known-reducing agents or compounds which form in situ in an acid medium reducing substance.
  • the photographic material used in the present invention can be fixed just after the colour development step, but normally has to be fixed also after the bleaching step for removing the oxidized silver metal.
  • the acid treatment is preferably carried out at room temperature.
  • the destruction of the primary dyes proceeds very quickly in the mentioned compositions. In a few seconds the decolorization of the primary quinoneimine or azomethine dyes is complete.
  • Example 1 To 280 g. of a light-sensitive silver halide emulsion containing /6 mol of highly sensitive silver bromide and 8% of gelatin, are successively added: (1) 20 cm. of a 0.1% alcoholic solution of a sensitizing agent for green light, (2) 45 cm. of a colour coupler solution consisting of 4.5 g. of N-(2-n-hexadecylsulfonyl-5'-sulfophenyl)-1-hydroxy-Z-naphthoic acid amide sodium salt dissolved in a mixture of 40.5 cm. of water and 4.5 cm. of 2 N sodium hydroxide, and (3) 15 cm. of a solution consisting of 5 g.
  • This emulsion is coated onto a cellulose triacetate support which has been provided with a usual subbing layer and dried.
  • a strip of the light-sensitive material obtained is exposed behind a grey-wedge and a green filter, and then developed for 10 min. at 20 C. in a developing bath of the following composition:
  • Example 2 The light-sensitive material is prepared in an analogous way as that of Example 1 with the difference, however,
  • Example 3 The light-sensitive material is prepared in an analogous way as that of Example 1 with the difference, however, that the emulsion is not green-sensitized, that the cyan color coupler N- (2'-n-hexadecylsulfonyl-S'-sulfophenyl 1-hyd1'oxy-2-naphthoic acid amide sodium salt is replaced by a same amount of the magenta color coupler 1-p-sulfophenyl-3-pentadecyl-pyrazolone-3 prepared according to British patent specification No.
  • Example 4 To 280 g. of a light-sensitive silver halide emulsion containing /6 mol of highly sensitive silver bromide and 8% of gelatin, are successively added: (1) 20 cm. of a 0.1% alcoholic solution of an optical sensitizer for green light, (2) 45 cm. of a color coupler solution consisting of 4.5 g. of N-(2'-n-hexadecylsulphonyl-5'-sulphophenyl)-1-hydroxy-2-naphthoic acid amide sodium salt dissolved in a mixture of 40.5 cm. of water and 4.5 cm. of 2 N aqueous sodium hydroxide, and (3) 6 g.
  • This emulsion is coated onto a cellulose triacetate support which has been provided with a usual subbing layer and dried.
  • a strip of the light-sensitive material obtained is exposed behind a grey wedge and then developed for 10 min. at 20 C. in a developing bath of the following composition:
  • the bleached material is then rinsed for 5 min. in running water of 20 C. and the negative colors are 31 bleached for min. in a color bleach bath of the following composition:
  • Example 5 The lightensitive material is prepared in an analogous way as that of Example 4 with the difference, however, that the emulsion is not green-sensitized and that the naphthol color coupler is replaced by a same amount of 1 (m sulfophenyl) 3 (m stearoylaminophenyl)-5- pyrazolone. After exposure behind a grey wedge to blue light and processing as described in Example 4, a positive yellow Wedge image is obtained on the film strip. Absorption maximum: 450 m
  • Example 6 The light-sensitive material is prepared in an analogous way as that of Example 4 with the dillerence, however,
  • Example 8 To 500 g. of a red-sensitized silver halide emulsion .containing 0.16 mol of silver halide (4 mol percent of silver iodide and 96 mol percent of silver bromide) and 80 g. of gelatin per liter digested for 1 h. at 36 C.,
  • the emulsion After neutralizing the emulsion with N acetic acid and after adding the usual ingredients such a stabilizing agents, surface-active agents and hardening agents, the emulsion is coated onto a transparent cellulose triacetate support provided with a gelatin subbing layer, in such a way that it covers 10 sq. m.
  • a positive cyan dye image with an absorption maximum: 655 mg is obtained (see FIG. 1).
  • Example 9 The composition of the silver halide emulsion is the same as in Example 8 except that the 8 g. of l-methyl- 2 ('o-chlorophenyl)-4-quinolone-n-hexadecylsulfonlyhydrazone hydrochloride are replaced by 8 g. of 1-methyl- 2 phenyl 4-quinolone-(2'-n-hexadecyloxy-5'-carboxyphenyl)-sulfonyl hydrazone prepared according to Preparation 8 and dissolved at 50 C. in 80 om. of 0.3 N potassium hydroxide in methanol.
  • Example 10 To 500 .g. of a green-sensitized silver halide emulsion containing 0.16 mol of silver halide (4 mol percent of silver iodide and 96 mol percent of silver bromide) and 80 g. of gelatin .per liter digested for 1 h. at 36 C. are successively added: (1) 250 cm? of distilled water, (2) 8 g. (12.5 millimol) of N-(2'-n-h-exadecylsulfonyl-5'-sulfophenyl)-1-hydroxy-2-naphthoic acid amide sodium salt dissolved in 80 cm. of 0.15 N sodium hydroxide, (3) 8 g. (26 millimol) of 1,2-dimethyl-4-amino-5-tridecylpyrazolone-3 dissolved in 80 cm. of methanol.
  • the emulsion After neutralizing the emulsion with N acetic acid and after adding the usual ingredients such as stabilizing agents, surface-active agents and hardening agents the emulsion is coated onto a transparent cellulose triacetate support provided with a gelatin subbing layer in such a Way that it covers 1-0 sq. m.
  • a positive magenta dye image with absorption maximum: 540 m is obtained.
  • Example 11 The light-sensitive material is prepared in an analogous way as that of Example 4 with the difierence, however, that the emulsion is not green-sensitized, that the naphthol color coupler is replaced by a same amount of 1-(4-nhexadecylsulfonylphenyl) 3 (2-sulfobenzoylamin o)-5- pyrazolone sodium salt and that the oxidatively coupling compound of Preparation 5 is rep-laced by a same amount of the oxidatively coupling compound having the formula:
  • Example 12 A photographic multilayer material is used for preparing direct positive color images.
  • This multilayer material consists of the following superposed layers in the indicated sequence: a support, an anti halation layer, a gelatin layer, a red-sensitive halide emulsion layer containing as color coupler the sodium salt of N(2"-n-hexadecylsulfonyl-S'-sulfophenyl)-1-hydroxy-2-naphthoic acid amide and the oxdizinig coupling compound of Example 7, a gelatin interlayer, a green-sensitive silver halide emulsion layer containing the same color coupler as the redsensitive silver halide emulsion layer and the oxidizing coupling compound of Example 4, a yellow filter layer, a blue-sensitive silver halide emulsion layer containing as color coupler 1(p-sulfophenyl)-3-palmitoylamino S-pyrazolone and the oxidizing coupling compound of Example 4 and
  • the red-sensitive emulsion layer is prepared as follows:
  • the green-sensitive emulsion layer is prepared as follows:
  • the blue-sensitive emulsion layer is prepared as follows:
  • gelatino silver bromoiodide emulsion (2% iodide) containing mol of silver halide are added: 10 g. of the potassium salt of l-(p-sulfophenyD-3-palmitoylam-ino-Spyrazolone dissolved in a slightly alkaline mixture of alcohol and water, and 10 g. of 11phenyl-4- methyl-2-quinolone-n-hexadecylsulfonyl hydrazone prepared according to Preparation 5, dissolved by heating till 60 C. in a mixture of 100* cm. of diacetone alcohol, 10 cm. of 2 N sodium hydroxide and 80 cm. of water.
  • This emulsion is acidified with N acetic acid to pH 7.5. After adding the usual additives such as hardeners, wetting agents and stabilizers, the emulsion is coated.
  • the obtained multilayer color material is exposed to a colored original and processed as described in Example 4. A positive color image of the original is obtained.
  • a photographic process for preparing a direct positive colour image which comprises the steps of:
  • exposing to an object a photographic element comprising (a) at least one water-permeable layer which contains light-sensitive silver halide grains,
  • a photographic process for preparing a direct positive colour image wherein the photographic element contains a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, each of said layers containing a colour coupler capable of forming on development a dye which by treatment with a strong acidic solution can be transformed in colourless products, the red-sensitive emulsion layer also containing a compound which is capable of forming by oxidative coupling with the colour coupler present in that layer an acid-resistant cyan dye, the green-sensitive emulsion layer also containing a compound which is capable of forming by oxidative coupling with the colour coupler present in that layer an acid-resistant magenta dye, and the blue-sensitive emulsion layer also containing a compound which is capable of forming by oxidative coupling with the colour coupler present in that layer an acid-resistant yellow dye, whereby a positive colour image is formed consisting of the superposed
  • step 2 comprises a primary amino developing agent and said colour coupler is capable of forming with said developing agent upon development therewith, a dyestuif selected from the group consisting of a quinone-imine and azo-methine dyestuffs.
  • step (10) is selected from the group consisting of a 4- amino-pyrazolone-3 compound, a hydrazone compound, and an amidrazone compound.
  • a photographic process for preparing a direct positive colour image which comprises the steps of:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
US342305A 1961-08-02 1964-02-03 Process for the preparation of colour images Expired - Lifetime US3293032A (en)

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DE (1) DE1146751B (fr)
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3384484A (en) * 1963-04-11 1968-05-21 Agfa Ag Silver halide photographic materials containing organic hydrazone compounds
US3443942A (en) * 1964-07-24 1969-05-13 Agfa Gevaert Ag Colored photographic direct positive images
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
US3537850A (en) * 1966-12-02 1970-11-03 Polaroid Corp Color transfer image-forming process utilizing coupler-developers whose oxidation products can couple intermolecularly
US3622327A (en) * 1969-02-04 1971-11-23 Agfa Gevaert Nv Process for preparing color images
US3753395A (en) * 1970-04-09 1973-08-21 Agfa Gevaert Nv Photo-thermographic recording process with 5-pyrazolane
US4022616A (en) * 1974-06-03 1977-05-10 Eastman Kodak Company Photographic process involving amplification with CO (III) complexes, silver-dye-bleaching and colorless dye formers which form bleachable dyes
US4514494A (en) * 1982-11-12 1985-04-30 Agfa-Gevaert N.V. Photographic color material incorporating developing agents for color development
US5202224A (en) * 1990-01-09 1993-04-13 Fuji Photo Film Co., Ltd. Dye-forming coupler, a silver halide color photographic material using same, and a method for processing the silver halide color photographic material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2020775A (en) * 1930-11-07 1935-11-12 Bela Gaspar Method of producing photographic pictures in colors
US2263012A (en) * 1937-12-23 1941-11-18 Eastman Kodak Co Process for making natural color photographs
US3047385A (en) * 1959-11-30 1962-07-31 Gevaert Photo Prod Nv Production of color photographic images
US3186840A (en) * 1958-12-11 1965-06-01 Agfa Ag Direct positive colored photographic elements containing dihydrazones and process for forming colored masks therefrom

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2020775A (en) * 1930-11-07 1935-11-12 Bela Gaspar Method of producing photographic pictures in colors
US2263012A (en) * 1937-12-23 1941-11-18 Eastman Kodak Co Process for making natural color photographs
US3186840A (en) * 1958-12-11 1965-06-01 Agfa Ag Direct positive colored photographic elements containing dihydrazones and process for forming colored masks therefrom
US3047385A (en) * 1959-11-30 1962-07-31 Gevaert Photo Prod Nv Production of color photographic images

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3384484A (en) * 1963-04-11 1968-05-21 Agfa Ag Silver halide photographic materials containing organic hydrazone compounds
US3467520A (en) * 1964-03-20 1969-09-16 Agfa Ag Production of colored direct positive photographic images
US3443942A (en) * 1964-07-24 1969-05-13 Agfa Gevaert Ag Colored photographic direct positive 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
US3537850A (en) * 1966-12-02 1970-11-03 Polaroid Corp Color transfer image-forming process utilizing coupler-developers whose oxidation products can couple intermolecularly
US3622327A (en) * 1969-02-04 1971-11-23 Agfa Gevaert Nv Process for preparing color images
US3753395A (en) * 1970-04-09 1973-08-21 Agfa Gevaert Nv Photo-thermographic recording process with 5-pyrazolane
US4022616A (en) * 1974-06-03 1977-05-10 Eastman Kodak Company Photographic process involving amplification with CO (III) complexes, silver-dye-bleaching and colorless dye formers which form bleachable dyes
US4514494A (en) * 1982-11-12 1985-04-30 Agfa-Gevaert N.V. Photographic color material incorporating developing agents for color development
US5202224A (en) * 1990-01-09 1993-04-13 Fuji Photo Film Co., Ltd. Dye-forming coupler, a silver halide color photographic material using same, and a method for processing the silver halide color photographic material

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GB990628A (en) 1965-04-28
CH424478A (fr) 1966-11-15
DE1146751B (de) 1963-04-04
FR1335232A (fr) 1963-08-16
BE620977A (fr)
AT250784B (de) 1966-11-25

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