Classifications

• • 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 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 proportion 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.
• Correction of the colors on printing is therefore desirable, and this is usually done by masking. Since separate masks are difiicult 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 with the oxidation product of an aromatic amino developing agent to form by colordevelopment 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, 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 compensating the unwanted absorption of blue and/or green light by the cyan image dye, respectively the unwanted absorption of blue light by the magenta dye image.
• an oxidizing solution such as a photographic bleaching bath
• mask forming compounds are used containing the following general structures:
• Mask forming compounds containing in their molecule groupings according to the foregoing general structures ing of a hydrogen atom, a lower alkyl radical and an aralkyl radical;
• R represents a member selected from the group consisting of a hydrogen atom, an alkyl radical, an aralkyl radical, and an aryl radical;
• X represents a member selected from the group consisting of an alkyl radical, a substituted alkyl radical, an
• aralkyl radical a substituted aralkyl radical, an aryl radical and a substituted aryl radical
• Y represents a member selected from the group consisting of an aryl radical such as a phenyl radical or a substituted phenyl radical such as a 4-methoxyphenyl radical, a 4-[/3-(fi-n-butoxy-ethoxy)-ethoxy]-phenyl radical, a 4-n-hexadecyl sulfonamido-phenyl radical, a 3- amino 4-[/3-(4'-isooctylphenoxy) -ethoXy]-phenyl radical, a 4-hexadecenyl succinoyl amino phenyl radical, a 4-decyloxyphenyl radical, a 3-(w-carboxydecyl-sulfonamidophenyl) radical, a 3-(4-carboxy-phenyl sulfonamido)-4-(n-hexadecyloxy)-phenyl radical, and a 4-(wcarbox
• the mask forming compounds according to our invention and more particularly the hydrazides according to the general Formula I can be prepared by reacting carboxylic acid esters with hydrazine or hydrazine hydrochloride.
• Preparation 1 2.-5 (w-carboay-decylsul fonami do isophzhalic acid dihydrazide (I) ONHNH2 13.5 g. (0.05 mol) of ll-bromohendecanoic acid and 3.8 -g. (0.05 mol) of thioureum are refluxed for 2 h. in 100 cm. of ethanol. After evaporating the solvent, the residue is Washed with ether and recrystallized from dioxane. 10.2 g. of S-(w-carboxydecyD-isotbiouronium bromide is obtained. Melting point: 148 C.
• 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 wherein the 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 comprising a linear chain of 5 to 20 carbon atoms.
• the process of color correction of the present invention may be practised, i.a., by using a color photographic material containing a coupler for magenta belonging to the class of the pyrazolone color couplers and/ or a conr pler for cyan belonging to the class of the phenolor naphthol color couplers.
• a color photographic material containing a coupler for magenta belonging to the class of the pyrazolone color couplers and/ or a conr pler for cyan belonging to the class of the phenolor naphthol color couplers.
• an oxidizing substance such as present in a potassium ferricyanide bleaching bath.
• Pyrazolone color couplers which are especially useful for obtaining a mask image for magenta by reaction with the mask forming substances according to the present invention are e.g. those represented by the general formula:
• D represents an aliphatic radical making the molecule fast to diffusion and comprising a linear chain of at least and at most 20 carbon atoms, preferably 14, 16 or 18 carbon atoms.
• Naphthol color couplers which are especially useful for obtaining a mask image for cyan by reaction with the mask forming substances according to the present invention are, e.g., these 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 CO NH- group, a --SO NH group, a --NHSO group, a
• III-alkyl group and a sulfonyl group
• Y' represents a member selected from the group consist- .ing of an hydrogen atom and a halogen atom
• M represents a member selected from the group consisting of an hydrogen atom, an alkali metal atom and an ammonium group
• Suitable color couplers of the above general formula are for instance:
• color couplers for cyan can be prepared, e.g., by condensation of 1-hydroxy-2-n'ap'hthoic acid or its derivatives with the suitable aromatic amines according to German patent application No. G 30,287, fi1ed August 13, 1960, now German Patent No. 1,121,061.
• 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, collodion 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 greensensitive 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 non-light-sensitive layer which is separated from the light-sensitive 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 the same time oxidized.
• the oxidized developing agent reacts with the color coupler and forms a dyestutf on the exposed areas, the mask forming compound according to the invention not being affected.
• the material comes into the bleaching bath wherein the oxidation of the maskforrning compound takes place, and the remaining color coupler still available at the nonexposed areas of the material oxidatively couples with the oxidation product of the mask compound thus forming the mask dyestuff. In this way the colored mask image is formed.
• the photographic color material is washed with water, fixed and dried.
• aromatic amino-compounds can be use as developers for such material: mono-, diand triaminoaryl compounds, more especially N,N-dialkyl-p-phenylenediamines, such as N,N-diethyl-p-phenylenediamine and N,N-diethyl-Z-methyl-p-phenylene diamine, and derivatives thereof such as N,N-dialkyl-N-sulfomethylor carboxymethyl-p-phenylenediamine.
• monoamino-developers should be cited: aminophenols and aminocresols or their halogen derivatives and also the amino-naphthols.
• the bleaching bath generally contains potassium bromide, borax, magnesium sulfate and especially potassium ferricyanide. These elements are dissolved in precisely determined amounts of water so that a solution with a determined pH value is obtained.
• Example 1 To /2 kg. of a green-sensitized silver bromo-iodide emulsion containing mol. of silver halide are added a slightly alkaline alcoholic solution containing 9 g. of 1-psulfophenyl-3-heptadecyl-5-pyrazolone, and a solution in 40 cm. of ethanol of 4 g. of p-decyloxy benzoic acid :hydnazide obtained according to Preparation 6. After acidification with acetic acid to pH 5.8 and after addition of the usual additives such as hardeners, wetting agents 11 and stabilizers, the emulsion obtained is coated on a suitable support and dried.
• a slightly alkaline alcoholic solution containing 9 g. of 1-psulfophenyl-3-heptadecyl-5-pyrazolone, and a solution in 40 cm. of ethanol of 4 g. of p-decyloxy benzoic acid :h
• the photographic material After exposure through a grey-wedge with a constant 0.15, the photographic material is developed for 9 at 20 C. in a color develop- This material is rinsed for 30 minutes at 18 to 20 C. and fixed for minutes at 20 C. in a fixing bath of the following composition:
• Trisodium salt of ethylene diamine tetraacetic acid 1 Sodium thiosulfate 130 Sodium carbonate 6 Sodium bicarbonate 14 Sodium sulfite 10 Water to 1000 cm.
• a mainly magenta colored image is obtained together with a yellow dye image, said yellow image being of opposite gradation in respect of the magenta dye image and reducing the disturbing influence of the unwanted absorption in the blue region of the spectrum of the magenta image.
• Example 2 To /2 kg. of a green-sensitized silver bromo-iodide emulsion containing Vs mol. of silver halide are added a slightly alkaline alcoholic solution containing 9 g. of 1-p-sulfophenyl-3-heptadecyl-5-pyrazolone and a solution in 40 cm. of ethanol of 4 g. of p-decyloxybenzoic acid hydrazide obtained according to Preparation 6. After acidification with acetic acid to pH 6 and after addition of the usual additives such as hardeners, wetting agents and stabilizers, the emulsion obtained is ready to be coated.
• a slightly alkaline alcoholic solution containing 9 g. of 1-p-sulfophenyl-3-heptadecyl-5-pyrazolone and a solution in 40 cm. of ethanol of 4 g. of p-decyloxybenzoic acid hydrazide obtained according to Preparation
• this emulsion forms part of a multilayer photographic material consisting of the following superposed layers in the indicated sequence: a support, an antihalation layer, a gelatin insulating layer, a red-sensitized emulsion layer containing a color coupler for cyan, a gelatin interlayer, the above-mentioned greensensitized emulsion layer, a yellow filter layer, a bluesensitive emulsion layer containing a color coupler for yellow and at last a gelatin overcoat as antistress layer.
• this emulsion forms part of a multilayer photographic material consisting of the following superposed layers in the indicated sequence: a supporting antihalation 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, a yellow filter layer, a blue-sensitive emulsion layer containing a color coupler for yellow and at last a gelatin overcoat as antistress layer.
• a mainly cyan-colored image is obtained together with a red dye image in the red-sensitive layer, said'red image being of opposite gradation in respect of the cyan dye image and reducing the disturbing influence of the sideabsorption in the blue and in the green in the formed cyan image.
• Example 5 To kg. of a green-sensitive silver bromo-iodide emulsion containing Ms mol of silver halide are added a slightly alkaline alcoholic solution containing 9 g. of l-p-sulfophenyl-3-heptadecyl-5-pyrazolone and a solution of 5-(nhexadecylsulfonamido)-isophthalic acid dihydrazide prepared according to Preparation 7 in a mixture of 12 cm. aqueous 2 N sodium hydroxide and 4 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 antihalation layer, a gelatin insulating layer, a redsensitized emulsion layer containing a color coupler for cyan, a gelatin interlayer, the above-mentioned greensensitized emulsion layer, a yellow filter layer, a blue-sensitive emulsion layer containing a color coupler for yellow and at last a gelatin overcoat as antistress layer.
• Example 1 After exposure through a grey-wedge with a constant 0.15 the photographic material is developed and further treated as in Example 1.
• a mainly magenta colored image is obtained together with a yellow dye image in the green-sensitized layer, said yellow image being of opposite gradation in respect of the magenta dye image and reducing the disturbing influence of the unwanted absorption in the blue region of the spectrum of the formed magenta image.
• Example 6 A photographic multilayer material is manufactured as in the foregoing example, the red-sensitive and the green-sensitive emulsion layers being prepared as follows:
• the red-sensitive emulsion layer is prepared by adding to /2 kg. of a gelatino silver bromo-iodide emulsion (2% of iodide) containing /6 mol of silver halide a solution of 9 g. of N-(6'-cetylsulfonyl-phenyl)-l-hydroxy-2-naphthoic acid amide-3-sodium sulfonate in a mixture of 175 cm. of water and 6.3 cm. of aqueous 2 N sodium hydroxide and a solution of 4 g.
• the green-sensitive emulsion layer is prepared by adding to /2 kg. of gelatino silver bromo-iodide emulsion (2% of iodide) containing mol of silver halide 9 g. of a slightly alkaline alcoholic solution of l-p-sulfophenyl-3- heptadecyl-S-pyrazolone and a solution of 4 g. of the mask compound S-(nhexadecylsulfonamido)-isophthalic acid dihydrazide prepared according to Preparation 7, in a mixture of 12 cm. of aqueous 2 N sodium hydroxide and 4 cm. of distilled water. Next, this emulsion is acidified with acetic acid to pH 5.8 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 light-sensitive multilayer photographic material is exposed through a grey-wedge, developed and further treated as described in Example 1.
• red-sensitive emulsion layer a red dye mask image is formed in addition to the cyan image 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.
• a yellow dye mask image is formed in addition to the magenta dye image with a gradation opposed to that of the magenta image, and which reduces the disturbing influence of the unwanted absorption in the blue region of the spectrum of the formed magenta image.
• Y is a member of the group consisting of an aryl radical and a heterocyclic 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 magenta 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.
• Ar is a member of the group consisting of a phenyl radical and a phenyl radical containing a solubilizing group
• D is an aliphatic radical comprising a linear chain of 5-20 carbon atoms.
• Y is a member of the group consisting of 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.
• Z is a member of the group consisting of hydrogen and halogen
• D is an aliphatic radical comprising a linear chain of -20 carbon atoms
• i M is a member of the group consisting of hydrogen
• alkali metal alkali metal, and ammonium.
• Y is a member of the group consisting of an aryl radical and a heterocyclic radical; said color coupler for cyan also being reactive with the oxidation product of said mask-forming compound to form asecondary 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 regions but transmitting substantially all the light in said major absorption region.
• X is a member of the group consisting of O-, S-, NHCO-, CONH, SO NH--, NHSO lTl-alkyl and --SO Z is a member of the group consisting of hydrogen-and halogen,
• D is an aliphatic radical comprising a linear chain-of I 5-20 carbon atoms
• M is a member of the group consisting of hydrogen ⁇ alkali metal, and ammonium.

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

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• 0
  • BE BE601938D patent/BE601938A/xx unknown
• 1960
  • 1960-03-29 GB GB11036/60A patent/GB979992A/en not_active Expired
• 1961
  • 1961-03-27 US US112140A patent/US3249431A/en not_active Expired - Lifetime
  • 1961-03-29 DE DEG31940A patent/DE1157482B/de active Pending

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