US3622327A - Process for preparing color images - Google Patents

Process for preparing color images Download PDF

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Publication number
US3622327A
US3622327A US8525A US3622327DA US3622327A US 3622327 A US3622327 A US 3622327A US 8525 A US8525 A US 8525A US 3622327D A US3622327D A US 3622327DA US 3622327 A US3622327 A US 3622327A
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United States
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color
photographic element
color coupler
silver halide
coupler
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US8525A
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English (en)
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Jan Jaeken
Wilhelmus Janssens
Marc Godfried Mennens
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Agfa Gevaert NV
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Agfa Gevaert 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
    • C07D215/42—Nitrogen atoms attached in position 4
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains

Definitions

  • the present invention relates to a process for preparing direct positive color images, to hydrazone compounds of use in said process and to photographic materials containing such hydrazone compounds.
  • a process for the preparation of direct positive color images comprises the steps of l imagewise exposing a photographic element comprising (a) at least one water-permeable layer which contains light-sensitive silver halide grains, (b) a color coupler in effective contact with said silver halide grains, said color coupler being capable of forming on development a dye which by treatment with a strong acidic solution can be converted into colorless products, and (c) a compound in effective contact with said color coupler, said compound being capable of forming an acid-resistant dye by oxidative coupling with said N-NHSO R color coupler (2) developing the photographic element in a color-forming developer, (3) treating the photographic ele- MO;,S
  • tive coupling at the nondeveloped areas of the photographic Ar stands for aryl including substituted aryl e.g phenyl and element where color coupler is still present after the developphenyl substituted by alkyl including substituted alkyl,
  • aryl including substituted aryl, aralkyl including sub- According to a preferred embodiment of the process of the stituted aralkyl, cycloalkyl, carboxyl or sulpho in acid or' above United States patent specification a photographic mulal m, h g a y c ng Substituted yi tilayer material is used which comprises a red-sensitive, a aryloxy including substituted aryloxy, alkylthio including green-sensitive and a blue-sensitive silver halide emulsion substituted alkylthio, arylthio including substituted layer each of said layers containing a color coupler capable of arylthio, alkylsulphonyl including substituted alkylforming on development a quinone-imine or azomethine dye sulphonyl, arylsulphonyl including substituted arylwhich by treatment with a strong acidic solution can be transsulphonyl
  • a compound which is capable of forming an R stands for alkyl including substituted alkyl, aryl including acid-resistant cyan dye by oxidative coupling with the color substituted aryl, aralkyl including substituted aralkyl or coupler present in that emulsion layer the green-sensitive amino including substituted amino,
  • emulsion layer also containing a compound which is capable R, stands for alkyl including substituted alkyl such as methyl of forming an acid-resistant magenta dye by oxidative and chloroethyl,
  • emulsion layer M stands for hydrogen or an alkali metal atom such as and the blue-sensitive emulsion layer also containing a compotassium, sodium.
  • pound which is capable of forming an acid-resistant yellow The oxidatively coupling hydrazone compounds cordye by oxidative coupling with the color coupler present in responding to the above general formula can be prepared as is that emulsion layer.
  • quinolone hydrazone oxidatively coupling compounds according to the present invention can be represented by the following general formula:
  • the qunolones (B) are converted into the Melting Point chloroquinolones (C) by means of phosphorus oxychloride or y 'p y 1'4-chlol'o'fluomsulphonylquinolinium thionyl chloride whereupon by quaternization compounds methy! Sulfata (D), having an unsharp melting point, are formed.
  • the 100 8( mole) of 'p y sulphonyl hydrazones E are f d b reaction f 10 fluorosulphonylquinoline and 88 ml.
  • adecylsulphonyl hyldrazone are prepared Two-hundred thirty-five gram (0.525 mole) of l-methyl-Z- phenyl-4-chloro-6-fluorosulphonyl-quinolinium methyl Preparation 20 sulphate and 168 g. (0.525 mole) of n-hexadecyl sulphonylhydrazide were refluxed for 4 hours in 2 liters of chloroform.
  • color couplers there may be mentioned phenol and a-naphthol compounds, which in the common color development with aromatic primary amino developing agents form cyan, indophenol or quinone-imine dyes that are not completely acid resistant, and m-acylamino-N,N-dialkylanilines and a-naphthylsulphamoyl compounds, which form on color development with aromatic primary amino developing agents indoamine dyes that are also not completely acid resistant.
  • the a-naphthol color couplers for which there can be referred to the above US. Pat. specification and the patent literature referred to therein, to Belgian Pat. Nos. 548,880 and 596,509 and to United Kingdom Pat. No. 1,104,729, are preferably used, the a-naphthylsulphamoyl and m-acyl-amino- N,N-dialkylaniline color couplers corresponding to the following general formulas having also been found to be particularly suitable:
  • the color coupler and quinoline hydrazone compound are preferably incorporated into a light-sensitive silver halide emulsion layer of the said element. They may however, also be added to the composition of a water-permeable non-light-sensitive layer, which is in direct contact with the light-sensitive silver halide emulsion layer, or they may be incorporated into a non-light-sensitive layer, which is separated from the light-sensitive layer by a water-permeable non-light-sensitive layer.
  • a color coupler in effective contact with said silver halide grains, said coupler being capable of forming on color development a dye, which by treatment with a strong acidic solution can be converted into colorless products, and
  • quinolone hydrazone compound which corresponds to the above general formula and which is capable of forming an acid-resistant cyan dye by oxidative coupling with said color coupler.
  • the oxidatively coupling compound can oxidatively couple with the color coupler in the colloid layer wherein the latter is present on treatment in oxidative medium.
  • the photographic element for producing direct positive color images comprises more specifically at least one water-permeable colloid layer wherein light-sensitive silver halide grains are present and wherein said water-permeable colloid layer or a colloid layer in water-permeable relationship therewith comprises at least one color coupler which on development couples in the exposed areas with the oxidation product of an aromatic primary amino developing agent to form on these areas a dye which can be destroyed or transformed into colorless products by treatment with a strong acidic solution, and wherein the said water-permeable colloid layer containing the silver halide or a colloid layer in water-permeable relationship therewith contains a quinolone hydrazone compound corresponding to the above general formula, which on treatment of the color developed photographic element in an oxidizing solution oxidatively couples with said color coupler to form in the nondeveloped areas a secondary cyan dye which cannot be destroyed or transformed into colorless products by the said treatment with a strong acidic solution.
  • the quinolone hydrazone oxidatively coupling compounds described in the present invention are usually incorporated into a red-sensitive silver halide emulsion forming one of the difierently sensitized silver halide emulsion layers of a photographic multilayer color material suitable for producing a direct positive multicolor image according to the method of the above U.S. Pat. specification.
  • a photographic multilayer material therefore comprises a support, a red-sensitized silver halide emulsion layer, a green-sensitized silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer each of said emulsion layers containing a color coupler capable of forming on development a quinone-imine or azomethine dye and an oxidatively coupling compound which, after development, on treatment with an oxidative bleaching bath, reacts with the residual color coupler so as to form an acid-resisting cyan, magenta, and yellow dye respectively wherein the oxidatively coupling compound of the red-sensitive emulsion layer is a hydrazone com pound corresponding to the above general formula.
  • the color couplers and oxidatively coupling compounds can of course be present not only in their respective light-sensitive silver halide emulsion layers but also in adjacent nonlight-sensitive colloid layers.
  • the yellow separation image is formed by oxidative coupling of a pyrazolone color coupler with a benzothiazolone hydrazone coupling compound
  • the magenta separation image is formed by oxidative coupling of an a-naphthol color coupler with a 4-amino-pyrazolone-3 coupling compound
  • the cyan separation image is formed by oxidative coupling of an a-naphthol color coupler with a quinolone hydrazone coupling compound according to the present invention.
  • the a-naphthol color coupler used for the formation of the magenta separation image may be the same as that used for the formation of the cyan separation image.
  • the ratio in moles of light-sensitive silver halide to color coupler is preferably comprised between 6:] and 15:1 and the ratio of color coupler to oxidatively coupling compound preferably varies from 1:1 to 1:3.
  • the color couplers and oxidatively coupling compounds can be incorporated into the photographic material according to any technique known .by those skilled in the art for incorporation of photographic ingredients, more particularly color couplers and mask-forming compounds, into colloid compositions.
  • the water-soluble compounds can be incorporated into the coating composition of the layer in question from an aqueous solution or alkaline aqueous solution and the water-insoluble or insufficiently water-soluble compounds from a solution in the appropriate water-miscible or water-immiscible high-boiling or low-boiling organic solvents or mixtures thereof whereupon the solution obtained is dispersed, if necessary in the presence of a wetting or dispersing agent, in a hydrophilic colloid composition forming or forming part of the binding agent of the colloid layer.
  • the hydrophilic colloid composition may of course comprise in addition to the colloid carrier all other sorts of ingredients.
  • solutions of the color couplers and oxidatively coupling compounds need not necessarily be dispersed or dissolved directly in the coating composition of the silver halide emulsion layer or other water-permeable layer.
  • Said solution may advantageously be first dispersed or dissolved in an aqueous non-lightosensitive hydrophilic colloid solution whereupon the resultant mixture, if necessary after the removal of the organic solvents employed, is intimately mixed with the said coating composition of the light-sensitive silver halide emulsion layer or other water-permeable layer just before coating.
  • the hydrophilic colloid used as the vehicle for the silver halide may be, for example, gelatin, colloidal albumin, zein, casein, a cellulose derivative, a synthetic hydrophilic colloid such as polyvinyl-alcohol, poly-N-vinylpyrrolidone etc. If desired, compatible mixtures of two or more of these colloids may be employed for dispersing the silver halide.
  • silver salts may be used as the sensitive salt, such as silver bromide, silver iodide, silver chloride, or mixed silver halides, such as silver chlorobromide, silver bromoiodide and silver chlorobromoiodide.
  • a photographic element comprising differently sensitized silver halide emulsion layers each containing a color coupler and an oxidatively coupling compound
  • photographic materials can be used containing mixed packet photographic silver halide emulsions.
  • this kind of emulsions there can be referred to the above U.S. Pat. No. 3,293,032 and the patent literature referred to therein.
  • the light-sensitive silver halide emulsions of use in the preparation of a photographic material according to the present invention may be chemically as well as optically sensitized. They may be chemically sensitized by effecting the ripening in the presence of amounts of sulphur containing compounds such as allyl thiocyanate, allyl thiourea, sodium thiosulphate, etc.
  • the emulsions may also be sensitized by means of reductors for instance tin compounds as described in French Pat. No. 1,146,955 and in Belgian Pat. No. 568,687, imino-amino methane sulphinic acid compounds as described in United Kingdom Pat. No. 789,823 and small amounts of noble metal compounds such as of gold, platinum, palladium, iridium, ruthenium and rhodium. They may be optically sensitized by means of cyanine and merocyanine dyes.
  • the said emulsions may also comprise compounds which sensitized the emulsions by development acceleration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in U.S. Pat. Nos. 2,531,832 and 2,533,990, in United Kingdom Pat. No. 920,637, 940,051, 945,340 and 991,608 and in Belgian Pat. No. 648,710 and onium derivatives of amino-N-oxides as described in United Kingdom Pat. No. 1,121,696.
  • compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in U.S. Pat. Nos. 2,531,832 and 2,533,990, in United Kingdom Pat. No. 920,637, 940,051, 945,340 and 991,608 and in Belgian Pat. No. 648,710 and onium derivatives of amino-N-oxides as described in United Kingdom Pat. No. 1,121,696.
  • the emulsions may be stabilized with heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline-Z-thione and 1-phenyl2-tetrazoline-5-thione and compounds of the hydroxy-triazolo-pyrimidine type. They can also be stabilized with mercury compounds such as the mercury compounds described in Belgian Pat. Nos. 524,121, 677,337, 707,386 and in U.S. Pat. No. 3,179,520,
  • the light-sensitive emulsions may also comprise all other kinds of ingredients such as plasticizers, hardening agents, wetting agents, etc.
  • the emulsions can be coated on a wide variety of photographic emulsion supports.
  • Typical supports include cellulose ester film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film, and related films of resinous materials, as well as paper and glass.
  • photographic direct positive cyan images are produced by the steps of:
  • imagewise exposing a photographic element comprising a. at least one water-permeable layer which contains lightsensitive silver halide grains,
  • a color coupler in efiective contact with said silver halide grains, said coupler being capable of forming on development a dye which by treatment with a strong acidic solution can be transformed in colorless products, and
  • the strong acidic solution which causes the destruction of the non-acidresistant primary dye formed on color development at the exposed areas is an acidic solution the pH of which is preferably at least 1 i.e. an acidic solution the hydrogen ion concentration of which is preferably at least 1 i.e. an acidic solution the hydrogen ion concentration of which is preferably at least 10" gram equivalent per liter.
  • this process comprises the steps of imagewise exposing a photographic element comprising a red-sensitive, a green-sensitive and a blue-sensitive silver halide emulsion layer each of said layers containing a color coupler capable of forming on development a dye which by treatment with a strong acidic solution can be transformed into colorless products, the bluesensitive and green-sensitive layers also containing compounds capable of forming acid-resistant yellow and magenta dyes respectively by oxidative coupling with the color couplers present in the said layers and the red-sensitive layer also containing a quinolone hydrazone compound corresponding to the above general formula and capable of forming an acid-resistant cyan dye by oxidative coupling with the color coupler present in the red-sensitive layer, developing the photographic element in a color-forming developer, treating the photographic element in an oxidative bleaching bath, occasionally fixing the photographic element, treating the photographic element in a strong acidic solution containing at least one reducing agent or oxidizing
  • Example 1 To a light-sensitive silver bromoiodide emulsion containing 4.5 mole percent of silver iodide are added per 150 millimole of silver halide:
  • the emulsion After the addition of the common emulsion additives such as wetting agent, hardener and stabilizer the emulsion is coated on a support and dried, 3 5
  • the light-sensitive material is imagewise exposed to an original and then processed at 20' C. in the following baths:
  • the total processing lasts about 34 min. A positive cyan image of high density is obtained. The absorption maximum of the dye lies at 660 nm.
  • Example 2 in an analogous way as described in example I, the oxidatively coupling compound 1 of the above table is incorporated in a silver bromoiodide emulsion together with one of the anaphthylsulphamoyl or m-acylamino-N,N-diethylaniline color couplers given above.
  • Example 4 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 antihalation layer, a red-sensitive silver halide emulsion layer, a gelatin interlayer, a green-sensitive silver halide emulsion layer, a yellow filter layer, a blue-sensitive silver halide emulsion layer and a gelatin antistress layer.
  • the red-sensitive emulsion layer has the composition given in example 1.
  • the gelatin interlayer may comprise a magenta to magentared colored dyestuff as screening dye.
  • the green-sensitive emulsion layer is prepared as follows:
  • the emulsion After the addition of the usual additives such as hardeners, stabilizers and wetting agents the emulsion is coated.
  • the yellow filter layer may comprise colloidal silver or organic yellow dyes.
  • the blue-sensitive silver halide emulsion layer is prepared as follows:
  • the multilayer material formed is exposed to a colored original and processed as described in example 1.
  • a positive color image of the original is obtained having brilliant colors and correct color rendition and having a high stability on storing under various circumstances of heat, light, and humidity.
  • the yellow, magenta and cyan separation images have absorption maxima: 440 nm., 540 nm. and 660 nm. respectively.
  • FIG. 1 the absorption curves are given of the cyan dyes formed by oxidative coupling of the color coupler l of example 2, with oxidative coupling compound 1 according to the present invention (solid line curve) and with the oxidative coupling compound of preparation 7 of the above U.S. Pat. specification (dashline curve).
  • a photographic element comprising a quinolone hydrazone compound corresponding to the formula:
  • Ar stands for an aryl group
  • R stands for an alkyl group, an aryl group, an aralkyl group
  • R stands for an alkyl group
  • M stands for hydrogen or an alkali metal atom.
  • a photographic element comprising at least one water-permeable lightsensitive silver halide layer, and a color coupler in effective contact with said silver halide and with the said quinolone hydrazone compound said color cougler being capable of forming on color development a dye, w ich by treatment with a strong acidic solution can be converted into colorless products, and of forming an acid-resistant cyan dye by oxidative coupling with the said quinolone hydrazone compound.
  • a photographic element according to claim 2, wherein said element is a multilayer color element comprising three silver halide emulsion layers which are differently spectrally sensitized of which a red-sensitized silver halide emulsion layer or a non-light-sensitive colloid layer in water-permeable relationship therewith comprises a color coupler capable of forming on development a quinone-imine or azomethine dye which can be destroyed or transformed into colorless products by treatment with a strong acidic solution and a said quinolone hydrazone compound which on treatment of the color developed photographic element in an oxidizing solution oxidatively couples with said colorless color coupler to form in the nondeveloped areas a cyan dye which cannot be destroyed or transformed into colorless products by the said treatment with a strong acidic solution.
  • Process for the production of direct-positive color images which comprises the steps of imagewise exposing a photographic element according to claim 2, developing the photographic element in a color forming developer, treating the photographic element in an oxidative bleaching bath, treating the photographic element in a strong acidic solution and fixing the photographic element no later than after the said acid treatment step but not before the said color development step, thus forming colorless reaction products at the exposed areas where development occurred, and a positive color image as a result of oxidative coupling at the unexposed areas.
  • oxidative beaching bath is an alkaline bleaching bath containing potassium hexacyanoferrate (III).

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
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US8525A 1969-02-04 1970-02-04 Process for preparing color images Expired - Lifetime US3622327A (en)

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US (1) US3622327A (en, 2012)
BE (1) BE745438A (en, 2012)
DE (1) DE2005091A1 (en, 2012)
FR (1) FR2037061A6 (en, 2012)
GB (1) GB1299441A (en, 2012)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3293032A (en) * 1961-08-02 1966-12-20 Gevaert Photo Prod Nv Process for the preparation of colour images

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3293032A (en) * 1961-08-02 1966-12-20 Gevaert Photo Prod Nv Process for the preparation of colour images

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FR2037061A6 (en, 2012) 1970-12-31
GB1299441A (en) 1972-12-13
DE2005091A1 (de) 1970-09-17
BE745438A (en, 2012) 1970-08-04

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