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EP0397086A2 - Méthode pour la fabrication de matériaux photosensibles à halogénue d'argent pour photographies en couleurs - Google Patents

Méthode pour la fabrication de matériaux photosensibles à halogénue d'argent pour photographies en couleurs Download PDF

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Publication number
EP0397086A2
EP0397086A2 EP90108586A EP90108586A EP0397086A2 EP 0397086 A2 EP0397086 A2 EP 0397086A2 EP 90108586 A EP90108586 A EP 90108586A EP 90108586 A EP90108586 A EP 90108586A EP 0397086 A2 EP0397086 A2 EP 0397086A2
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EP
European Patent Office
Prior art keywords
silver halide
light sensitive
manufacturing
color photographic
photographic light
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP90108586A
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German (de)
English (en)
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EP0397086A3 (fr
Inventor
Masahiro C/O Fuji Photo Film Co. Ltd. Fukuoka
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0397086A2 publication Critical patent/EP0397086A2/fr
Publication of EP0397086A3 publication Critical patent/EP0397086A3/fr
Withdrawn legal-status Critical Current

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    • 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
    • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
    • 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
    • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function

Definitions

  • This invention concerns a method for the manu­facture of silver halide color photographic light sensi­tive materials.
  • Silver halide color photographic light sensitive materials are generally manufactured by coating at least one light sensitive silver halide emulsion layer which contains hydrophobic additives, such as couplers, and non-light sensitive hydrophilic colloid layers which contain hydrophobic photographically useful additives, such as ultraviolet absorbers, onto a support.
  • hydrophobic additives such as couplers
  • non-light sensitive hydrophilic colloid layers which contain hydrophobic photographically useful additives, such as ultraviolet absorbers
  • the manufacture of color light sensitive materials has involved first preparing a hydrophilic colloid dispersions which contains a hydrophobic photographically useful additive and then, storing it for from 3 to 100 days at a temperature about 27°C or below, remelting as small lots, mixing it with the remainder of the coating liquid, such as the silver halide emulsion, to form a coating liquid for a photographic layer of the type mentioned above, and coating it onto a support.
  • JP-A-63-296046, JP-A-63-296038 and JP-A-61-­90154 for preventing the coating irregularities and loss of photographic speed for example which arise when the coupler dispersion and the silver halide emulsion are mixed together and left to stand before coating, but the effect on photographic performance and the coated surface quality due to aging after preparing the hydrophilic colloid dispersion which contains the hydrophobic photographically useful additives is not fully elucidated.
  • JP-A as used herein signifies an "unexamined published Japanese patent application”.
  • the first object of the present invention is to provide a method for manufacturing a silver halide color photographic light sensitive materials which provide a high Dmax (high contrast), and which provide colored images which have excellent fastness after color development processing and with which, moreover, the coated surface quality is good.
  • the second object of the present invention is to provide a method for manufacturing silver halide color photosensitive materials in which problems with the coated surface quality and with the change in photographic performance due to aging after preparing the coating liquids are slight.
  • hydrophilic colloid dispersion mixing the hydrophilic colloid emulsified dispersion (hereinafter referred to hydrophilic colloid dispersion) with the remaining coating composition is conducted within 24 hours, preferably within 12 hours, more desirably within 6 hours and most desirably within 3 hours afater preparing the hydrophilic colloid dispersion of the hydrophobic photographically useful additives (hereinafter referred to hydrophobic additives).
  • the standing time is preferable as short as possible.
  • the temperature of the hydrophilic colloid dispersion during the standing time is preferably from about 6°C to 70°C, and most desirably from about 6°C to 50°C.
  • the coating of thus prepared mixture is generally conducted within 3 hours, preferably within 2 hours, more preferably within one hour and most preferably within 30 minutes.
  • the standing time is preferably as short as possible that it may be 5 minutes or less.
  • the temperature of the mixture during the standing time is preferably from about 30°C to 60°C, and more desirably from about 35°C to 50°C.
  • the hydrophobic colloid emulsified dispersion of at least one hydrophobic additive can be obtained by a conventional method which is used in preparation of silver halide color photographic materials.
  • the dispersion is prepared as follows.
  • hydrophilic colloidal aqueous solution As a dispersion medium a hydrophilic colloidal aqueous solution is used.
  • a hydrophilic colloid gelatin is advantageously used but other hydrophilic colloids can also be used alone or together with gelatin. Any gelatin can be used in the present invention. Examples of gelatin include lime-treated gelatin and acid-treated gelatin with lime-treated gelatin being preferrred.
  • the concentration of gelatin in the colloidal aqueous solution is preferably of from 10 to 50 weight%, more preferably 20 to 40 weight%.
  • the hydrophilic colloidal aqueous solution usually contains a surfactant as an emulsifying agent.
  • hydrophobic photographically useful additives examples include couplers, anti-color mixing agents, antifoggants, anti-color fading agents, anti-­staining agents, ultraviolet absorbers, and slidability improving agents.
  • additives are dispersed into a hydrophilic colloid aqueous solution as an organic solvent solution thereof.
  • concentration of the additive in a solvent is from 50 to 150 weight%, based on the weight of the solvent.
  • organic solvents those which has a high boiling point (described hereinafter in detail) can be used alone or in combination with an organic solvent having a low boiling point, such as alcohol and acetone.
  • an organic solvent having a low boiling point such as alcohol and acetone.
  • the additive When the additive is soluble to the organic solvent having a low boiling point, the additive may be added to a colloidal solution as a solution of such an organic solvent. This solvent is removed by evaporation prior to the mixing in the same manner as in conventional methods for preparation of silver halide photographic materials.
  • the high boiling point organic solvent is usually used in an amount of from 0 weight% (in the case when a low boiling point organic solvent is used alone) to 10 weight% based on the total weight of the dispersion.
  • the remaining coating composition which is mixed with the hydrophilic colloid dispersion of the hydrophobic additives is typically a silver halide emulsion in the case for coating a light sensitive silver halide emulsion layer, and in the case for coating a non-light sensitive layer it is typically an aqueous colloidal solution.
  • aqueous colloidal solution the same solution as described for the dispersion medium for the hydrophobic additives can be used.
  • the remaining coating composition preferably does not contain any hydrophobic additive, especially, the silver halide emulsion (as the remaining coating composition) preferably does not contain any hydrophobic additive.
  • Photographically useful additives other than the hydrophobic additives can be incorporated either to the hydrophilic colloid dispersion or to the remaining coating composition.
  • a sensitizing dye is incorporated.
  • non-light sensitive layer is a protective layer, an antihalation layer, and an inter-­ mediate layer (such as an ultraviolet absorbing layer, an anti-color mixing layer and an anti-irradiation layer).
  • An ultraviolet absorber is usually contained in the non-light sensitive layer, and a slidability improving agent is contained in a protective layer.
  • the amount of the hydrophilic colloid emulsified dispersion is usually from about 1 to 70 weight% based on the total weight of the coating composition obtained by mixing the dispersion with the remained coating composition.
  • the hydrophobic additive is a liquid paraffin which is used as a slidability improving agent the amount is preferably about 1 to 10 weight%, and when the hydrophobic additive is a coupler, an anti-color mixing agent, an antifoggant, an anti-color fading agent, an anti-staining agent or an ultraviolet absorber, the amount is preferably from about 10 to 60 weight%.
  • the average particle size of the hydrophobic additives in the coating liquid which are used in the present invention is preferably not more than 0.2 ⁇ m, more preferably not more than 0.15 ⁇ m, and most preferably not more than 0.1 ⁇ m.
  • the size may be as small as, for example, about 0.01 ⁇ m.
  • the average particle size of the fine particle dispersions in such a coating liquid can be measured using the well known turbidity method or using apparatus such as the Nanosizer made by the British Coal Tar Co.
  • the effect of the present invention is especially pronounced when applied to systems where cyan couplers are used among the couplers, and this is desirable.
  • the present invention is more effective in cases where dispersions of hydrophobic cyan, magenta and yellow couplers are used in systems in which high silver chloride-content emulsions (not less than 80 mol% of silver chloride) are used, and this is desirable.
  • the silver halide emulsion may be either a system wherein a silver chlorobromide emulsion is used or a system wherein a high silver chloride-­ content emulsion is used, in order to obtain a high D max (high contrast).
  • the improving effect on the light fastness of the colored image is especially pronounced in systems where a high silver chloride-content emulsion is used and processing is carried out in an essentially benzyl alcohol free color development bath.
  • the term "essentially benzyl alcohol free” signifies that there is not more than 2 ml of benzyl alcohol per liter of color development bath, and a pronounced fastness improving effect is obtained when the benzyl alcohol concentration is not more than 0.5 ml/l, and especially when the color development bath contains no benzyl alcohol at all.
  • the color photographic light sensitive materials of this present invention can be formed by coating at least one blue sensitive silver halide emulsion layer, at least one green sensitive silver halide emulsion layer and at least one red sensitive silver halide emulsion layer on a support. Normally, these layers are coated on the support in the order indicated above for a general color printing paper, but different orders can be adopted. Furthermore, they may have a infrared sensitive silver halide emulsion layer in place of at least one of the aforementioned emulsion layers.
  • Color reproduction can be achieved with these color light sensitive emulsion layers with the subtractive color method using silver halide emulsions which are sensitive to the different wavelength regions and couplers which forms dyes relating to the complementary color of the light to which the layers are sensitive, which is to say by including a color coupler which forms a yellow color in the blue sensitive layer, a color coupler which forms magenta in the green sensitive layer and a color coupler which forms cyan in the red sensitive layer.
  • the structure may take a form which does not have the above-mentioned correspondence between the light sensitive layers and the hues formed by the couplers.
  • essentially silver iodide free silver chlorobromide or silver chloride for the silver halide in the present invention is preferred.
  • the term "essentially silver iodide free” signifies that the silver iodide content is not more than 1 mol%, and preferably not more than 0.2 mol%.
  • the halogen composition in the emulsion may differ from grain to grain or it may be uniform. The nature of the grains can easily be made homogeneous when emulsions which have a halogen composition which is the same from grain to grain are used.
  • the halogen composition distribution within the grains of the silver halide emulsion may be such that the grains have a so-called uniform structure in which the composition is the same in all parts of the silver halide grain, or it may be such that the grains have a so-called laminated structure in which the core inside the silver halide grain has a different halogen composition from the shell (a single layer or a plurality of layers) which surrounds the core, or it may be such that the grains are of a structure which has parts which have a different halogen composition which are not in the form of a layer within the grains or at the grain surface (when present at the grain surface, the structure is such that the parts which have a different composition are jointed on the edge, corner, or plane of the grain) for example, and grains which have any such halogen composition distribution can be selected appropriately for use.
  • the use of either of the latter two types of grain is preferable to the use of grains which have a uniform halogen composition for obtaining higher photo­graphic speeds, and it is also preferred from the viewpoint of pressure resistance.
  • the boundaries between the parts which have different halogen compositions may be distinct boundaries, or there may be an indistinct boundary with the formation of mixed crystals due to the difference in composition, or there may be a positive continuous variation in the structure.
  • the halogen composition of these silver chloro­bromide emulsions can have any silver bromide/silver chloride ratio. This ratio can have a wide range, depending on the intended purpose, but the use of those which have a silver chloride content of at least 2 mol% are preferred.
  • high silver chloride-content emulsions which have a high silver chloride content is preferred in light sensitive materials which are suitable for rapid processing.
  • the silver chloride content of these high silver chloride-­content emulsions is preferably at least 90 mol%, and most desirably at least 95 mol%.
  • a structure which has a silver bromide local phase in the form of a layer or in some other form, as described above, within and/or at the surface of the silver halide grain is desirable for these high silver chloride-content emulsions.
  • the halogen composition of the above-mentioned local phase preferably has a silver bromide content of at least 10 mol%, and most desirably it has a silver bromide content in excess of 20 mol%.
  • This local phase can be present within the grain, or at the edge, corner, or plane of the grain, and in a preferred embodiment the local phase is grown epitaxially on the corner of the grain.
  • the use of grains which have a uniform type structure with a small halogen composition distribution within the grain is also desirable in high silver chloride-content emulsions which have a silver chloride content of at least 90 mol% for greatly suppressing the fall in sensitivity which occurs when pressure is applied to a photographic material.
  • the average grain size (where the grain size is taken to be the diameter of a circle which has an area equal to the projected area of the grain and the average grain size is taken to be the average of these values) of the silver halide grains which are included in the silver halide emulsions which are used in this present invention is preferably from 0.1 ⁇ to 2 ⁇ .
  • the size distribution of these grains is preferably a mono-dispersion of which the variation coefficient (the value obtained by dividing the standard deviation of the grain size distribution by the average grain size) is not more than 20%, and preferably not more than 15%. Blending of the above-­mentioned mono-disperse emulsions in the same layer, or lamination coating of the above-mentioned mono-disper­sions, is desirable for obtaining a wider latitude.
  • the form of the silver halide grains which are contained in a photographic emulsion may be a regular crystalline form, for example, a cubic, tetradecahedral or octahedral form, an irregular crystalline form, for example, a spherical or tabular form, or it may be a form which is a composite of these forms.
  • the emulsion may also be comprised of grains which have various crystalline forms. In the present invention, the inclusion of at least 50%, preferably at least 70%, and most desirably at least 90%, of grains which have the above-mentioned regular crystalline forms is preferred.
  • emulsions in which tabular grains of which the average aspect ratio (diameter of the calculated circle/thickness) is at least 5, and preferably at least 8, account for more than 50% of all the grains in terms of projected area is also desirable.
  • the silver chlorobromide emulsions used in the present invention can be prepared using the methods disclosed, for example, by P. Glafkides in Chimie et Physique Photographique , published by Paul Montel, 1967, by G.F. Duffin in Photographic Emulsion Chemistry , published by Focal Press, 1966, and by V.L. Zelikmann et al. in Making and Coating Photographic Emulsions , published by Focal Press, 1964. That is to say, they can be prepared using acidic.methods, neutral methods and ammonia methods for example, and a single jet method, a double jet method, or a combination of such methods, can be used for reacting the soluble silver salt with the soluble halide.
  • Various multi-valent metal ion impurities can be introduced into the silver halide emulsions which are used in the present invention during the formation or physical ripening of the emulsion grains.
  • salts of cadmium, zinc, lead, copper or thallium, or salts or complex salts of iron, ruthenium, rhodium, palladium, osmium, iridium and platinum, for example, which are group VIII elements in the Periodic Table can be used as compounds of this type.
  • group VIII elements which are group VIII elements in the Periodic Table
  • the use of the above-mentioned group VIII elements is especially desirable.
  • the amount of these compounds added varies over a wide range, depending on the intended purpose, but an amount of from 10 ⁇ 9 to 10 ⁇ 2 mol per mol of silver halide is preferred.
  • the silver halide emulsions used in this present invention are normally subjected to chemical sensitiza­tion and spectral sensitization.
  • Sulfur sensitization which is typified by the addition of unstable sulfur compounds
  • precious metal sensitization which is typified by gold sensitization
  • reduction sensitization for example, can be used individually or conjointly as chemical sensitization methods.
  • the use of the compounds disclosed from the lower right hand column on page 18 to the upper right and column on page 22 of JP-A-62-215272 for the compounds which are used for chemical sensitization is preferred.
  • Spectral sensitization is carried out with a view to rendering each emulsion layer in a photosensi­tive material of the present invention sensitive to light of the prescribed wavelength region.
  • this is preferably achieved by adding dyes (spectrally sensitizing dyes) which absorb light in the wavelength regions corresponding to the necessary spectral sensitivity.
  • dyes spectrally sensitizing dyes
  • Examples of spectrally sensitiz­ing dyes which can be used are disclosed, for example, by F.M. Harmer in Heterocyclic Compounds, Cyanine Dyes and Related Compounds , (John Wiley & Sons [New York, London], 1964). Examples of actual preferred compounds which can be used have been disclosed from the upper right hand column on page 22 to page 38 of the specification JP-A-62-215272.
  • the emulsions used in the present invention may be of the so-called surface latent image type in which the latent image is formed principally on the grain surfaces, or of the so-called internal latent image type in which the latent image is formed principally within the grains.
  • Yellow couplers, magenta couplers and cyan couplers which form yellow, magenta and cyan colors respectively on coupling with the oxidized product of a primary aromatic amine color developing agent are normally used in color photographic materials of the present invention.
  • cyan couplers, magenta couplers and yellow couplers which can be represented by the general formulae (C-I), (C-II), (M-I), (M-II) and (Y) which are indicated below is preferred in this present invention.
  • R1, R2 and R4 each represents substituted or unsubstituted aliphatic, aromatic, or heterocyclic groups
  • R3, R5 and R6 each represents hydrogen atoms, halogen atoms, aliphatic groups, aromatic groups or acylamino groups
  • R3 together with R2 may represent a group of non-­metal atoms which is required to form a 5- or 6-membered nitrogen containing ring
  • Y1 and Y2 each represents hydrogen atoms or groups which can be eliminated at the time of a coupling reaction with the oxidized product of a developing agent.
  • n represents 0 or 1.
  • R5 in general formula (C-II) is preferably an aliphatic group, for example, methyl, ethyl, propyl, butyl, pentadecyl, tert-butyl, cyclohexyl, cyclohexyl­methyl, phenylthiomethyl, dodecyloxyphenylthiomethyl, butanamidomethyl or methoxymethyl.
  • R1 in general formula (C-I) is preferably an aryl group or a heterocyclic group, and aryl groups substituted with halogen atoms, alkyl groups, alkoxy groups, aryloxy groups, acylamino groups, acyl groups, carbamoyl groups, sulfonamido groups, sulfamoyl groups, sulfonyl groups, oxycarbonyl groups and cyano groups are most desirable.
  • R2 is preferably a substituted or unsubstituted alkyl group or aryl group, and most desirably a substituted aryloxy substituted alkyl group, and R3 is preferably a hydrogen atom.
  • R4 in general formula (C-II) is preferably a substituted or unsubstituted alkyl group or aryl group, and most desirably a substituted aryloxy substituted alkyl group.
  • R5 in general formula (C-II) is preferably an alkyl group which has from 2 to 15 carbon atoms or a methyl group which has a substituent group having at least 1 carbon atom, and the preferred substituent groups are arylthio groups, alkylthio groups, acylamino groups, aryloxy groups and alkyloxy groups.
  • R5 in general formula (C-II) is most desirably an alkyl group which has from 2 to 15 carbon atoms, and alkyl groups which have from 2 to 4 carbon atoms are especially desirable.
  • R6 in general formula (C-II) is preferably a hydrogen atom or a halogen atom, and most desirably it is a chlorine atom or a fluorine atom.
  • Y1 and Y2 in general formulae (C-I) and (C-II) each preferably represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group or a sulfonamido group.
  • R7 and R9 each represents aryl groups
  • R8 represents a hydrogen atom, an aliphatic or aromatic acyl group, or an aliphatic or aromatic sulfonyl group
  • Y3 represents a hydrogen atom or a releasing group.
  • the substituent groups permitted for the aryl groups (preferably phenyl groups) represented by R7 and R9 are the same as those permitted as substituent groups for R1, and when there are two or more substituent groups these may be the same or different.
  • R8 is preferably a hydrogen atom, an aliphatic acyl group or sulfonyl group, and most desirably it is a hydrogen atom.
  • Y3 is preferably a group of the type which is eliminated at a sulfur, oxygen or nitrogen atom, and most desirably it is a sulfur atom releasing group of the type disclosed, for example, in U.S. Patent 4,351,897 or International Patent Publication WO88/04795.
  • R10 represents a hydrogen atom or a substituent group such as a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclyloxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, an ureido group, an imido group, a sulfamoylamino group, a carbamoylamino group, an alkylthio group, an arylthio group, a heterocyclylthio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, a carbamoyl group[, an acyl group, a sulf
  • Y4 represents a hydrogen atom or a releasing group such as a halogen atom, a carboxy group, or a coupling releasing group which is attached to the carbon atom located at the couling position through its oxygen, nitrogen or sulfur atom, and it is preferably a halogen atom or an arylthio group
  • Those cases where the Zb-Zc bond is a carbon-carbon double bond include cases in which this bond is part of an aromatic ring.
  • the imidazo[1,2-­b]pyrazoles disclosed in U.S. Patent 4,500,630 are preferred from the point of view of the slight yellow side absorbance and the light fastness of the colored dye, and the pyrazolo-[1,5-b][1,2,4]triazole disclosed in U.S. Patent 4,540,654 is especially desirable.
  • the use of the pyrazolotriazole couplers in which a branched alkyl group is bonded directly to the 2-, 3- or 6-position of the pyrazolotriazole ring as disclosed in JP-A-61-65245, the pyrazoloazole couplers which have a sulfonamido group within the molecule as disclosed in JP-A-61-65246, the pyrazoloazole couplers which have alkoxyphenylsulfonamido ballast groups as disclosed in JP-A-61-147254, and the pyrazolotriazole couplers which have an alkoxy group or an aryloxy group in the 6-position as disclosed in European Patents (laid open) 226,849 and 294,785 is also desirable.
  • R11 represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group
  • R12 represents a hydrogen atom, a halogen atom or an alkoxy group.
  • A represents -NHCOR13, -NHSO2- R13, -SO2NHR13, -COOR13 or where R13 and R14 each represents an alkyl, an aryl group or an acyl group.
  • Y5 represents a releasing group.
  • the substituent groups for R12, R13 and R14 are the same as the substituent groups permitted for R1, and the releasing group Y5 is preferably a group of the type with which elimination occurs at an oxygen atom or a nitrogen atom, and it is most desirably of the nitrogen atom releasing type.
  • Couplers which can be represented by general formulae (C-I), (C-II), (M-I), (M-II) and (Y) are indicated below.
  • the couplers represented by the above-mentioned general formulae (C-I) to (Y) are normally include in the silver halide emulsion layers which form the light sensitive layer in an amount of from 0.1 to 1.0 mol, and preferably of from 0.1 to 0.5 mol, per mol of silver halide.
  • couplers in hydrophilic colloids.
  • they can be added by means of oil in water dispersion method using the oil protection method where, after being dissolved in a solvent, the solution is emulsified and dispersed in an aqueous gelatin solution which contains a surfactant.
  • water or an aqueous gelatin solution can be added to a coupler solution which contains a surfactant to form oil in water dispersion by phase reversal.
  • the coupler dispersion can be mixed with photographic emulsion after removing low boiling point organic solvents by distillation, noodle washing or ultrafiltration for example.
  • W1, W2 and W3 each represents a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group
  • W4 represents W1, OW1 or S-W1
  • n represents an integer of from 1 to 5, and when n is 2 or more the W4 groups may be the same or different.
  • W1 and W2 in general formula (E) may form a condensed ring.
  • Water immiscible compounds of having melting point of 100°C or lower and of boiling point or 140°C or higher other than those of general formulae (A) to (E) can also be used as high boiling point organic solvents in the present invention provided that they are good solvents for the coupler.
  • the melting point of the high boiling point organic solvent is preferably not more than 80°C.
  • the boiling point of the high boiling point organic solvent is preferably at least 160°C, and most desirably at least 170°C.
  • couplers can be loaded onto a loadable latex polymer (for example, U.S. Patent 4,203,716) in the presence or absence of the aforemen­tioned high boiling point organic solvents, or they can be dissolved in a water insoluble but organic solvent soluble polymer and the solution can be emulsified and dispersed in an aqueous hydrophilic colloid solution.
  • a loadable latex polymer for example, U.S. Patent 4,203,716
  • these couplers can be loaded onto a loadable latex polymer (for example, U.S. Patent 4,203,716) in the presence or absence of the aforemen­tioned high boiling point organic solvents, or they can be dissolved in a water insoluble but organic solvent soluble polymer and the solution can be emulsified and dispersed in an aqueous hydrophilic colloid solution.
  • the hydrophobic additive other than couplers is contained in the silver halide emulsion of the present invention in an amount of from 1x10 ⁇ 4 to 1.0 mol per mol of silver halide, and in a non-light sensitive layer of the present invention in an amount of from 1x10 ⁇ 4 to 1.0 g/m2.
  • Light sensitive materials which is prepared using the present invention may contain hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives and ascorbic acid derivatives, for example, as anti-color fogging agents.
  • anti-color fading agents can be used in light sensitive materials of the present invention. That is to say, hydroquinones, 6-hydroxychromans, 5-­hydroxycoumarans, spirochromans, p-alkoxyphenols, bisphenols such as hindered phenols, gallic acid deriva­tives, methylenedioxybenzenes, aminophenols, hindered amines, and the ether and ester derivatives in which the phenolic hydroxyl groups of these compounds is silylated or alkylated, are typical organic anti-color mixing agents which can be used for cyan, magenta and/or yellow images.
  • metal complexes as typified by (bis-salicylaldoximato)nickel and (bis-N,N-dialkyldi­thiocarbamato)nickel complexes, for example, can also be used for this purpose.
  • hydroquinones are disclosed, for example, in U.S. Patents 2,360,290, 2,418,613, 2,700,453, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944 and 4,430,425, British Patent 1,363,921, and U.S. Patents 2,710,801 and 2,816,028, 6-hydroxychromans, 5-­hydroxychromans and spirochromans are disclosed, for example, in U.S. Patents 3,432,300, 3,573,050, 3,574,627, 3,698,909 and 3,764,337, and JP-A-52-152225, spiroindanes are disclosed in U.S.
  • Patent 4,360,589, p-­alkoxyphenols are disclosed, for example, in U.S. Patent 2,735,765, British Patent 2,066,975, JP-A-59-10539 and JP-B-57-19765, hindered phenols are disclosed, for example, in U.S. Patent 3,700,455, JP-A-52-72224, U.S. Patent 4,228,235, and JP-B-52-6623, gallic acid derivatives, methylenedioxybenzenes and aminophenols are disclosed, for example, in U.S. Patents 3,457,079 and 4,332,886, and JP-B-56-21144, hindered amines are disclosed, for example, in U.S.
  • Patents 3,336,135 and 4,268,593, British Patents 1,326,889, 1,354,313 and 1,410,846, JP-B-51 1420, JP-A-58-114036, JP-A-59-53846 and JP-A-59-78344, and metal complexes have been disclosed, for example, U.S. Patents 4,050,938 and 4,241,155, and British Patent 2,027,731(A).
  • JP-B as used herein signifies an "examined Japanese patent publication”.
  • the intended purpose can be attained by adding these compounds to the photosensitive layer after co-emulsification with the corresponding color coupler, usually in an amount of from 5 to 100 wt% with respect to the coupler.
  • the inclusion of ultraviolet absorbers in the cyan color forming layer and in the layers on both sides adjacent thereto is effective for preventing deterioration of the cyan dye image by heat and, more especially, by light.
  • benzotriazole compounds substituted with aryl groups for example, those disclosed in U.S. Patent 3,533,794), 4-thiazolidone compounds (for example, those disclosed in U.S. Patents 3,314,794 and 3,352,681), benzophenone compounds (for example, those disclosed in JP-A-46-2784), cinnamic acid ester compounds (for example, those disclosed in U.S. Patents 3,705,805 and 3,707,395), butadiene compounds (for example, those disclosed in U.S. Patent 4,045,229), or benzoxidol compounds (for example, those disclosed in U.S. Patents 3,406,070, 3,677,672 and 4,271,307) can be used as ultraviolet absorbers.
  • Ultraviolet absorbing couplers for example, ⁇ -naphthol based cyan dye forming couplers
  • ultraviolet absorbing polymers for example, can also be used for this purpose. These ultraviolet absorbers may be mordanted in a specified layer.
  • compounds (F) which chemically bond with the aromatic amine developing agents remaining after color development processing and form compounds which are chemically inert and essentially colorless and/or compounds (G) which chemically bond with the oxidized product of the aromatic amine color developing agents remaining after color development processing and form compounds which are chemically inert and essentially colorless, either in combination or individually, is desirable for preventing the occurrence of staining and other side effects on storage due to colored dye formation resulting from reactions between couplers and color developing agents or oxidized products thereof which remain in the film after processing for example.
  • the compounds themselves are unstable if k2 has a value above this range, and they will react with gelatin or water and be decomposed. If, on the other hand, the value of k2 is below this range, reaction with the residual aromatic amine developing agent is slow and consequently it is not possible to prevent the occurrence of side effects due to the residual aromatic amine developing agent.
  • R1 and R2 each represent an aliphatic group, an aromatic group or a heterocyclic group.
  • n 1 or 0.
  • A represents a group which reacts with an aromatic amine developing agent and forms a chemical bond
  • X represents a group which is eliminated by reaction with an aromatic amine developing agent.
  • B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group
  • Y represents a group which promotes the addition of an aromatic amine developing agent to the compound of general formula (FII).
  • R1 and X, and Y and R2 or B can be joined together to form a cyclic structure.
  • R in this formula represents an aliphatic group, an aromatic group or a heterocyclic group.
  • Z represents a nucleophilic group or a group which breaks down in the light sensitive material and releases a nucleophilic group.
  • the compounds represented by the general formula (GI) are preferably compounds in which Z is a group of which the Pearson nucleophilicity n CH3I value (R.G. Pearson et al., J. Am. Chem. Soc. , 90 , 319 (1968)) is at least 5, or a group derived therefrom.
  • Water soluble dyes and dyes which become water soluble as a result of photographic processing may be included as filter dyes, or for antiirradiation or anti­halation or other purposes, in the hydrophilic colloid layers of light sensitive materials which is prepared using the present invention.
  • Dyes of this type include oxonol dyes, hemi-oxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.
  • the oxonol dyes, hemi-­ oxonol dyes and merocyanine dyes are useful among these dyes.
  • Gelatin is useful as a binding agent or protective colloid which can be used in the emulsion layers of light sensitive materials of the present invention, but other hydrophilic colloids, either alone or in combination with gelatin, can be used for this purpose.
  • the gelatin used in the invention may be a lime treated gelatin, or it may be acid treated gelatin. Details of the preparation of gelatins have been disclosed by Arthur Weise in The Macromolecular Chemistry of Gelatin (published by Academic Press, 1964).
  • the transparent films such as cellulose nitrate films and poly(ethylene terephthalate) films, and reflective supports normally used in photographic light sensitive materials can be used as the supports which are used in thfe present invention.
  • the use of reflec­tive supports is preferred in view of the aims of the invention.
  • the “reflective supports” used in this present invention are supports which have a high reflectivity and make the dye image which is formed in the silver halide emulsion layer clear, and they include supports which are covered with a hydrophobic resin containing a dispersion of light reflecting material, such as titanium oxide, zinc oxide, calcium carbonate or calcium sulfate, and supports comprised of a hydrophobic resin in which contains a dispersion of a light reflecting substance.
  • Such supports include baryta paper, polyethylene coated paper, polypropylene based synthetic paper and transparent supports, such as glass plates, polyester films such as poly(ethylene tere­phthalate), cellulose triacetate and cellulose nitrate films, polyamide films, polycarbonate films, polystyrene films and vinyl chloride resins, on which a reflective layer is provided or in which a reflective substance is used conjointly.
  • Supports which have a metal surface with mirror like reflection properties or a type secondary diffuse reflective metal surface can be used as reflective type supports.
  • the spectral reflectance in the visible wavelength region of the metal surface is at least 0.5, and diffuse reflection properties can be attained by roughening the metal surface, or by using a metal powder.
  • Aluminum, tin, silver, magnesium or their alloys are used, for example, as the metal, and the surface may be a metal sheet, a metal foil or a thin metal layer obtained by rolling, vapor deposition or plating for example. From among these materials, those obtained by vapor depositing metal on some other substrate are preferred. It is preferrred to provide a water insoluble resin layer, preferably a thermoplastic resin layer over the metal surface.
  • An anti-static layer may also be provided on the opposite side to the metal surface side of the support in the preesnt invention. Details of such supports is disclosed, for example, in JP-A-61-210346, JP-A-63-24247, JP-A-63-24251 and JP A-63-24255.
  • the blue sensitive sensitizing dyes indicated below were added in an amount of 2.0 ⁇ 10 ⁇ 4 mol per mol of silver for the large size emulsion and 2.5 ⁇ 10 ⁇ 4 mol per mol of silver halide for the small size emulsion to a silver chlorobromide emulsion (a 3:7 (mol ratio) mixture; cubic; average grain size: 0.88 ⁇ m and 0.70 ⁇ m; variation coefficients of the grain size distributions: 0.08 and 0.10; which contained locally 0.2 mol% of silver bromide on the grain surfaces), and sulfur sensitization was carried out.
  • a silver chlorobromide emulsion a 3:7 (mol ratio) mixture; cubic; average grain size: 0.88 ⁇ m and 0.70 ⁇ m; variation coefficients of the grain size distributions: 0.08 and 0.10; which contained locally 0.2 mol% of silver bromide on the grain surfaces
  • the afore­mentioned emulsified dispersion was mixed under the conditions indicated below with the emulsion which was prepared in the way described above to provide the coating liquids (a), (b), (c) and (d) indicated below.
  • Coating Liquid Storage Time of the Emulsified Dispersion Before Preparing the Coating Liquid Storage Temp. of the Emulsified Dispersion Remarks (a) 6 hrs 35°C Invention (b) 24 hrs 35°C " (c) 48 hrs 35°C Comp. Ex. (d) 72 hrs 35°C "
  • 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent.
  • the following dyes were used as the spectrally sensitizing dyes: (2.0 ⁇ 10 ⁇ 4 mol per mol of silver halide in the large size emulsion, and 2.5 ⁇ 10 ⁇ 4 mol per mol of silver halide in the small size emulsion)
  • 1-(5-methylureidophenyl)-5-­mercaptotetrazole was added in an amount of 8.5 ⁇ 10 ⁇ 5 mol per mol of silver halide.
  • Second Layer Blue Sensitive Layer The aforementioned silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 Second Layer : Protective Layer Gelatin 1.33 Acrylic modified copolymer of poly(vinyl alcohol) (17% modification) 0.17 Liquid paraffin 0.03
  • each sample was subjected to a gradation exposure using a sensitometer (FWH model, made by Fuji Photo Film Co., Ltd. light source color temperature 3200°K).
  • the exposure at this time was 250 CMS with an exposure time of 0.1 second.
  • the exposed samples were color developed using a paper processor in accordance with the processing operations indicated below.
  • Procession Operation Temperature Time Color Development 35°C 45 seconds Bleach-fixing 30-35°C 45 seconds Rinse (1) 30-35°C 20 seconds Rinse (2) 30-35°C 20 seconds Rinse (3) 30-35°C 20 seconds Drying 70-80°C 60 seconds (Three tank counter-flow system from Rinse (3) to Rinse (1)).
  • each of the processing baths is indicated below.
  • Ethyl acetate (27.2 ml) and 28.7 grams of solvent (Solv-2) were added to 14.14 grams of magenta coupler (EXM), 8.84 grams of color image stabilizer (Cpd-3), 1.33 grams of color image stabilizer (Cpd-8), 0.44 grams of color image stabilizer (Cpd-4) and 1.77 grams of color image stabilizer (Cpd-9) and the solution was emulsified and dispersed in 200 ml of 10% aqueous gelatin solution which contained 5.5 ml of 10% sodium dodecylbenzenesulfonate. The particle size immediately after emulsification was 0.15 ⁇ m.
  • the green sensitive sensitizing dyes indicated below were added to a silver chloride emulsion (a 1:3 (silver mol ratio) mixture of cubic silver halide grain emulsions of average grain size 0.55 ⁇ m and 0.39 ⁇ m, of which the variation coefficients of the grain size distributions were 0.10 and 0.08, respectively, which contained locally 0.8 mol% of silver bromide on the grain surfaces), and sulfur sensitization was carried out.
  • the aforementioned emulsified dispersion was mixed under the conditions indicated below with the emulsion which was prepared in the way described above to provide the coating liquids 2-(a), 2-(b), 2-(c) and 2-(d) indicated below.
  • 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent.
  • the following dyes were used for the spectrally sensitizing dyes: (4.0 ⁇ 10 ⁇ 4 per mol of silver halide in the large size emulsion, 5.6 ⁇ 10 ⁇ 4 mol per mol of silver halide in the small size emulsion) and: (7.0 ⁇ 10 ⁇ 5 mol per mol of silver halide in the large size emulsion, and 1.0 ⁇ 10 ⁇ 5 mol per mol of silver halide in the small size emulsion)
  • 1-(5-methylureidophenyl)-5-­mercaptotetrazole was added in an amount of 7.7 ⁇ 10 ⁇ 4 mol per mol of silver halide, respectively.
  • Second Layer Blue Sensitive Layer
  • Second Layer Protective Layer Same as in Example 1
  • the red sensitive sensitizing dye indicated below was added in an amount of 0.9 ⁇ 10 ⁇ 4 mol of per mol of silver for the large size emulsion and 1.1 ⁇ 10 ⁇ 4 mol per mol of silver halide for the small size emulsion to a silver chlorobromide emulsion (a 1:4 (silver mol ratio) mixture of cubic silver halide grain emulsions of average grain size 0.58 ⁇ m and 0.45 ⁇ m, of which the variation coefficients of the grain size distributions were 0.09 and 0.11, respectively, and which contained locally 0.6 mol% of silver bromide on the grain surfaces), and sulfur sensitization was carried out.
  • a silver chlorobromide emulsion a 1:4 (silver mol ratio) mixture of cubic silver halide grain emulsions of average grain size 0.58 ⁇ m and 0.45 ⁇ m, of which the variation coefficients of the grain size distributions were 0.09 and 0.11, respectively, and which contained locally 0.6 mol% of silver
  • 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent.
  • the following dyes were used for the spectrally sensitizing dyes: (0.9 ⁇ 10 ⁇ 4 mol per mol of silver halide in the large size emulsion, 1.1 ⁇ 10 ⁇ 4 mol per mol of silver halide in the small size emulsion)
  • the compound indicated below was added in an amount of 2.6 ⁇ 10 ⁇ 3 mol per mol of silver halide.
  • 1-(5-methylureidophenyl)-5-­mercaptotetrazole was added in an amount of 2.5 ⁇ 10 ⁇ 4 mol per mol of silver halide, respectively.
  • Second Layer Protective Layer Same as in Example 1
  • This emulsified dispersion was mixed with 15% aqueous gelatin solution to provide the coating liquids 4-(a), 4-(b), 4-(c) and 4-(d).
  • coating liquids the coating liquid (a) described in Example 1 as an under-layer and the protective layer coating liquid described in Example 1 as an over-layer were coated onto paper supports which had been laminated on both sides with polyethylene to obtain single layer color printing paper samples 401, 402, 403 and 404, respectively.
  • the average standing times of the coating liquids were 3 hours.
  • 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent.
  • 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent in each layer.
  • the dyes indicated below were added to the emulsion layers for anti-irradiation purposes.
  • composition of each layer was as indicated below.
  • the numerical values indicate coated weights (g/m2).
  • the coated weights of silver halide emulsion are indicated as calculated coated silver weights.
  • Support Polyethylene Laminated Paper White pigment (TiO2) in the polyethylene on the first layer side]
  • First Layer Blue Sensitive Layer
  • Second Layer Anti-color Mixing Layer Gelatin 0.99 Anti-color mixing agent (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third Layer : Green Sensitive Layer
  • each sample was subjected to a gradation exposure using a sensitometer (FWH model, made by the Fuji Photo Film Co., Ltd. light source color temperature 3200°K) with sensitometric tri-color (blue, green and red) separation filters.
  • the exposure at this time was 250 CMS with an exposure time of 0.1 second.
  • Color photographic photosensitive materials which are manufactured in accordance with the present invention have a high photographic speed and a high maximum density, and they also provide color photographs which have excellent fastness. Furthermore, the invention is also effective in that staining in non-­colored parts is suppressed. Furthermore, coating troubles can be prevented by the application of this present invention.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Colloid Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19900108586 1989-05-10 1990-05-07 Méthode pour la fabrication de matériaux photosensibles à halogénue d'argent pour photographies en couleurs Withdrawn EP0397086A3 (fr)

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JP11683589A JPH02294634A (ja) 1989-05-10 1989-05-10 ハロゲン化銀カラー写真感光材料の製造方法
JP116835/89 1989-05-10

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993003420A1 (fr) * 1991-07-29 1993-02-18 Eastman Kodak Company Procede de preparation de dispersions de copulants

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JPS55129136A (en) * 1979-03-27 1980-10-06 Fuji Photo Film Co Ltd Emulsifying method
JPS6190154A (ja) * 1984-10-10 1986-05-08 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の製造方法
JPS6232459A (ja) * 1985-08-05 1987-02-12 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
JP2542852B2 (ja) * 1987-02-23 1996-10-09 富士写真フイルム株式会社 ハロゲン化銀カラ−写真感光材料
JPS63296038A (ja) * 1987-05-28 1988-12-02 Konica Corp ハロゲン化銀カラ−写真感光材料
JPS63307448A (ja) * 1987-06-10 1988-12-15 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993003420A1 (fr) * 1991-07-29 1993-02-18 Eastman Kodak Company Procede de preparation de dispersions de copulants
US5380628A (en) * 1991-07-29 1995-01-10 Eastman Kodak Company Method of preparing coupler dispersions

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