EP0459331A1 - Matériau photographique couleur à l'halogénure d'argent sensible à la lumière - Google Patents

Matériau photographique couleur à l'halogénure d'argent sensible à la lumière Download PDF

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Publication number
EP0459331A1
EP0459331A1 EP91108545A EP91108545A EP0459331A1 EP 0459331 A1 EP0459331 A1 EP 0459331A1 EP 91108545 A EP91108545 A EP 91108545A EP 91108545 A EP91108545 A EP 91108545A EP 0459331 A1 EP0459331 A1 EP 0459331A1
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EP
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Prior art keywords
group
silver halide
formula
hydrogen atom
coupler
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EP91108545A
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German (de)
English (en)
Inventor
Keiichi Konica Corporation Hoshino
Susumu Konica Corporation Ohkawachi
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0459331A1 publication Critical patent/EP0459331A1/fr
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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
    • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element

Definitions

  • the present invention relates to a color photographic light-sensitive material improved in color tone, particularly to a silver halide color photographic light-sensitive material used in making a color proof from plural black-and-white dot images obtained by color separation and image conversion in the color photomechanical process.
  • the overlay method is very simple and low in manufacturing costs, and has an advantage that preparations for color proofing can be made by simply laying four color film sheets, the subtractive three primary colors and black, one over another; but overlaying of such film sheets yields gloss which causes a disadvantage of giving a texture different from that of printed matter.
  • the surprint method is to overlay colored images one over another on a support.
  • techniques to obtain colored images utilizing tackiness of photopolymerizable materials are disclosed in U.S. Patent Nos. 3,582,327, 3,607,264 and 3,620,726.
  • Japanese Patent O.P.I. Publication No. 97l40/l984 discloses a method to form colored images on a support by transfer, in which colored photosensitive sheets are used to expose corresponding color separation films and images obtained by development are transferred on a support.
  • This method has an advantage of providing a color proof having a tone similar to that in printed matter, because a colorant used in an printing ink can be employed as a toner and colorant for the colored sheet to form these images.
  • the color proof prepared by this method has been found to have a defect of causing a large variation in color tone of dots when dots are small; therefore, it cannot properly perform the function as a color proof.
  • the object of the present invention is to provide a silver halide color photographic light-sensitive material used to prepare a color proof from plural black-and-white dot images obtained by color separation and dot image conversion, which is capable of reproducing dots in good state and giving a color tone approximate to that of a printing ink.
  • the silver halide color photographic light-sensitive material of the invention has, on a support, having thereon a silver halide emulsion layer containing a magenta coupler represented by the following Formula M-I and a yellow coupler, and the silver halide emulsion layer and/or a layer adjacent thereto contains at a compound represented by the following Formula I .
  • Z represents a group of atoms necessary to form a nitrogen-containing heterocyclic ring, which may have a substituent.
  • X represents a hydrogen atom or a substituent capable of being split off upon reaction with an oxidized product of a color developing agent.
  • R represents a hydrogen atom or a substituent.
  • R l and R2 independently represent a hydrogen atom or an alkyl, alkoxy, alkylthio or alkylamide group each of which has l to 8 carbon atoms.
  • R3 represents a hydrogen atom or an alkyl group having carbon atoms of l to ll. The total number of carbon atoms in R l , R2 and R3 are 8 to 22.
  • magenta dye forming couplers contained in a magenta dye image forming layer of the silver halide color photographic light-sensitive material are those pyrazoloazole couplers which are represented by the following Formula M-I .
  • Z represents a group of atoms necessary to form a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent.
  • X represents a hydrogen atom or a group capable of being split off upon reaction with an oxidized product of a color developing agent.
  • R represents a hydrogen atom or a substituent.
  • R is not particularly limited, but typical examples thereof include an alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl groups.
  • halogen atoms a cycloalkenyl, alkynyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl and heterocyclic thio groups; and spiro residues and bridged hydrocarbon residues.
  • the alkyl group represented by R is preferably one having l to 32 carbon atoms and may be a straight or branched chain.
  • the aryl group represented by R is preferably a phenyl group.
  • Examples of the acylamino group represented by R include alkylcarbonylamino and arylcarbonylamino groups.
  • Examples of the sulfonamide group represented by R are alkylsulfonylamino and arylsulfonylamino groups.
  • Examples of the alkyl and aryl components in the alkylthio and arylthio groups represented by R are the alkyl and aryl groups each represented by R.
  • the alkenyl group represented by R is preferably one having 2 to 32 carbon atoms; the cycloalkyl group represented by R is preferably one having 3 to l2, particularly 5 to 7 carbon atoms; and the alkenyl group may be of straight or branched chain.
  • the cycloalkenyl group represented by R is preferably one having 3 to l2 carbon atoms, more preferably 5 to 7 carbon atoms.
  • Examples of the sulfonyl group represented by R include alkylsulfonyl and arylsulfonyl groups.
  • sulfinyl group examples include alkylsulfinyl and arylsulfinyl groups.
  • Examples of the phosphonyl group include alkylphosphonyl, alkoxyphosphonyl aryloxyphosphonyl and arylphosphonyl groups.
  • acyl group examples include alkylcarbonyl and arylcarbonyl groups.
  • carbamoyl group examples include alkylcarbamoyl and arylcarbamoyl groups.
  • sulfamoyl group examples include alkylsulfamoyl and arylsulfamoyl groups.
  • acyloxy group examples include alkylcarbonyloxy and arylcarbonyloxy groups.
  • carbamoyloxy group examples include alkylcarbamoyloxy and arylcarbamoyloxy groups.
  • ureido group examples include alkylureido and arylureido groups.
  • sulfamoylamino group examples include alkylsulfamoylamino and arylsulfamoylamino groups.
  • the heterocyclic group is preferably a five- to seven-membered one, and examples thereof include 2-furil, 2-thienyl, 2-pyrimidinyl and 2-benzothiazolyl groups.
  • the heterocyclic oxy group is preferably one having a five- to seven-membered heterocycle, and examples thereof include 3,4,5,6-tetrahydropyranyl-2-oxy and l-phenyltetrazole-5-oxy groups.
  • the heterocyclic thio group is preferably one having a five- to seven-membered heterocycle, and examples thereof include 2-pyridylthio, 2-benzothiazolylthio and 2,4-diphenoxy-l,3,5-triazole-6-thio groups.
  • siloxy group examples include trimethylsiloxy, triethylsiloxy and dimethylbutylsiloxy groups.
  • imido group examples include succinimido, 3-heptadecyl succinimido, phthalimido and glutarimido groups.
  • Examples of the spiro residue include [3.3]heptane-l-yl.
  • bridged hydrocarbon residue examples include bicyclo[2,2,l]heptane-l-yl, tricyclo[3,3,l,l 3,7 ]decane-l-yl and 7,7-dimethyl-bicyclo[2,2,l]heptane-l-yl.
  • Examples of the substituent that is represented by X and is capable of being split off upon reaction with an oxidation product of a color developing agent include halogen atoms, e.g., chlorine, bromine and fluorine atoms; alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, N-atom bonded nitrogen-containing heterocycle, alkyloxycarbonylamino, aryloxycarbonylamino and carboxyl groups; and where R l ' is the same as the above R, Z' is the same as the above Z; and R2' and R3' are independently a hydrogen atom, or an aryl, alkyl or heterocycl
  • halogen atom especially a chlorine atom.
  • nitrogen-containing heterocycle formed by Z or Z' include pyrazole, imidazole, triazole and tetrazole rings. The substituent which any of these rings may have is the same as that defined for R.
  • Couplers represented by Formula M-I are more specifically expressed by the following Formuras M-II to M-VII :
  • R l to R8 and X are the same as those defined for R and X previously.
  • R l , X and Z l are the same as those defined for R, X and Z previously.
  • magenta couplers represented by Formulas M-II to M-VII the particularly preferred are those represented by Formula M-II or Formula III.
  • R in Formula M-I or R l in Formulas M-II to M-VIII meet the following requisite l; the more preferred is that they meet the following requisites 1; and the most preferred is that they meet the following requisites 1 and 2.
  • R9, R l0 and R ll are the same as those defined for R previously; two of these R9, R l0 and R ll , for example, R9 and R l0 , may form a saturated or unsaturated ring such as cycloalkane, cycloalkene or heterocycle; and the rings may link with R ll to form a bridged hydrocarbon residue.
  • R9 to R ll be alkyl groups, or that (ii) one of R9 to R ll , for example, R ll be a hydrogen atom and the other two, namely R9 and R l0 , link with each other to form a cycloalkyl residue in conjunction with the root carbon atom.
  • R9 to R ll be alkyl groups, while the other one be a hydrogen atom or an alkyl group.
  • R l represents an alkylene group
  • R2 represents an alkyl, cycloalkyl or aryl group.
  • the alkylene group represented by R l possesses a straight chain portion having preferably 2 or more carbon atoms, more preferably 3 to 6 carbon atoms, and may be of either straight or branched structure.
  • the cycloalkyl group represented by R2 is preferably a five- to six-membered one.
  • R in Formula M-I or R l in Formulas M-II to M-VIII meet the following requisite l; it is more preferable that they meet the following requisites l and 2.
  • R l2 is the same as that defined for R previously.
  • R l2 is preferably a halogen atom or an alkyl group.
  • couplers can be synthesized by referring to Journal of the Chemical Society, Perkin I (l977), pp. 2047-2052; U.S. Patent No. 3,725,067; and Japanese Patent O.P.I. Publication Nos. 99437/l984, 42045/l983, l62548/l984, l7l956/l984, 33552/l985, 43659/l985, l72982/l985 and l90779/l985.
  • the couplers of the invention are normally used in an amount of l X l0 ⁇ 3 mol to l mol, preferably l X l0 ⁇ 2 mol to 8 X l0 -l mol, per mol of silver halide.
  • couplers may be used in combination with other types of magenta couplers.
  • preferred yellow couplers which is to be contained in the silver halide emulsion layer together with the magenta coupler are those couplers represented by the following Formula Y-I .
  • Particularly preferred yellow couplers among those represented by Formula Y-I are yellow couplers having a pKa value at most 3 lower than the pKa value of said magenta coupler.
  • R l represents a halogen atom or an alkoxy group
  • R2 represents a hydrogen or halogen atom, or an alkoxy group which may have a substituent
  • R3 represents an acylamino, alkoxycarbonyl, alkylsulfamoyl, arylsulfamoyl, arylsulfonamido, alkylureido, arylureido, succinimido, alkoxy or aryloxy group, each of which may have a substituent
  • Z2 represents a hydrogen atom, or a monovalent organic group or halogen atom each capable of being split off upon reaction with an oxidation product of a color developing agent.
  • yellow coupler used in the invention are as follows:
  • the ratio of the content of the magenta coupler to that of the yellow coupler may be determined so as to have the spectral absorption of color images obtained by color developing of said magenta image forming layer approximate to the spectral absorption of printed images of a magenta printing ink.
  • an appropriate value of the ratio is normally within a range of 0.02 mol to 0.5 mol of the yellow coupler per l mol of the magenta coupler.
  • the yellow coupler contained in a yellow image forming layer of the silver halide color photographic light-sensitive material of the invention the yellow coupler represented by the above Formula Y-I is also preferably used.
  • cyan dye image forming couplers of phenol type or naphthol type as a coupler to be contained in a cyan image forming layer.
  • couplers represented by the following Formula C-I or C-II are preferred.
  • R l represents an aryl, cycloalkyl or heterocyclic group.
  • R2 represents an alkyl or phenyl group each of which may have a substituent.
  • R3 represents a hydrogen atom, halogen atom, alkyl group or alkoxy group which may have a substituent.
  • Z l represents a hydrogen atom or a group capable of being split off upon reaction with an oxidized product of an aromatic primary amine color developing agent.
  • R4 represents an alkyl group such as methyl, ethyl, propyl, butyl, nonyl.
  • R5 represents an alkyl group such as methyl, ethyl.
  • R6 represents a hydrogen atom, halogen atom such as fluorine, chlorine, bromine or alkyl group such as methyl, ethyl.
  • Z2 represents a hydrogen atom or a group capable of being split off upon reaction with an oxidized product of an aromatic primary amine color developing agent.
  • the coupler used in the invention may be used normally in each silver halide emulsion layer in an amount of l X l0 ⁇ 3 mol to l mol, preferably l X l0 ⁇ 2 mol to 8 X l0 -l mol, per mol of silver halide.
  • the coupler is dissolved in a high boiling organic solvent having a boiling point of l50°C or more, jointly using a low boiling or water-soluble organic solvent when necessary, after dispersing the solution in a hydrophilic binder such as gelatin aqueous solution with an aid of surfactants, and then the dispersion is added to an objective hydrophilic colloidal layer.
  • a hydrophilic binder such as gelatin aqueous solution with an aid of surfactants
  • a process to remove the low boiling organic solvent may be provided after or concurrently with dispersing process.
  • the ratio of the high boiling organic solvent to the low boiling organic solvent is normally l:0.l to l:50, and preferably l:l to l:20.
  • the high boiling solvent used in the invention may be any of compounds having a dielectric constant of 6.0 or less.
  • the lower limit of the dielectric constant is not particularly provided, but it is preferably l.9 or more.
  • Preferable solvents are esters such as phthalates and phosphates, organic acid amides, ketones and hydrocarbons, each of which have a dielectric constant of 6.0 or less. Of these compounds, phthalates and phosphates are particularly preferred.
  • R l and R2 independently represent a hydrogen atom, or a group having 8 or less carbon atoms such as alkyl group such as methyl, ethyl, t-butyl, sec-hexyl, t-octyl, alkoxy group such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, alkylthio group such as methylthio, butylthio, octylthio and alkylamido group such as methaneamido, propaneamido, 2-ethylpentanoylamido; and R3 represents a hydrogen atom or alkyl group having carbon atoms of ll or less such as methyl, n-propyl, iso-propyl, heptyl, undecyl, l-ethylpentyl.
  • the total number of carbon atoms in R l , R2 and R3 is 8 to 22.
  • R l and R2 are preferably an alkyl group having 6 or less carbon atoms, respectively.
  • R3 is preferably an alkyl group having 7 or less carbon atoms. The total number of carbon atoms in R l , R2 and R3 is 8 to l7.
  • Typical examples of the compound represented by Formula I are as follows.
  • the addition amount of the compound represented by Formula [I] is l X l0 ⁇ 8 mol/m2 to l X l0 ⁇ 2 mol/m2, preferably l X l0 ⁇ 7 mol/m2 to l X l0 ⁇ 3 mol/m2, more preferably l X l0 ⁇ 6 mol/m2 to l X l0 ⁇ 4 mol/m2.
  • the compound is preferably added in an emulsion layer and/or a layer adjacent thereto.
  • R4 and R5 independently represent a hydrogen atom, or an alkyl, alkoxy, alkylthio or alkylamide group, each of which have 8 or less carbon atoms.
  • the silver halide emulsion used in the invention may employ any of silver halides used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride.
  • the construction of silver halide grains may be uniform from inner part to outer part of the grains, or the construction may be different from outer part to inner part. Further, when the composition of the grains are different from outer part to inner part, the composition may change either continuously or discontinuously.
  • the grain size of silver halide grains is not particularly limited. But in view of rapid processability, sensitivity and other photographic properties, it is preferably 0.2 to l.6 ⁇ m, more preferably 0.25 to l.2 ⁇ m.
  • the grain size distribution of silver halide grains may be of either monodisperse system or polydisperse system.
  • the silver halide emulsion used in the invention may be prepared by any of the acid method, neutral method and ammonical method. Said grains may be grown in one step, or may be grown from seed grains prepared beforehand. The method of preparing seed grains may be the same with, or different from, the method of growing seed grains.
  • a soluble silver salt with a soluble halogen salt there may be employed any of the single jet method, reverse jet method, double jet method and combination thereof.
  • pAg-controlled double jet method described in Japanese Patent O.P.I. Publication No. 4852l/l979 as a version of the double jet method.
  • a halogenated solvent such as thioether may be used.
  • the silver halide grains used in the invention may be of any form. They may be composed of grains having a uniform form, or may be a mixture of grains different in forms.
  • metal ions in the silver halide emulsion by adding a cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex thereof, rhodium salt or complex thereof, or iron salt or complex thereof, so that the metal ions can be included in the inner part and/or outer part of the grains; moreover, there can be provided reduction-sensitized specks in the inner part and/or outer part of the grains by keeping the grains in an appropriate reducing environment.
  • the silver halide emulsion used in the invention may be subjected to a desalting treatment after completion of silver halide grain formation to remove excessive soluble salts, or such salts may be left unremoved.
  • a desalting treatment after completion of silver halide grain formation to remove excessive soluble salts, or such salts may be left unremoved.
  • the methods described in Research Disclosure No. l7643 are applicable.
  • the silver halide emulsion used in the invention may be composed of grains in which a latent image is formed mainly on the surface, or of grains in which a latent image is formed mainly at the inner portion.
  • the silver halide emulsion is chemically sensitized by a conventional method. That is, there can be used, singly or in combination, the sulfur sensitization using a sulfur compound reactive to silver ions or an active gelatin, selenium sensitization employing a selenium compound, reduction sensitization using a reducing agent and precious metal sensitization with a compound of gold or other precious metals.
  • the chemical sensitization can be carried out, for example, by a chalcogen sensitizer.
  • chalcogen sensitizer is a general term for a sulfur sensitizer, selenium sensitizer and tellurium sensitizer; of these, a sulfur sensitizer and selenium sensitizer are preferred.
  • sulfur sensitizer examples include thiosulfate, allylthiocarbazide, thiourea, allylisocyanate, cystine, p-toluene thiosulfonate and rhodanine.
  • Other usable sulfur sensitizers are those described, for example, in U.S. Patent Nos. l,574,974, 2,4l0,689, 2,278,947, 2,728,668, 3,50l,3l3, 3,656,955, West Germany OLS No. l,422,869 and Japanese Patent O.P.I. Publication Nos. 24937/l98l and 450l6/l980.
  • the addition amount of the sulfur sensitizer greatly varies depending on conditions such as pH, temperature and size of silver halide grains, but it is roughly l0 ⁇ 7 to l0 -l mol per mol of silver halide.
  • the selenium sensitization may be used instead of the sulfur sensitization.
  • the selenium sensitizer are aliphatic isoselenocyanates such as allylisoselenocyanate; selenoureas; selenoketones; selenoamides; selenocarboxylates, selenophosphates; and selenides such as diethyl selenide and diethyl diselenide.
  • aliphatic isoselenocyanates such as allylisoselenocyanate; selenoureas; selenoketones; selenoamides; selenocarboxylates, selenophosphates; and selenides such as diethyl selenide and diethyl diselenide.
  • typical ones can be seen in U.S. Patent l,574,944, l,602,592 and l,623,499.
  • reduction sensitization may also be performed in conjunction.
  • Usable reducing agents are not particularly limited in types, but preferable examples are stannous chloride, thiourea dixide, hydrazine and polyamines.
  • Precious metal compounds other than gold such as palladium compounds, may be jointly used.
  • an internal latent image type silver halide emulsion may be used.
  • conversion type silver halide emulsions according to the conversion method described in U.S. Patent No. 3,592,250; silver halide emulsions which contain silver halide grains internally and chemically sensitized as described in U.S. Patent Nos. 3,206,3l6, 3,3l7,322 and 3,367,778; silver halide emulsions which have silver halide grains internally containing polyvalent metal ions as described in U.S. Patent Nos.
  • Such silver halide grains can be prepared in the same manner as with grains of ordinary layered structure.
  • a layered structure by a method in which silver chloride grains formed beforehand are converted into silver bromide grains with the addition of a bromide, and then different layers are successively formed thereon with the further addition of halides and silver nitrate; or a method in which silver iodobromide grains are formed under conditions of less excessive halogen, and then silver chloride and silver bromide are successively deposited in layers.
  • the internal latent image type silver halide emulsion used in the invention may contain a conventional stabilizer such as an azaindene-ring-containing compound or mercapto-group-containing heterocyclic compound, in order to control reverse side sensitivity as low as possible and to give a lower minimum density and stable photographic characteristics.
  • a conventional stabilizer such as an azaindene-ring-containing compound or mercapto-group-containing heterocyclic compound
  • a preferable example of the azaindene-ring-containing compound is 4-hydroxy-6-methyl-l,3,3a,7-tetrazaindene.
  • Preferable nitrogen-containing heterocyclic compound in the mercapto-group-containing heterocyclic compound are ones having pyrazole ring, l,2,4-triazole ring, l,2,3-triazole ring, l,3,4-thiadiazole ring, l,2,3-thiadiazole ring, l,2,4-thiadiazole ring, l,2,5-thiadiazole ring, l,2,3,4-tetrazole ring, pyridazine ring, l,2,3-triazine ring, l,2,4-triazine ring and l,3,5-triazine ring.
  • the compound having condensation products of two or three of these heterocycles such as triazolotriazole ring, diazaindene ring, triazaindene ring, tetrazaindene ring, pentazaindene ring; phthalazinone ring; and imidazole ring.
  • l-phenyl-5-mercaptotetrazole is particularly preferred.
  • the following sensitizing dyes are used to have at least three silver halide emulsion layers different in spectral sensitivities from one another.
  • sensitizing dye employed in a blue-sensitive silver halide emulsion layer include those described in West Germany Patent No. 929,080, U.S. Patent Nos. 2,23l,658, 2,493,748, 2,503,776, 2,5l9,00l, 2,9l2,329, 3,656,959, 3,672,897, 3,694,3l7, 4,025,349, 4,046,572, British Patent No. l,242,588 and Japanese Patent Examined Publication l4030/l969 and 24844/l977.
  • Typical examples of the sensitizing dye useful for a green-sensitive silver halide emulsion layer are those cyanine dyes, merocyanine dyes and complex cyanine dyes which are described in U.S. Patent Nos. l,939,20l, 2,072,098, 2,739,l49, 2,945,763, British Patent No. 505,979.
  • Typical examples of the sensitizing dye used in a red-sensitive emulsion layer are those cyanine dyes, merocyanine dyes and complex cyanine dyes which are described in U.S. Patent Nos. 2,269,234, 2,270,378, 2,442,7l0, 2,454,629 and 2,776,280.
  • cyanine dyes or complex cyanine dyes described in U.S. Patent Nos. 2,2l3,995, 2,493,748, 2,5l9,00l and West Germany Patent No. 929,080.
  • sensitizing dyes may be used singly or in combination. Combination of sensitizing dyes is often practiced for the purpose of supersensitization. Typical examples thereof can be seen in Japanese Patent Examined Publication Nos. 4932/l968, 4933/l968, 4936/l968, 32753/l969, 2583l/l970, 26474/l970, ll627/l97l, l8l07/l97l, 874l/l972, llll4/l972, 25379/l972, 37443/l972, 28293/l973, 38406/l973, 38407/l973, 38408/l973, 4l204/l973, 6207/l974, 40662/l975, l2375/l978, 34535/l979, l569/l980, Japanese Patent O.P.I.
  • dyes having no spectral sensitizing effect by themselves or compounds absorbing no visible light substantially and having a supersensitizing effect.
  • examples thereof include aromatic acid formaldehyde condensates such as those described in U.S. Patent No. 3,473,5l0, cadmium salts, azaindene compounds and aminostilbene compounds substituted with a nitrogen-containing heterocycle such as those described in U.S. Patent Nos. 2,933,390 and 3,635,72l.
  • the particularly useful are combinations described in U.S. Patent Nos. 3,6l5,6l3, 3,6l5,64l, 3,6l7,295 and 3,635,72l.
  • the silver halide color photographic light-sensitive material of the invention may use other conventional additives.
  • dihydroxyalkane for example, may be used.
  • an aqueous dispersion of fine particle polymeric substance prepared by emulsion polymerization such as copolymer of alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid, styrene-maleic acid copolymer or styrene-maleic anhydride half alkyl ester copolymer.
  • the coating aid include saponin, polyethylene glycol and lauryl ether.
  • photographic additives which may be optionally used in the invention are gelatin plasticizers, surfactants, ultraviolet absorbents, pH regulators, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brightening agents, development control agents, matting agents and anti-irradiation dyes.
  • ultraviolet absorbents such as thiazolidone type, benzotriazole type, acrylonitrile type and benzophenone type compounds.
  • the image forming layer of the invention may contain gelatin including oxidized gelatin or derivatives thereof appropriate to a specific requirement.
  • gelatin derivatives are acylated gelatin, guanidinated gelatin, carbamylated gelatin, cyanoethylated gelatin, estrified gelatin, etc.
  • the color light-sensitive material of the invention may contain other hydrophilic binders in its hydrophilic colloid layers.
  • hydrophilic binders may be added, according to specific requirements, in photographic structural layers such as emulsion layer, intermediate layer, filter layer and subbing layer. Further, these hydrophilic binders may use a plasticizer, lubricant, etc., depending on required photographic properties.
  • the color light-sensitive material of the invention may have, according to specific requirements, various photographic structural layers such as filter layer, intermediate layer, protective layer, subbing layer, backing layer and anti-halation layer, in addition to the emulsion layer that constitutes a layer that carries images on a support.
  • various photographic structural layers such as filter layer, intermediate layer, protective layer, subbing layer, backing layer and anti-halation layer, in addition to the emulsion layer that constitutes a layer that carries images on a support.
  • various methods including dip coating, air doctor coating, extrusion coating, slide hopper coating and curtain flow coating.
  • typical examples of the support are polyethylene terephthalate film which may be subbed when necessary, polycarbonate film, polystyrene film, polypropylene film and cellulose acetate film, baryta paper, paper laminated with polyolefin such as polyethylene, and polyethylene terephthalate film in which a white pigment is compounded.
  • the light-sensitive material of the invention can be exposed with electromagnetic waves having a spectral region to which the emulsion layer of said light-sensitive material is sensitive.
  • a light source there can be used any of the known light sources such as natural light (sunlight); tungsten lamp; fluorescent lamp; mercury lamp; xenon arc lamp; carbon arc lamp; xenon flash tube; cathode ray tube flying spot; various laser beams; light emitting diode beams; and beams emitted from a luminescent body excited by electron beams, X-rays, ⁇ -rays or ⁇ -rays.
  • the silver halide color photographic light-sensitive material of the invention can be made into a structure of ordinary color paper having color sensitive layers of blue-sensitivity, green-sensitivity and red-sensitivity.
  • three-color separation filters such as Wratten Nos. 25, 29, 58, 6l, 47B, can be used as an optical filter.
  • Exposure can be completed within an exposure time as short as less than l millisecond, not to mention the exposure time for ordinary printers which ranges from l millisecond to l0 seconds.
  • an exposure of l00 microseconds to l millisecond can be practiced with a cathode ray tube or xenon flash tube.
  • an exposure time longer than l0 seconds is also applicable.
  • Said exposure may be made continuously or intermittently.
  • the color developing agent used in a color developer includes conventional ones widely used in various color photographic processes.
  • the developer contains an aminophenol derivative and p-phenylenediamine derivative. These compounds are more stable when dissociated; therefore, they are generally used in the form of salt such as hydrochloride or sulfate. These compounds are generally used in an amount of approx. 0.l to approx. 30 g per liter of color developer, preferably in an amount of approx. l to approx. l5 g per liter of color developer.
  • aminophenol type developing agent examples include o-aminophenol, p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene and 2-oxy-3-amino-l,4-dimethylbenzene.
  • aromatic primary amine color developing agent are N,N-dialkyl-p-phenylenediamine compounds, of which alkyl and phenyl groups may be substituted or unsubstituted.
  • the particularly preferred are N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)toluene, N-ethyl-N- ⁇ -methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, 4-amino-N-ethyl-N-( ⁇ -hydroxyethyl)aniline sulfate, 4-amino-3-methyl-N,N-diethylaniline and 4-amino-N-(2-meth
  • a color developer for processing light-sensitive material of the invention there may be optionally added, besides the above aromatic primary amine color developing agent, conventional developer component compounds such as alkali agents including sodium hydroxide, sodium carbonate and potassium carbonate; alkali metal bisulfites; alkali metal thiocyanates; alkali metal halides; benzyl alcohol; water-softening agents; and thickeners.
  • alkali agents including sodium hydroxide, sodium carbonate and potassium carbonate
  • alkali metal bisulfites alkali metal thiocyanates
  • alkali metal halides alkali metal halides
  • benzyl alcohol benzyl alcohol
  • water-softening agents benzyl alcohol
  • the pH value of the color developer is normally more than 7, typically approx. l0 to approx. l3.
  • the developing temperature is normally higher than l5°C, typically within the range from 20°C to 50°C. For rapid processing, a temperature not less than 30°C is preferred.
  • the color developing time is generally within the range from 20 to 60 seconds, preferably within the range from 30 to 50 seconds.
  • the light-sensitive material according to the invention contains, in the hydrophilic colloid, the above color developing agents in their original forms, or as precursors thereof to be treated in an alkaline activating bath.
  • the precursor of a color developing agent which is capable of forming a color developing agent under alkaline conditions, falls into various types; namely, a Schiff's base precursor obtained by condensation with an aromatic aldehyde, polyvalent metal ion complex precursor, phthalimide derivative precursor, phosphorimide derivative precursor, sugar amine reactant precursor and urethane precursor.
  • These precursors of aromatic primary amine color developing agents are described, for example, in U.S. Patent Nos. 3,342,599, 2,507,ll4, 2,695,234, 3,7l9,492, British Patent No. 808,783, Japanese Patent O.P.I. Publication Nos. l85628/l978, 79035/l979 and Research Disclosure Nos. l5l59, l2l46, l3924.
  • addition amount of these aromatic primary amine color developing agents or precursors thereof be large enough to give activated products sufficient for proper color developing.
  • the addition amount is roughly 0.l to 5 mols, preferable 0.5 to 3 mols per mol of silver halide, though it greatly varies depending on types of light-sensitive material.
  • These color developing agents or precursors thereof may be used singly or in combination.
  • a light-sensitive material When contained in a light-sensitive material, they can be added therein in the form of solution in a suitable solvent such as water, methanol, ethanol or acetone, or in the form of dispersion in a high boiling organic solvent such as dibutyl phthalate, dioctyl phthalate or tricresyl phosphate, or may be added using a latex polymer impregnated with them as described in Research Disclosure No. l4850.
  • a suitable solvent such as water, methanol, ethanol or acetone
  • a high boiling organic solvent such as dibutyl phthalate, dioctyl phthalate or tricresyl phosphate
  • the principal process is to subject an internal latent image type light-sensitive material which is not fogged beforehand to imagewise exposing, and then to subject it to surface developing after a fogging treatment or while fogging it.
  • a fogging treatment can be performed by giving an overall uniform exposure to the light-sensitive material or using a fogging agent.
  • a fogging agent is preferred.
  • Usable fogging agents range over various chemical types, and fogging can be performed by simply having a fogging agent exist in the developing system.
  • a silver halide emulsion layer of an internal latent image type silver halide photographic light-sensitive material or in a developer may be contained, or it may be contained in treating solution used in a process that proceeds developing.
  • an internal latent image type silver halide photographic light-sensitive material is preferred, particularly addition in a silver halide emulsion is preferred.
  • Typical examples of the preferred fogging agent are those represented by the following Formula FA-I or FA-II.
  • Z represents a group of atoms necessary to form a five- or six-membered heterocycle; R ll is an aliphatic group; and R l2 represents a hydrogen atom, or an aliphatic or aromatic group.
  • R ll and R l2 may be substituted; R l2 may form a ring by bonding with the heterocyclic group which is completed by Z; provided that at least one of groups respectively represented by R ll , R l2 and Z contain a alkynyl, acyl, hydrazine or hydrazone group, or R ll and R l2 jointly form a six-membered ring, namely, a dihydropyridinium skeleton.
  • Y is a counter ions for balancing electric charge.
  • n is an integer of 0 or l.
  • R 2l represents an aliphatic, aromatic or heterocyclic group
  • R22 represents a hydrogen atom, or an alkyl, aralkyl, aryl, alkoxy, aryloxy or amino group
  • R23 and R24 are both hydrogen atoms, or one of them is a hydrogen atom and the other is an alkylsulfonyl, arylsulfonyl or acyl group
  • the above groups may be substituted if possible.
  • Typical examples of the compound represented by Formula FA-II are as follows.
  • these are dissolved in water-miscible organic solvents such as alcohols, such as methanol, ethanol, esters such as ethyl acetate or ketones such as acetone, or in water when these are water-soluble, and then added to a hydrophilic colloid solution.
  • water-miscible organic solvents such as alcohols, such as methanol, ethanol, esters such as ethyl acetate or ketones such as acetone
  • the addition may be made any time in a period between start of chemical ripening and before coating, but the addition after chemical ripening is preferred.
  • the fogging agent represented by Formula FA-I or FA-II may be contained in a hydrophilic colloid layer adjacent to a silver halide emulsion layer, but it is preferably contained in a silver halide emulsion layer.
  • the addition amount of the compound varies over a wide range, since it depends on many factors such as characteristics of the silver halide emulsion, chemical structure of the fogging agent and developing conditions. But it is practically in a range from l X l0 ⁇ 8 to l X l0 ⁇ 2 mol per mol of silver halide, preferably from l X l0 ⁇ 7 to l X l0 ⁇ 2 mol per mol of silver halide.
  • the preferred fogging agents used in the invention are those having the structure of Formula FA-I. Among them, those in which R l2 forms a ring in conjunction with the heterocycle completed by Z are particularly preferred.
  • speck formation accelerator in order to enhance the function of the fogging agent.
  • Preferable speck forming accelerators include tetrazaindenes, triazaindenes and pentazaindenes, each having at least one mercapto group which may be substituted by an alkali metal atom or ammonium group, as well as the compounds described in the specification of Japanese Patent O.P.I. Publication No. l06656/l988 (pp.6-l6).
  • the speck forming accelerator may be incorporated in a light-sensitive material or treating solution, but it is preferable to incorporate it in an internal latent image type silver halide emulsion layer or other hydrophilic colloid layers, e.g., as intermediate layer and protective layer, of a light-sensitive material.
  • the particularly preferable is to incorporate it in a silver halide emulsion layer or a layer adjacent thereto.
  • the light-sensitive material of the invention When the light-sensitive material of the invention is embodied in the form of internal latent image type silver halide photographic light-sensitive material, positive images are directly formed by imagewise exposing followed by overall exposing or developing in the presence of the fogging agent. Though developing of said light-sensitive material may be performed by any of developing methods, the surface developing method is preferred.
  • the surface developing method means a treatment with a developer substantially devoid of a silver halide solvent.
  • positive images corresponding to original images are formed by subjecting an exposed silver halide color photographic light-sensitive material to development and then to treatment with a treating solution having a fixing capability.
  • the above development includes combination of black-and-white development used in reverse color processing and color development. Further, there are also included overall exposure and development in the presence of the fogging agent, which are used in processing of the internal latent image type silver halide photographic light-sensitive material.
  • a black-and-white developer used in the development is equivalent to a conventional developer called black-and-white first developer, which is used in processing of a color photographic light-sensitive material, or to a conventional developer for a black-and-white photographic light-sensitive material.
  • This black-and-white developer can contain various additives used in conventional black-and-white developers.
  • Examples of typical additives include developing agents such as l-phenyl-3-pyrazolidone, metol and hydroquinone; preservatives such as sulfites; alkaline accelerators such as sodium hydroxide, sodium carbonate and potassium carbonate; inorganic and organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzothiazole; water softeners such as polyphosphates; and inhibitors against excessive surface developing containing traces of iodides and mercapto compounds.
  • developing agents such as l-phenyl-3-pyrazolidone, metol and hydroquinone
  • preservatives such as sulfites
  • alkaline accelerators such as sodium hydroxide, sodium carbonate and potassium carbonate
  • inorganic and organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzothiazole
  • water softeners such as polyphosphates
  • the light-sensitive material of the invention is subjected to bleaching and fixing.
  • Bleaching may be carried out concurrently with fixing.
  • the preferred are polyvalent metal compounds such as compounds of ion (III), cobalt (III) and copper (II).
  • the especially preferred are their complex salts with organic acids such as aminopolycarboxylic acids including ethylenediamine tetracetate, nitrilotriacetic acid, N-hydroxyethyl ethylenediamine diacetate; and malonic acid, tartaric acid, malic acid, diglycolic acid and thioglycolic acid.
  • Other usable bleaching agents are ferricyanates and bichromates. These bleaching agents may be used singly or in combination.
  • a soluble complexing agent which solubilizes silver halide as a complex salt is used.
  • the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea and thioether.
  • Fixing is usually followed by washing. But washing may be replaced by stabilizing or carried out concurrently with stabilizing.
  • a stabilizer solution there may be added a pH regulator, chelating agent and mildewproofing agent. Specific conditions on them can be seen in Japanese Patent O.P.I. Publication No. l34636/l983.
  • Green-sensitive emulsion EM-G was prepared in the same manner as with the blue-sensitive emulsion, except that sensitizing dye D-6 was used in the optical sensitization.
  • Red-sensitive emulsion EM-R was prepared in the same manner as with the blue-sensitive emulsion, except that sensitizing dye D-7 was used in the optical sensitization.
  • Each sample prepared as above was exposed as follows. A 0.075-step gray scale tablet and a dot positive scale of l50 line/in l% to 5% were closely contacted with a printer DSF-605F (product of Dainippon Screen Co.) and the sample was exposed to the light passed through a Wratten filter No. 58 (green).
  • a printer DSF-605F product of Dainippon Screen Co.
  • the original film was removed and subjected to exposure first through a Wratten filter No.47B (blue), then through a Wratten filter No.25 (red).
  • the exposure was carried out in a minimum exposing time in order to hold the color formation at a white portion to a minimum level.
  • the exposed sample was treated by the following processes to confirm the effect of the invention.
  • the evaluation results are shown in Table 3.
  • the stabilizing was carried out with a two-tank counter-flow apparatus.
  • Samples 4 and 6 of Example l were subjected to dot exposure and then processed in the same manner as in Example l, except that the following developing agents were used in place of 4-amino-N-ethyl-N-( ⁇ -hydoxyethyl)-aniline sulfate.

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  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP91108545A 1990-05-28 1991-05-25 Matériau photographique couleur à l'halogénure d'argent sensible à la lumière Withdrawn EP0459331A1 (fr)

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JP2137455A JPH0430164A (ja) 1990-05-28 1990-05-28 ハロゲン化銀カラー写真感光材料
JP137455/90 1990-05-28

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0585062A1 (fr) * 1992-08-25 1994-03-02 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière et son procédé de formation d'image
EP0588640A1 (fr) * 1992-09-16 1994-03-23 Konica Corporation Matériau photographique couleur à halogénure d'argent sensible à la lumière de type positif pour emploi comme épreuve en couleurs
EP0588641A1 (fr) * 1992-09-16 1994-03-23 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière et procédé pour préparation d'épreuve en couleurs
EP0588639A1 (fr) * 1992-09-16 1994-03-23 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière et procédé de préparation d'épreuve en couleurs
EP0607013A1 (fr) * 1993-01-14 1994-07-20 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
US5415988A (en) * 1992-11-25 1995-05-16 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP0671656A3 (fr) * 1994-03-11 1995-11-15 Konishiroku Photo Ind Matériau photographique couleur à l'halogénure d'argent sensible à la lumière et procédé de préparation d'épreuve en couleurs.
US5536629A (en) * 1994-12-23 1996-07-16 Eastman Kodak Company Chromogenic black-and-white motion picture film

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1474994A (en) * 1974-06-19 1977-05-25 Fuji Photo Film Co Ltd Multilayer colour photographic silver halide material
EP0355818A2 (fr) * 1988-08-24 1990-02-28 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent
JPH02124568A (ja) * 1988-07-04 1990-05-11 Konica Corp ハロゲン化銀カラー写真感光材料によるカラー画像の形成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1474994A (en) * 1974-06-19 1977-05-25 Fuji Photo Film Co Ltd Multilayer colour photographic silver halide material
JPH02124568A (ja) * 1988-07-04 1990-05-11 Konica Corp ハロゲン化銀カラー写真感光材料によるカラー画像の形成方法
EP0355818A2 (fr) * 1988-08-24 1990-02-28 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0585062A1 (fr) * 1992-08-25 1994-03-02 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière et son procédé de formation d'image
US5486450A (en) * 1992-08-25 1996-01-23 Konica Corporation Silver halide color photographic light sensitive material and the image-forming process thereof
US5382506A (en) * 1992-08-25 1995-01-17 Konica Corporation Silver halide color photographic light sensitive material and the image-forming process thereof
EP0588639A1 (fr) * 1992-09-16 1994-03-23 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière et procédé de préparation d'épreuve en couleurs
EP0588641A1 (fr) * 1992-09-16 1994-03-23 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière et procédé pour préparation d'épreuve en couleurs
US5436116A (en) * 1992-09-16 1995-07-25 Konica Corporation Silver halide color photographic photosensitive material and color proof preparation process
US5436117A (en) * 1992-09-16 1995-07-25 Konica Corporation Positive type silver halide color photographic light-sensitive material for color proofing use
US5462844A (en) * 1992-09-16 1995-10-31 Konica Corporation Light-sensitive silver halide color photographic material and process for preparing color proof
EP0588640A1 (fr) * 1992-09-16 1994-03-23 Konica Corporation Matériau photographique couleur à halogénure d'argent sensible à la lumière de type positif pour emploi comme épreuve en couleurs
US5415988A (en) * 1992-11-25 1995-05-16 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP0607013A1 (fr) * 1993-01-14 1994-07-20 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
US5368998A (en) * 1993-01-14 1994-11-29 Konica Corporation Silver halide color photographic light sensitive material
EP0671656A3 (fr) * 1994-03-11 1995-11-15 Konishiroku Photo Ind Matériau photographique couleur à l'halogénure d'argent sensible à la lumière et procédé de préparation d'épreuve en couleurs.
US5536629A (en) * 1994-12-23 1996-07-16 Eastman Kodak Company Chromogenic black-and-white motion picture film

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