EP0327274B1 - Lichtempfindliches photographisches Silberhalogenidmaterial - Google Patents

Lichtempfindliches photographisches Silberhalogenidmaterial Download PDF

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Publication number
EP0327274B1
EP0327274B1 EP19890300813 EP89300813A EP0327274B1 EP 0327274 B1 EP0327274 B1 EP 0327274B1 EP 19890300813 EP19890300813 EP 19890300813 EP 89300813 A EP89300813 A EP 89300813A EP 0327274 B1 EP0327274 B1 EP 0327274B1
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EP
European Patent Office
Prior art keywords
light
silver halide
group
sensitive silver
coupler
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EP19890300813
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English (en)
French (fr)
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EP0327274A2 (de
EP0327274A3 (en
Inventor
Hirokazu Sato
Akiyoshi Tai
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Konica Minolta Inc
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Konica Minolta Inc
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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
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39212—Carbocyclic
    • G03C7/39216—Carbocyclic with OH groups
    • 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

  • This invention relates to a light-sensitive silver halide photographic material with little color turbidity and excellent color reproducibility.
  • a light-sensitive silver halide color photographic material has three kinds of silver halide emulsion layers for photography. These are each spectrally sensitized selectively so as to be sensitive to blue light, green light and red light. They are each coated on a support.
  • a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer are generally provided by coating, and further an intermediate layer or a protective layer, including an UV-ray absorbing layer are also provided.
  • the reaction rate between the diffusion-resistant couplers contained in each light-sensitive silver halide emulsion layer with a color developing agent's oxidized product is generally different between the respective emulsion layers. For this reason, excessive oxidized product of the color developing agent generated in an emulsion layer containing a diffusion-resistant coupler with small reaction rate will diffuse to other silver halide emulsion layers. Thus color turbidity is likely to occur and color reproducibility will be lowered.
  • Light-sensitive silver halide color photographic materials are subjected to automatic developing by a machine provided in laboratories.
  • By way of an improvement of service for customers there have been demands to perform development processing and return the processed product within the same day that the development was ordered. Recently, there have been further demands to return the product within several hours from the order.
  • development of a light-sensitive silver halide color photographic material capable of rapid processing has been increasingly desired.
  • the present invention has been accomplished in view of the state of the art as described above.
  • the object of the present invention is to provide a light-sensitive silver halide color photographic material having little color turbidity and excellent color reproducibility.
  • This object has been accomplished by a particular light-sensitive silver halide photographic material comprising at least two light-sensitive silver halide emulsion layers containing diffusion-resistant couplers and at least one non-light-sensitive intermediate layer sandwiched between them, all provided on a support.
  • This non-light-sensitive intermediate layer contains a compound which deactivates the oxidized product of a color developing agent.
  • the relative color formation speed ratio k1/k2 (wherein k1 is less than or equal to k2) between the diffusion-resistant couplers contained in the respective two light-sensitive silver halide emulsion layers adjacent to said non-light-sensitive intermediate layer (wherein k1 and k2 are each the absorbances at the maximum absorption wavelength in the visible region of colour dyes extracted into a mixture of methanol and ethyl acetate (present in a volume ratio of 1:2 respectively, based on the volume of the reaction mixture), said dyes being formed from mixing a coupler solution A (wherein the respective diffusion resistant coupler is dispersed by use of 0.5 g of dioctyl phthalate per 1 mmol of coupler and the coupler concentration is 2 x 10 ⁇ 2 mol and silver chloride concentration is 4 x 10 ⁇ 3 mol using a silver chloride emulsion with an AgCl content of 100 % and an average particle size of 0.14 ⁇ m) and a color developer B (comprising 2 x
  • the relative color formation speed of a coupler for example as described in Japanese Unexamined Patent Publication No. 60437/1984, can be determined by adding a mixture of two different dyes which can be separated from each other into an emulsion and measuring the amounts of the respective dyes obtained by color developing the emulsion.
  • the relative color formation speed ratio k1/k2 between the diffusion-resistant couplers used in the present invention is determined as described below on the basis of a principle which is basically similar to the above method.
  • a coupler is dispersed by use of 0.5 g of dioctyl phthalate per 1 mmol of coupler.
  • a coupler solution A (wherein the coupler concentration is 2 x 10 ⁇ 2 mol and silver chloride concentration is 4 x 10 ⁇ 3 mol using a silver chloride emulsion with an AgCl content of 100 % and an average particle size of 0.14 ⁇ m) and a color developer B (comprising 2x10 ⁇ 2 mol of N-ethyl-N- ⁇ -methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, 40g/liter of anhydrous potassium carbonate, 1g/liter of sodium sulfite, and having pH 10.0) at 25 °C at a volume ratio of 1 : 1 (coupler solution A : color developer B).
  • the ratio of the absorbances obtained is defined as k1/k2.
  • the absorbance k1 is less than or equal to k2.
  • the ability Sc of the compound to deactivate the oxidized product of the color developing agent in the non-light sensitive intermediate layer in the present invention is determined according to the method as described below.
  • the diffusion-resistant couplers and compounds which deactivate the oxidised product of a colour developing agent used in the present invention are defined by the above k1/k2 and Sc, and are not limited by their chemical structures.
  • the above ratio k1/k2 is required to be 0.25 or more and 1 or less, preferably 0.30 or more and 1 or less.
  • the product of Sc represented by the above formula (I) and k1/k2 is required to be 0.2 or more, preferably 0.3 or more.
  • the light-sensitive silver halide color photographic material of the present invention preferably contains a hydroquinone type compound as the compound which deactivates the oxidized product of the color developing agent in the non-light-sensitive intermediate layer, and a yellow coupler in one of the two light-sensitive silver halide emulsion layers adjacent to said non-light-sensitive intermediate layer and a magenta coupler in the other of the emulsion layers.
  • the non-light-sensitive intermediate layer used in the present invention is required to have the ability (Sc) to deactivate the oxidized product of the color developing agent which satisfies the relationship of the above formula (I). Sc can be controlled as desired according to the nature of and amount added of the compound which deactivates the oxidized product of the color developing agent.
  • the compound which deactivates the oxidized product of the color developing agent used in the present invention is preferably a hydroquinone derivative, aminophenol derivative, gallic acid derivative, ascorbic acid derivative but, as mentioned above, more preferably a hydroquinone derivative.
  • hydroquinone type compounds which deactivate the oxidized product of the color developing agent preferably used in the present invention are represented by the formula (HQ) shown below.
  • R1 represents a substituted or unsubstituted alkyl group
  • n represents an integer of 1 to 3.
  • R2 represents a halogen atom, hydroxyl group, sulfo group, carboxyl group
  • m represents an integer of 0 to 3, and when m is 2 or more, R2 is the same or different.
  • the sum of n + m is 4 or less.
  • the alkyl group represented by R1 is preferably a straight or branched chain alkyl group having 1 to 20 carbon atoms, including, for example, methyl, ethyl, propyl, t-butyl, octyl, t-dodecyl groups.
  • substituents for R1 include a sulfo group, carboxyl group, cyano group, hydroxyl group, halogen atom (e.g. fluorine, chlorine, bromine), -COOR4, -COR5, -OR6, -SO2R7, -NHSO2R8.
  • R4, R5, R6, R7 and R8 represent an alkyl group, alkenyl group, cycloalkyl group, or aryl group.
  • alkyl group represented by R4 through R8 is preferably the same as the alkyl represented by the above R1.
  • cycloalkyl groups include cyclopentyl, cyclohexyl groups.
  • alkenyl group one having 2 to 18 carbon atoms is preferred, for example allyl, octenyl, octadecenyl groups.
  • aryl groups include phenyl, naphthyl groups.
  • R4, R5, R6, R7 and R8 are optionally substituted.
  • R2 in the formula (HQ) represents a halogen atom (e.g. fluorine, chlorine, or bromine), hydroxyl group, sulfo group, carboxyl group, preferably a sulfo group or a carboxyl group.
  • a halogen atom e.g. fluorine, chlorine, or bromine
  • n is preferably 1 or 2
  • m is preferably 0 or 1.
  • the compounds which deactivate the oxidized product of the color developing agent to be used in the present invention may include in addition to the above compounds, for example, those as described in U.S. Patents 2,360,290, 2,336,327, 2,418,613, 2,673,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,765, Japanese Unexamined Patent Publications. Nos. 92988/1975, 92989/1975, 93928/1975, 110337/1975, 146235/1977, Japanese Patent Publication No. 23813/1975, Japanese Unexamined Patent Publications Nos. 24141/1983, 5247/1984, 81639/1987 and further Japanese Unexamined Patent Publication No. 39851/1987, page 5 right lower col. to page 7 right lower col, and Japanese Unexamined Patent Application No. 93538/1986, page 19 to page 29. They can be synthesized easily according to the methods as described in the above patents.
  • the compound which deactivates the oxidized product of the color developing agent to be used in the present invention can be used either singly or in combination, Sc in this latter case is determined as the sum of the Sc's for the respective compounds.
  • Sc in this latter case is determined as the sum of the Sc's for the respective compounds.
  • the hydroquinone type compound it is also possible to add a quinone type compound which is its oxidized product.
  • the compound which deactivates the oxidized product of the color developing agent may be contained in the non-light-sensitive intermediate layer used in the present invention preferably in an amount of 2 x 10 ⁇ 4 to 1 x 10 ⁇ 2 mol per 1 m2, more preferably 3 x 10 ⁇ 4 to 5 x 10 ⁇ 3 mol.
  • the compound which deactivates the oxidized product of the color developing agent to be used in the present invention can be added in the coating solution for forming the layer or in a solution dissolved at an appropriate concentration in a solvent which does not deleteriously affect the light-sensitive material such as water, alcohol.
  • a solvent which does not deleteriously affect the light-sensitive material such as water, alcohol.
  • the yellow coupler preferably used in the present invention is preferably represented by the following formula (Y).
  • R Y1 represents a halogen atom.
  • R Y2 represents a hydrogen atom or a group substitutable on the benzene ring, and B represents a ballast group.
  • Z represents a hydrogen atom, a halogen atom or a group which is eliminated in a reaction with the oxidized product of the color developing agent.
  • the halogen atom represented by R Y1 is preferably chlorine atom, and R Y2 is preferably a hydrogen atom.
  • ballast group represented by B examples include acylamino, alkoxycarbonyl, aryloxycarbonyl, alkylsulfamoyl, arylsulfamoyl, alkylsulfonamide, arylsulfonamide, alkylureido, arylureido, succinimido, alkoxy, aryloxy, alkoxycarbonylamino, alkylcarbamoyl, arylcarbamoyl, alkylsulfamoylamino, arylsulfamoylamino, alkyl, alkenyl, acyloxy. It is particularly preferably a group having a total number of carbon atoms of 8 to 30.
  • Z is preferably a halogen atom or the group which is eliminated in a reaction with the oxidized product of the color developing agent.
  • the halogen atom chlorine atom is preferable
  • the group which is eliminated is preferably a group represented by (wherein R Z1 represents a group of non-metal atoms necessary for forming an optionally substituted nitrogen-containing heterocyclic ring) or -OR Z2 (wherein R Z2 represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group).
  • a yellow coupler containing at least one functional group A shown below in at least one of the groups represented by B and Z in the above formula (Y) is most preferably used.
  • R1 - R4, R6, R7 and R10 each represent an alkyl group or an aryl group
  • R5, R8, R9 and R11 each represent a hydrogen atom, an alkyl group or an aryl group.
  • the alkyl group represented by R1 to R11 is preferably a straight or branched alkyl group having 1 to 20 carbon atoms.
  • the aryl group represented by R1 to R11 is preferably phenyl group. Both the alkyl group and the aryl group represented by R1 to R11 are optionally substituted.
  • the functional group A is contained in at least one of the groups represented by B and Z, but particularly preferably in the group represented by B.
  • the yellow coupler to be used in the present invention also includes, in addition to the above compounds, the yellow couplers as described in Japanese Unexamined Patent Publications Nos. 155538/1982, 6652/1986, 70841/1980, 24321/1972, 66834/1973, Japanese Patent Publication No. 19031/1971, Japanese Unexamined Patent Publications Nos. 87650/1975, 123342/1975, U.S. Patent 3,408,194, and further Japanese Unexamined Patent Publication No. 72239/1986, page 5 left lower col. to page 8 left upper col., Japanese Patent Applications Nos. 231525/1986, page 22 to page 40, 243865/1986, page 20 to page 38. They are also optionally synthesized according to the methods described in these documents.
  • known 5-pyrazolone type couplers and pyrazoloazole type couplers can be preferably used as the magenta coupler. More preferably, they are couplers represented by the following formulae (M-I) to (M-III).
  • Ar represents an aryl group
  • R P1 hydrogen atom or a substituent
  • R P2 represents a substituent
  • Y represents hydrogen atom or a group which is eliminated in the reaction with the oxidized product of the color developing agent
  • W represents -NH-, -NHCO- (N atom is bonded to the carbon atom of the pyrazolone nucleus) or -NHCONH-
  • m is an integer of 1 or 2.
  • X M represents hydrogen atom or a group which is eliminated in the reaction with the oxidized product of the color developing agent
  • each of R M1 and R M2 represents hydrogen atom or a substituent.
  • the aryl group represented by Ar is preferably a phenyl group, more preferably a phenyl group substituted by at least one halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, acylamino group or cyano group.
  • the substituent represented by R P1 is preferably a halogen atom or an alkoxy group, more preferably a chlorine atom.
  • the substituent represented by R P2 is not particularly limited, but at least one of R P2 is a ballast group.
  • the ballast group represented by R P2 known ballast groups in this field of art are preferably used.
  • W is preferably -NH-.
  • the group which is eliminated in the reaction with the oxidized product of the color developing agent represented by Y is preferably aryloxy, alkoxy, heterocyclicoxy, silyloxy, phosphoneoxy, alkylthio, arylthio, heterocyclicthio, acylthio, thiocyano, aminothiocarbonylthio, acylamino, sulfonamide, alkoxycarbonylamino, aryloxycarbonylamino or nitrogen-containing heterocyclic group bonded through nitrogen atom at the active site of the pyrazolone ring.
  • R M1 and R M2 are not particularly limited, but are preferably alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, halogen atoms and cycloalkenyl, alkynyl, heterocyclic ring, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocycl
  • R M1 on the above heterocyclic ring is one represented by the formula (M-IV) shown below. wherein R M4 , R M5 and R M6 have the same meanings as the above R M1 and R M2 .
  • R M4 , R M5 and R M6 may be bonded together to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene, heterocyclic ring), and further R M6 may be bonded to said ring to constitute a bridged hydrocarbon compound residue.
  • a saturated or unsaturated ring e.g. cycloalkane, cycloalkene, heterocyclic ring
  • R M6 may be bonded to said ring to constitute a bridged hydrocarbon compound residue.
  • R M4 to R M6 are alkyl groups and (ii) one of R M4 to R M6 (for example, R M6 ) is a hydrogen atom, and the other two (R M4 and R M5 ) are bonded together to form a cycloalkyl together with the root carbon atom.
  • (i) is the case wherein two of R M4 - R M6 are alkyl groups, and the other one is a hydrogen atom or an alkyl group, and most preferred is the case wherein all of R M4 to R M6 are alkyl groups.
  • Examples of the group which is eliminated in the reaction with the oxidized product of the color developing agent represented by X M in the formulae (M-II) and (M-III) include halogen atoms (chlorine, bromine, or fluorine) and alkoxy, aryloxy, heterocyclicoxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclicthio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded through the N-atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl groups; preferably halogen atoms, particularly preferably chlorine atom.
  • magenta coupler may also form a polymer dimer or higher through Y, Ar, R P1 or R P2 in the above formula (M-I), and through X M , R M1 or R M2 in the above formulae (M-II) and (M-III).
  • magenta coupler to be used in the present invention is not limited.
  • magenta couplers to be used in the present invention include, in addition to the above compounds, those disclosed in U.S. Patent 3,684,514, U.K. Patent 1,183,515, Japanese Patent Publications Nos. 6031/1965, 6035/1965, 15754/1969, 40757/1970, 19032/1971, Japanese Unexamined Patent Publications Nos. 13041/1975, 129035/1978, 37646/1976, 62454/1980, U.S. Patent 3,725,067, U.K. Patents 1,252,418, 1,334,515, Japanese Unexamined Patent Publications Nos. 171956/1984, 162548/1984, 43659/1985, 33552/1985, 39852/1987, Research Disclosure No.
  • the light-sensitive silver halide photographic material of the invention can be applied to, for example, color negative and positive film, as well as color printing paper. Above all the effect of the present invention is exhibited when it is applied to a color printing paper to be provided for direct viewing.
  • the light-sensitive silver halide photographic material including the color printing paper is a light-sensitive silver halide photographic material for multi-color use, and for effecting color reproduction by the color subtractive method. It generally has a structure (in addition to the one already defined) comprising silver halide emulsion layers containing the respective couplers of magenta, yellow and cyan laminated in a suitable number of layers and order of layers on a support. The number of layers and their order may be suitably changed depending on the desired performance, and purpose of use.
  • couplers of the above formula (Y) are preferred, and as the magenta coupler, couplers represented by the above formulae (M-I) to (M-III) are preferably used.
  • cyan coupler phenol type compounds, naphthol type compounds can be used.
  • hydrophobic compounds such as couplers, and/or compounds which deactivate the oxidized product of the color developing agent can optionally be added into the light-sensitive silver halide photographic material by use of various methods for example, the solid dispersion method, the latex dispersion method, the oil-in-water type emulsification and dispersion method.
  • the oil-in-water type emulsification and dispersion method may be carried out by dissolving a hydrophobic compound such as a coupler generally in a high boiling organic solvent with a boiling point of about 150 °C or higher, or optionally in a low boiling and/or water-soluble organic solvent in combination, emulsifying the solution in a hydrophilic binder such as an aqueous gelatin solution by use of a surfactant, and then adding the emulsion into the desired hydrophilic colloid layer.
  • a hydrophobic compound such as a coupler generally in a high boiling organic solvent with a boiling point of about 150 °C or higher, or optionally in a low boiling and/or water-soluble organic solvent in combination
  • a hydrophilic binder such as an aqueous gelatin solution by use of a surfactant
  • the silver halide used in the present invention may be any silver halide, for example silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide or silver chloroiodide.
  • silver halide grains containing 90 mol% or more of silver chloride are preferred, and the silver bromide content is preferably 10 mol% or less and the silver iodide content preferably 0.5 mol% or less. More preferably, silver chlorobromide having a silver bromide content of 0.1 - 2 mol% is employed.
  • the silver halide grains are used either alone or as a mixture with other silver halide grains having a different composition. Also, they can be used in a mixture with silver halide grains having a silver chloride content of 10 mol% or less.
  • the ratio of the silver halide grains having a silver chloride content of 90 mol% to the total number of silver halide grains contained in said emulsion layer is preferably 60 % by weight or more, more preferably 80 % by weight or more.
  • composition of the silver halide grain is either uniform from the inner portion to the outer portion of the grain, or different in the inner portion from the outer portion. When the compositions in the inner portion and the outer portion of the grain are different, the composition is either varied continuously or discontinuously.
  • the grain size of the silver halide grain is not specifically limited, but it is preferably within the range of 0.2 to 1.6 ⁇ m, more preferably 0.25 to 1.2 ⁇ m, taking into account photographic performances such as rapid processability and sensitivity.
  • the above grain size can be measured according to methods generally employed in the related field of art. Representative methods are described in Rabland "Grain Size Analytical Method” (A.S.T.M. Symposium on Light Microscopy, 1955, pp. 94 - 122) or "Theory of Photographic Process” (Mees and James, co-authors, third edition, McMillan Co., 1966, Chapter 2).
  • the grain size can be measured by use of the projected area or from an approximate value for the diameter of the grains.
  • the grain size distribution can be represented accurately by the diameter or projected area.
  • the distribution of the grain sizes of silver halide grains is either poly-dispersed or mono-dispersed.
  • mono-dispersed silver halide grains having a fluctuation coefficient of 0.22 or less, more preferably 0.15 or less, in the grain size distribution of the silver halide grains is employed.
  • ri represents the grain size of individual grains
  • ni represents their number.
  • the grain size as mentioned here refers to the diameter of a spherical silver halide grain, or the diameter of a projected image calculated from a circular image having the same area in the case of grains having a cubic shape or a shape other than a sphere.
  • the silver halide grains to be used can be obtained according to an acidic method, neutral method or ammonia method. Said grains are grown either simultaneously or after preparation of seed grains.
  • the method for making seed grains and the method for growing the grains is either the same or different.
  • the method of reacting the soluble silver salts with the soluble halogen salts can be a normal mixing method, reverse mixing method, simultaneous mixing method or combinations thereof. It is preferably the simultaneous mixing method. Further, as one mode of the simultaneous mixing method, it is also possible to use the pAg-controlled double jet method as described in Japanese Unexamined Patent Publication No. 48521/1979.
  • a silver halide solvent for example thioether
  • compounds such as mercapto-containing compounds, nitrogen-containing heterocyclic compounds or sensitizing dyes are also optionally added during formation of silver halide grains or after completion of grain formation.
  • Any shape of silver halide grains can be used.
  • a preferable example is the cubic shape having ⁇ 100 ⁇ plane as the crystal surface.
  • grains having octahedral, tetradecahedral, dodecahedral shapes can be made according to the methods as described in U.S. Patents 4,183,756, 4,225,666, Japanese Unexamined Patent Publication No. 26589/1980, Japanese Patent Publication No. 42737/1980, The Journal of Photographic Science (J. Photgr. Sci.), 21 , 39 (1973). These can also optionally be used. Further, grains having twin crystal surfaces may also optionally be used.
  • Silver halide grains comprising either a single shape or a mixture of various shapes are employed.
  • the silver halide grains to be used in the emulsion can contain metal ions, for example, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or a complex thereof, rhodium salt or a complex thereof, iron salt or a complex thereof. These are contained either internally and/or on the surface of the grains, either by adding them in the process of forming the grains and/or in the process of growing them. Optionally by placing the grains in an appropriate reducing atmosphere, reducing sensitizing nuclei can be imparted internally of the grains and/or the surface of the grains.
  • metal ions for example, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or a complex thereof, rhodium salt or a complex thereof, iron salt or a complex thereof.
  • the emulsion containing the silver halide grains has either had unnecessary soluble salts removed after completion of the growth of the silver halide grains, or just contains them.
  • said salts can be done by the method described in Research Disclosure No. 17643, for example.
  • the silver halide grains to be used in the emulsion are either grains in which latent images are formed primarily on the surface or grains in which latent images are formed primarily internally.
  • grains in which latent images are formed primarily on the surface are employed.
  • the emulsion to be used in the present invention is preferably chemically sensitized according to conventional methods.
  • Methods which may be employed are, for example, the sulfur sensitization method which uses a compound containing sulfur which can react with silver ions or active gelatin, the selenium sensitizing method which uses a selenium compound, the reducing sensitizing method which uses a reducing substance, the noble metal sensitizing method which uses gold or other noble metal compounds either individually or in combination.
  • the silver halide emulsion is optionally optically sensitized to a desired wavelength region by use of a dye known as a sensitizing dye.
  • the light-sensitive silver halide photographic material of the present invention there can optionally be used, as desired, color antifoggant, film hardener, plasticizer, polymer latex, UV-ray absorber, formalin scavenger, mordant, developing accelerator, developing retarder, fluorescent brighener, matting agent, lubricant, antistatic agent, or surfactant.
  • the light-sensitive silver halide photographic material may be developed by a variety of color developing processes.
  • the layers 1 - 7 shown below were successively provided by coating (simultaneous coating) on a paper support coated on the both surfaces with polyethylene to prepare light-sensitive silver halide color photographic materials 1 - 33 (in the following examples, the amount added is shown in an amount per 1 m2 of the light-sensitive material).
  • the blue light absorption density D'B at the unexposed portion, the blue light absorption density DB at the exposed portion, the green light absorption density D'G at the unexposed portion and the green light absorption density DG at the exposed portion were determined by a densitometer (Sakura Densitometer PDA-60, produced by Konishiroku Photo Industry).
  • Light-sensitive silver halide color photographic material samples No. 34 to 66 were prepared in entirely the same manner as in Example 1 except for replacing the blue-sensitive silver halide emulsion in Layer 1 of the light-sensitive silver halide color photographic material prepared in Example 1 with Em-4 shown in Table 1, the green-sensitive silver halide emulsion in Layer 3 with Em-5 in Table 1, and the red-sensitive silver halide emulsion in Layer 5 with Em-6 in Table 1, respectively and using the yellow coupler, magenta coupler and the compound which deactivates the oxidized product of the color developing agent in Layer 1, Layer 3 and Layer 2, respectively.

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  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (13)

  1. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial mit mindestens zwei lichtempfindlichen Silbehalogenidemulsionsschichten mit diffusionsfesten Kupplern und mindestens einer zwischen den lichtempfindlichen Silberhalogenidemulsionsschichten angeordneten nicht-lichtempfindlichen Zwischenschicht auf einem Schichtträger, wobei die nicht-lichtempfindliche Zwischenschicht eine das Oxidationsprodukt einer Farbentwicklerverbindung desaktivierende Verbindung enthält, das relative Farbbildungsgeschwindigkeitsverhältnis k₁/k₂ (wobei gilt: k₁ ≦ k₂) zwischen den diffusionsfesten Kupplern in den zu der nicht-lichtempfindlichen Zwischenschicht benachbart angeordneten beiden lichtempfindlichen Silberhalogenidemulsionsschichten (k₁ und k₂ sind die Extinktionswerte bei der maximalen Absorptionswellenlänge im sichtbaren Bereich von in ein Gemisch aus Methanol und Ethylacetat (vorhanden in einem Volumenverhältnis von 1/2, bezogen auf das Volumen des Reaktionsgemischs) extrahierten (farbigen) Farbstoffen, die durch Vermischen einer Kupplerlösung A (worin der betreffende diffusionsfeste Kuppler mit Hilfe von 0,5 g Dioctylphthalat pro 1 mmol Kuppler dispergiert ist und die Kupplerkonzentration 2 x 10⁻² mol und die mittels einer Silberchloridemulsion mit einem AgCl-Gehalt von 100% und einer durchschnittlichen Teilchengröße von 0,14 µm eingestellte Silberchloridkonzentration 4 x 10⁻³ mol betragen) mit einem Farbentwickler B (mit 2 x 10⁻² mol des zum Entwickeln des lichtempfindlichen Silberhalogenid-Aufzeichnungsmaterials zu verwendenden Farbentwicklers, 40 g/l wasserfreien Kaliumcarbonats und 1 g/l Natriumsulfit bei einem pH-Wert von 10,0) bei 25°C im Volumenverhältnis 1/1 (Kupplerlösung A/Farbentwickler B) gebildet wurden) 0,25 ≦ k₁/k₂ ≦ 1 beträgt und die Beziehung des Verhältnisses k₁/k₂ zur Fähigkeit Sc zur Deaktivierung des Oxidationsprodukts der Farbentwicklerverbindung in der nicht-lichtempfindlichen Schicht durch die Gleichung (I): Sc · k₁/k₂≧0,2
    Figure imgb0082
     worin Sc bedeutet: Sc = (ABS) R (ABS) S x Cs
    Figure imgb0083
     worin Sc in der Einheit mmol/m² angegeben ist und Cs die Menge in mnol der das Oxidationsprodukt der Farbentwicklerverbindung desaktivierenden Verbindung, die pro m² der nicht-lichtempfindlichen Zwischenschicht enthalten ist, (ABS)R die in entsprechender Weise wie bei k₁ oder k₂ bestimmte Extinktion ist, wobei jedoch als Kuppler ein solcher der Formel (C-1):
    Figure imgb0084
     verwendet wird, und (ABS)S die in entsprechender Weise wie (ABS)R ermittelte Extinktion darstellt, wobei jedoch der Kupplerlösung A eine unter Verwendung von 0,5 g Dioctylphthalat pro 1 mmol der das Oxidationsprodukt der Farbentwicklerverbindung desaktivierenden Verbindung zubereitete Dispersion zugesetzt wird (Konzentration der das Oxidationsprodukt der Farbentwicklerverbindung desaktivierenden Verbindung: 2·10³ mol)
    Figure imgb0085
     gegeben ist.
  2. Lichtempfindliches photographishces Silberhalogenid-Aufzeichnungsmaterial nach Anspruch 1, wobei das relative Farbbildungsgeschwindigkeitsverhältnis k₁/k₂ 0,30 ≦ k₁/k₂ ≦ 1 ist.
  3. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial nach Anspruch 1 oder 2, wobei die Beziehung k₁/k₂ zu der Fähigkeit Sc durch die Gleichung (I′): Sc·k₁/k₂ ≧ 0,3
    Figure imgb0086
     gegeben ist.
  4. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial nach einem der vorhergehenden Ansprüche, wobei die das Oxidationsprodukt einer Farbentwicklerverbindung desaktivierende Verbindung aus einem Hydrochinon-, Aminophenol-, Gallussäure- oder Ascorbinsäurederivat besteht.
  5. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial nach einem der vorhergehenden Ansprüche, wobei die das Oxidationsprodukt einer Farbentwicklerverbindung desaktivierende Verbindung aus einem Hydrochinonderivat der Formel (HQ):
    Figure imgb0087
     worin bedeuten:
    R₁ eine substituierte oder unsubstituierte Alkylgruppe;
    n eine ganze Zahl von 1 bis 3, wobei gilt, daß die Gesamtsumme der Kohlenstoffatome bei R₁ 8 oder mehr beträgt und, im Falle, daß n = 2 oder mehr bedeutet, die Reste R₁ gleich oder verschieden sind;
    R₂ ein Halogenatom, eine Hydroxylgruppe, eine Sulfogruppe, eine Carboxylgruppe und
    m eine ganze Zahl von 0 bis 3, wobei im Falle, daß m = 2 oder mehr ist, die Reste R₂ gleich oder verschieden sein können, und wobei die Summe n + m = 4 oder weniger ist, besteht.
  6. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial nach Anspruch 5, wobei die durch R₁ wiedergegebene Alkylgruppe aus einer Methyl-, Ethyl-, Propyl-, tert.-Butyl-, Octyl- oder tert.-Dodecylgruppe und der Substituent an R₁ aus einer Sulfo-, Carboxyl-, Cyano- oder Hydroxylgruppe, einem Halogenatom oder -COOR₄, -COR₅, -OR₆, -SO₂R₇ oder -NHSO₂R₈ mit R₄, R₅, R₆, R₇ und R₈ jeweils gleich einer Alkyl-, Alkenyl-, Cycloalkyl- oder Arylgruppe besteht.
  7. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial nach einem der vorhergehenden Ansprüche, wobei die das Oxidationsprodukt der Farbentwicklerverbindung desaktivierende Verbindung in der nicht-lichtempfindlichen Zwischenschicht in einer Menge von 2 x 10⁻⁴ bis 1 x 10⁻² mol pro m² enthalten ist.
  8. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial nach Anspruch 7, wobei die das Oxidationsprodukt der Farbentwicklerverbindung desaktivierende Verbindung in der nicht-lichtempfindlichen Zwischenschicht in einer Menge von 3 x 10⁻⁴ bis 5 x 10⁻³ mol pro m² enthalten ist.
  9. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial nach einem der vorhergehenden Ansprüche, wobei der diffusionsfeste Kuppler aus einem Gelbkuppler der Formel (Y):
    Figure imgb0088
     worin bedeuten:
    RY1   ein Halogenatom:
    RY2   ein Wasserstoffatom oder eine an den Benzolring substituierbare Gruppe;
    B   eine Ballastgruppe und
    Z   ein Wasserstoff- oder Halogenatom oder eine bei der Reaktion mit dem Oxidationsprodukt der Farbentwicklerverbindung abspaltbare Gruppe,
    besteht.
  10. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial nach Anspruch 9, wobei mindestens einer der Reste B und Z in Formel (Y) mindestens eine der folgenden funktionellen Gruppen:
    -COOH,-OH,-SO₂R¹,-SOR², -COOR³, -OCOR⁴,
    Figure imgb0089
     worin R¹ bis R⁴, R⁶, R⁷ und R¹⁰ jeweils für eine Alkyl- oder Arylgruppe stehen und R⁵, R⁸, R⁹ und R¹¹ jeweils ein Wasserstoffatom oder eine Alkyl- oder Arylgruppe darstellen,
    enthält.
  11. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial nach einem der vorhergehenden Ansprüche, wobei der diffusionsfeste Kuppler aus einem Gelbkuppler oder einem Purpurrotkuppler besteht und der Gelbkuppler in einer der zu der nicht-lichtempfindlichen Zwischenschicht benachbarten beiden lichtempfindlichen Silberhalogendemulsionsschichten untergebracht ist und der Purpurrotkuppler in der anderen (Emulsionsschicht) enthalten ist.
  12. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial nach einem der vorhergehenden Ansprüche, wobei die Silberhalogenidkörnchen in dem lichtempfindlichen photographischen Silberhalogenid-Aufzeichnungsmaterial 90 Mol-% oder mehr Silberchlorid enthalten.
  13. Verfahren zum Entwickeln des lichtempfindlichen photographischen Silberhalogenid-Aufzeichnungsmaterials nach einem der vorhergehenden Ansprüche, wobei der Farbentwickler aus N-Ethyl-N-β-methansulfonamidoethyl-3-methyl-4-aminoanilinsulfat besteht.
EP19890300813 1988-01-30 1989-01-27 Lichtempfindliches photographisches Silberhalogenidmaterial Expired - Lifetime EP0327274B1 (de)

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JPH07111565B2 (ja) * 1988-11-16 1995-11-29 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
WO1992003762A1 (en) * 1990-08-16 1992-03-05 Eastman Kodak Company Photographic material
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