EP0107112A2 - Matériels photographiques couleurs à l'halogénure d'argent sensibles à la lumière - Google Patents

Matériels photographiques couleurs à l'halogénure d'argent sensibles à la lumière Download PDF

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Publication number
EP0107112A2
EP0107112A2 EP83109820A EP83109820A EP0107112A2 EP 0107112 A2 EP0107112 A2 EP 0107112A2 EP 83109820 A EP83109820 A EP 83109820A EP 83109820 A EP83109820 A EP 83109820A EP 0107112 A2 EP0107112 A2 EP 0107112A2
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Prior art keywords
silver halide
group
sensitive
coupler
reaction rate
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EP83109820A
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German (de)
English (en)
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EP0107112A3 (en
EP0107112B1 (fr
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Noboru Sasaki
Seiji Ichijima
Kozo Aoki
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • 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
    • G03C7/32—Colour coupling substances
    • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material
    • 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
    • G03C2007/3034—Unit layer
    • 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
    • G03C7/32—Colour coupling substances

Definitions

  • This invention relates to a silver halide color photographic light-sensitive material and more particularly to a color photographic light-sensitive material for photographing having simultaneously improved graininess and sharpness.
  • a technique for improving graininess is described in U.S. Patent No. 3,726,681 wherein the graininess of a high-sensitive color photographic material is improved by using a coupler having a fast coupling reaction rate in a high-sensitive silver halide emulsion layer and a coupler having a slow coupling reaction rate in a low-sensitive silver halide emulsion layer.
  • a technique for improving sharpness involves using either a compound which forms a dye and also releases a development inhibitor by coupling iwth the oxidation product of a color developing agent as described in U.S. Patent Nos.
  • an MTF value (a value at a certain spatial frequency point on an MTF (modulation transfer function) curve) at a low spatial frequency region, that is to increase a so-called edge effect, without reducing the sensitivity or without increasing the development inhibiting property.
  • MTF curve is described in, for example, Mees, The Theory of the Photographic Process, 3rd edition, page 536 and followings, published by Macmillan Co.).
  • a DIR coupler or a DIR compound capable of releasing a development inhibitor having a high diffusibility (the diffusibility being defined hereinafter) due to a coupling reaction, (hereinafter, the DIR coupler or DIR compound releasing a development inhibitor having a high diffusibility is referred to simply as "a diffusible DIR compound").
  • a primary object of this invention is to simultaneously improve the granularity and the sharpness of a color photographic material.
  • a silver halide color photographic light-sensitive material comprising a support having formed thereon at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, and at least one blue-sensitive silver halide emulsion layer; and at least one of said color-sensitive emulsion layers being composed of plural silver halide emulsion layers (i.e., plural silver halide emulsion layers being snesitive to the same color), the highest-sensitive emulsion layer of said plural emulsion layers containing a high reaction rate coupler, and another layer or at least one of other layers of said plural emulsion layers containing a relatively low reaction rate coupler having a reaction rate in a range of 1/1.3 to 1/15 of that of the foregoing high reaction rate coupler and a diffusible DIR compound.
  • the ordinate is the MTF value, M(u): and the abscissa is spatial frequency u(c/mm).
  • MTF curves are controlled by light scattering, whereas in the low spatial frequency region they are controlled by the edge effect arising from development inhibition.
  • MTF curves change depending on the thicknesses of layers present, e.g., silver halide emulsion layers, from- which light is scattered.
  • the thicker the layers the greater the influence of light scattering becomes. Consequently, MTF curves are greatly lowered in the high spatial frequency region.
  • the edge effect extends to a great distance. Consequently, MTF curves are raised even in the low spatial frequency region.
  • the C-MTF curves of Figure 2 are those obtained by heightening the diffusibility from a to d under the condition that the light scattering does not occur at all and the development inhibiting materials used have the same inhibiting degree. As can be seen therefrom, the higher the diffusibility, the higher the MTF value in the low spatial frequency region.
  • the O-MTF values represent the MTF curve under the condition that there is no edge effect, but a certain level of light scattering is observed.
  • the actual MTF value is that which is obtained by multiplying the value on the C-MTF curve at each point, M C (u) , by the value on the 0-MTF curve at the corresponding point, M o (u). Therefore, the resultant MTF curves corresponding to the case that development inhibiting materials which have the same inhibiting degree, but differ only in diffusibility, are employed are as shown in Figure 1.
  • the purpose of increasing the edge effect can be attained by increasing the diffusibility of the development inhibitor released even though the inhibitive property of the development inhibitor is same.
  • the foregoing theory leads a method of improving the reduction of the edge effect by using a diffusible DIR compound-without deteriorating the sensitivity and coupling property, said edge effect reduction accurring at a side reaction in the case of improving the graininess by using a high reaction rate coupler in a high-sensitive silver halide emulsion layer and using a coupler having a reaction rate slower than that of the aforesaid high reaction rate coupler in a low-sensitive silver halide emulsion layer being sensitive to the same color as that of the high-sensitive silver halide emulsion layer.
  • the present invention is a silver halide color photographic light-sensitive material comprising a support having formed thereon at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, and at least one blue-sensitive silver halide emulsion layer; and at least one of said color-sensitive emulsion layers being composed of plural silver halide emulsion layers (i.e., plural silver halide emulsion layers being sensitive to the same color), the highest-sensitive emulsion layer of said plural emulsion layers containing a high reaction rate coupler, and another layer or at least one of other layers of said plural emulsion layers containing a relatively low reaction rate coupler having a reaction rate in a range of 1/1.3 to 1/15, preferably 1/1.5 to 1/10 of that of the foregoing high reaction rate coupler and a diffusible DIR compound.
  • the low-sensitive silver halide emulsion layer may be a lower sensitive emulsion layer of a double layer type silver halide emulsion layers being sensitive to the same color, or may be an intermediate sensitive emulsion layer or a lowest sensitive emulsion layer of a triple layer type silver halide emulsion layers being sensitive to the same color.
  • high reaction rate couplers used in the high-sensitive silver halide emulsion layer may be used solely or as a mixture of them, or may be a mixture of the high reaction rate coupler with a low reaction rate coupler if the mixture does not lose the high reactivity.
  • the low-sensitive silver halide emulsion layer containing a low reaction rate coupler may contain a high reaction rate coupler in an amount of 30% or less.
  • the amount of the diffusible DIR compound used in the low sensitive silver halide emulsion layer of this invention is 0.0001 mole to 0.05 mole, preferably 0.0003 to 0.01 mole, per mole of silver halide used in the low sensitive silver halide emulsion layer.
  • a conventional DIR coupler capable of releasing a development inhibitor having relatively less diffusibility or a precursor thereof may be used in the same low-sensitive silver halide emulsion layer or a different silver halide emulsion layer.
  • the activity of the DIR compound i.e., the activity of the diffusible DIR compound of-the present invention and also the activity of the conventional DIR compound
  • the amount of the diffusible DIR compound used in the low sensitive emulsion layer is 0.001 to 0.3 moles, preferably 0.005 to 0.1 mole, per mole of the low reaction rate coupler.
  • the addition amounts of the high reaction rate coupler and the low reaction rate coupler are 0.001 to 0.5 g/m 2 and 0.2 to 2 g/m 2 , preferably 0.005 to 0.5 g/m 2 and 0.5 to 2 g/m2, respectively.
  • the coupling reactivity (i.e., coupling reaction rate) of the high reaction rate coupler and the low reaction rate coupler are determined as relative value with using a different dye forming coupler as a standard (i.e., coupler N used herebelow). That is, a coupler M (of which coupling reaction rate should be determined) is mixed with a standard coupler N wherein the coupler M and the coupler N provide different dyes which can be clearly separated from each other. The mixture of the couplers M and N is added to a silver halide emulsion layer followed by color development to form a color image. The amounts of each dye formed in the color image are measured and, therefrom, the coupling reactivity of the coupler M is determined as a relative value in the following manner.
  • the silver halide emulsion containing a mixture of the couplers M and N is step-wise exposed and followed by color development to obtain several sets of DM and DN.
  • the combinations of DM and DN obtained are plotted as log(1-D D ) onto a graph of two axis perpen- max dicularly intersecting each other to obtain a straight line.
  • the coupling activity ratio RM/RN is obtained from the inclination of the straight line.
  • the following magenta coupler was used as the coupler N.
  • the following cyan coupler was used as the coupler N.
  • the magnitude of the diffusibility of a development inhibitor can be measured in the following manner.
  • sample A The other sensitive material (Sample A) was prepared in the same manner as Sample B except that the silver iodobromide emulsion which was incorporated in the second layer of Sample B was not present in the second layer of Sample A.
  • Sample A and Sample B each was subjected to wedgewise exposure and to development processing in the same manner as in the Example 1 except that the development time was changed to 2 minutes and 10 seconds.
  • different kinds of development inhibitors were added to the same developing solution as used in the Example 1 independently in such amounts that the image density of Sample A was reduced to one-half that obtained in the former experiment.
  • Sample B was examined for magnitudes of reduction of image densities. Degrees of reduction of image densities in Sample B are used as a measure of the diffusibility of the development inhibitor in the silver halide emulsion layer. The thus obtained results are set forth in Table 1.
  • a ratio of the reaction rate of the low reaction rate coupler to that of the high reaction rate coupler is in a range of 1/1.3 to 1/15, it is preferred to use a DIR compound capable of releasing, as a splitting-off group, a development inhibitor having a diffusibility of 0.4 or more.
  • DIR couplers capable of releasing highly diffusible development inhibitors having diffusibilities of 0.4 or more are DIR couplers represented by the following general formula (I): wherein A represents a coupler component, m represents 1 or 2, and-Y represents a group which is attached to the coupler component A at the coupling position thereof and can be eliminated from the coupler by reaction with the oxidation product of a color developing agent to produce a highly diffusible development inhibitor or a precursor capable of releasing a highly diffusible development inhibitor.
  • A represents a coupler component
  • m represents 1 or 2
  • -Y represents a group which is attached to the coupler component A at the coupling position thereof and can be eliminated from the coupler by reaction with the oxidation product of a color developing agent to produce a highly diffusible development inhibitor or a precursor capable of releasing a highly diffusible development inhibitor.
  • R 1 represents an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an alkoxycarbonyl group, a thiazolylideneamino group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, an N-alkylcarbamoyl group, an N,N-dialkylcarbamoyl group, a nitro group, an amino group, an N-arylcarbamoyloxy group, a sulfamoyl group, an N-alkylcarbamoyloxy group, a hydroxy group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group or an aryloxycarbonylamino group
  • n 1 or 2.
  • two R 1 's may be the same or different, and the number of carbon atoms contained in n R 1 's is 0 to 10 in total.
  • n R l 's contain no carbon atoms (for example, R l is a nitro group), the number of carbon atoms is 0 in total
  • R 2 represents an alkyl group, an aryl group or a heterocyclic group.
  • R 3 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group
  • R 4 represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkanesulfonamido group, a cyano group, a heterocyclic group, an alkylthio group or an amino group.
  • alkyl groups represented by R 1 , R 2 , R 3 or R 4 include both substituted and non-substituted ones. They may have a chain form or a cyclic form. Substituents for such alkyl groups include a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl-group, a carbamoyl group, a hydroxy group, an alkanesulfonyl group, an arylsulfonyl group, an alkylthio group, an arylthio group and so on.
  • Aryl groups represented by R 1 , R 2 , R 3 or R 4 may also have substituents. Suitable examples of such substituents include an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, a nitro group, an amino group, a sulfamoyl group, a hydroxy group, a carbamoyl group, an aryloxycarbonylamino group, an alkoxycarbonylamino group, an acylamino group, a cyano group, a ureido group and so on.
  • R 1 , R 2 , R 3 or R 4 represents a heterocyclic group
  • a hetero atom of such a group may be a nitrogen atom, an oxygen atom or a sulfur atom.
  • a heterocyclic ring of such a group may be a 5-membered ring, 6-membered ring, or a condensed ring containing such a ring.
  • heterocyclic groups include a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group, a thiazolyl group, a triazolyl group, a benzotriazolyl group, an imido group, an oxazinyl group and the like.
  • These groups may be further substituted with substituents set forth as examples of those for the above-described aryl groups.
  • R 2 can contain 1 to 15 carbon atoms.
  • Y in general formula (I) may be represented by the following general formula (VI): wherein the TIME moiety is attached to the coupler moiety at the coupling position thereof, can split off by reaction with a color developing agent, and after elimination from the coupler moiety, it can release the INHIBIT group with controlling the releasing time properly; and the INHIBIT moiety released becomes a development restrainer.
  • a -TIME-INHIBIT group in general formula (VI) can be specifically illustrated by the following general formulae (VII) to (XIII):
  • R 5 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an anilino group, an acylamino group, a ureido group, a cyano group, a nitro group, a sulfonamido group, a sulfamoyl group, a carbamoyl group, an aryl group, a carboxy group, a sulfo group, a hydroxy group, or an alkanesulfonyl group; in general formulae (VII), (VIII), (IX), (XI) and (XIII), l represents 1 or 2; in general formlae (VII), (XI), (XII) and (XIII), k represents 0, 1 or 2; in general formulae (VII), (X) and (XI
  • the number of carbon atoms contained in l, R 5 's per one molecule of general formula (VII) , (VIII) , (IX) (X), (XI), (XII) or (XIII) is 0 to 15 in total.
  • the number of carbon atoms contained in R 6 is 1 to 15.
  • the INHIBIT moiety is represented by general formulae (IIa) , (IIb) , (III), (IV) and (V) except for changing the number of carbon atoms contained in individual general formulae as shown below.
  • the number of carbon atoms contained in the INHIBIT moiety As for the number of carbon atoms contained in the INHIBIT moiety, the number of carbon atoms contained in n R 1 's per one molecule of general formula (IIa), (IIb) or (III) is 1 to 32 in total; the number of carbon atoms contained in R 2 of general formula (IV) is 1 to 32; and the number of carbon atoms contained in R 3 and R 4 of general formula (V) is 1 to 32 in total.
  • R 5 and R 6 represent alkyl groups
  • those alkyl groups may be substituted or unsubstituted, chain or cyclic.
  • Substituents therefor include those which are set forth in the case that R 1 to R 4 represent an alkyl group.
  • R 5 and R 6 represent aryl groups
  • those aryl groups may have substituents. Suitable examples of such substituents include those which are set forth in the case that R 1 to R 4 represent an aryl group.
  • Suitable examples of the yellow color image forming coupler residue represented by A include those of pivaloyl acetanilide type, benzoyl acetanilide type, malonic diester type, malondiamide type, dibenzoylmethane type, benzothiazolyl acetamide type, malonic ester monoamide type, benzothiazolyl acetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, benzimidazolyl acetamide type and benzimidazolyl acetate type; the coupler residues derived from hetero ring-substituted acetamides or hetero ring-substituted acetates involved in U.S.
  • Patent 3,841,880 the coupler residues derived from the acyl acetamides described in U.S. Patent 3,770,446, British Patent 1,459,171, West German Patent Application (QLS) No. 2,503,099, Japanese Patent Application (OPI) No. 139738/75 (the term "OPI” as used herein refers to a "published unexamined Japanese patent application") and Research Disclosure, No. 15737; and the hetero ring type coupler residues described in U.S. Patent 4,046,574.
  • magenta color image forming coupler residue represented by A include coupler residues having 5-oxo-2-pyrazoline nuclei, pyrazolo-[1,5-a]benzimidazole nuclei or cyanoacetophenone type coupler residues.
  • cyan color image forming coupler residue represented by A include the coupler residues having a phenol nucleus or an ⁇ -naphthol nucleus.
  • couplers Even if couplers cannot produce dyes substantially after they couple with an oxidation product of a developing agent and release development inhibitors, they can exhibit their effects as DIR couplers to the same extent as the above-described color compound forming couplers.
  • Examples of the above-described type of coupler residue represented by A include those which are described in U.S. Patents 4,052,213, 4,088,491, 3,632,345, 3,958,993 and 3,961,959.
  • a in the general formula (I) may represent a residue having the following general formula (IA), (IIA), (IHA), (IVA) (VA), (VIA), (VIIA) or (VIIIA):
  • R 11 represents an aliphatic group, an aromatic group, an alkoxy group or a heterocyclic group
  • R 12 and R 13 each represents an aromatic group or a heterocyclic group.
  • Aliphatic groups represented by R 11 are preferably those containing 1 to 22 carbon atoms, and may have substituents or not, and further, may have a chain form or a cyclic form.
  • Preferable substituents therefor include an alkoxy group, an aryloxy group, an amino group, an acylamino group, a halogen atom and so on, which each may further have a substituent(s).
  • aliphatic groups useful as R 11 include an isopropyl group, an isobutyl group, a tert-butyl group, an isoamyl group, a tert-amyl group, a 1,1-dimethylbutyl group, a 1,1-dimethylhexyl group, a 1,1-diethylhexyl group, a dodecyl group, a hexadecyl group, an octadecyl group, a cyclohexyl group, a 2-methoxy- isopropyl group, a 2-phenoxvisopronyl group, a 2-p-tert-butylphenox.yisooropyl group, an a-aminoisopropyl group, an ⁇ -(diethylamino)isopropyl group, an ⁇ -(succinimido)-isopropyl group, an ⁇ -(phthalo
  • R 11 , R 12 or R 13 represents an aromatic group (especially a phenyl group), it may have a substituent.
  • Such an aryl group as phenyl or the like may be substituted with a 32 or less carbon atoms containing alkyl, alkenyl, alkoxy, alkoxycarbonyl, alkoxycarbonylamino, aliphatic amido, alkylsulfamoyl, alkylsulfonamido, alkylureido, alkyl-substituted succinimido or like group.
  • the alkyl group therein may include one which contains an aromatic group such as phenylene in its main chain.
  • a phenyl group represented by R 11 , R 12 or R 13 may be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group, an arylureido group or the like, the aryl moiety of which groups each may be substituted with one or more alkyl groups wherein the number of carbon atoms is 1 to 22 in total.
  • a phenyl group represented by R 11 R 12 or R 13 may be substituted with an amino group which includes one containing a lower (C 1 to C 6 ) alkyl group as a substituent, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group or a halogen atom.
  • R 11' R 12 or R 13 may represent a substituent formed by condensing a phenyl group and another ring, such as naphthyl, quinolyl, isoquinolyl, chromanyl, coumaranyl, tetrahydronaphthyl or the like. These substituents may further have substituents in themselves.
  • R 11 represents an alkoxy group
  • the alkyl moiety thereof represents a C i to C 40 , preferably C, to C 22 , straight chain or branched chain alkyl, alkenyl, cycloalkyl or cycloalkenyl group, which each may be substituted with a halogen atom, an aryl group, an alkoxy group or so on.
  • R 11 , R 12 or R 13 represents a heterocyclic group
  • the heterocyclic group is bonded to the carbon atom of the acyl moiety or the nitrogen atom of the amido moiety of an a-acylacetamido group through one of the carbon atoms forming the ring.
  • a heterocyclic ring mention may be made of thiophene, furan, pyran, pyrrole, pyrazole, pyridine,. pyrazine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, oxazine and the like. These rings may further have substituents on the individual rings.
  • R 15 in the general formula (IVA) represents a C 1 to C 40 , preferably C 1 to C 22 , straight chain or branched chain alkyl (e.g., methyl, isopropyl, tert-butyl, hexyl, dodecyl, etc.), alkenyl (e.g., allyl, etc.), cyclic alkyl (e.g., cyclopentyl, cyclohexyl, norbornyl, etc.), aralkyl (e.g., benzyl, ⁇ -phenylethyl, etc.), cyclic alkenyl (e.g., cyclopentenyl, cyclohexenyl, etc.), or like group, which groups each may be substituted with a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an alkylthio
  • R 15 in general formula (IVA) may further represent an aryl group (e.g., phenyl, a- or ⁇ -naphthyl, etc.).
  • the aryl group may have one or more substituents. Specific examples of such a substituent include an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido group,
  • R 15 are phenyl groups which are substituted by an alkyl group, an alkoxy group, a halogen atom or the like at at least one of the o-positions, because they can contribute to reduction of photocoloration or thermocoloration of couplers remaining in film layers.
  • R 15 may represent a heterocyclic ring residue (e.g., a 5- or 6-membered heterocyclic one containing as a hetero atom a nitrogen atom, an oxygen atom or a sulfur atom, or the condensed ring residues thereof, with specific examples including pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl, naphthoxazolyl, etc.), a heterocyclic ring residue substituted with one of substituents set forth as examples for the above-described aryl group, an aliphatic or an aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group, or an arylthiocarbamoyl group.
  • a heterocyclic ring residue e.g.,
  • R 14 in formula (IVA) or (VA) represents a hydrogen atom, a C 1 to C 40 , preferably C 1 to C 22 , straight chain or branched chain alkyl, alkenyl, cyclic alkyl, aralkyl or cyclic alkenyl group (which each may have one of the substituents set forth as examples for the above-described substituent R 15 ), an aryl group or a heterocyclic ring residue (which each also may have one of the substituents set forth as examples for the above-described substituent R 15 ), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, stearyloxy- carbonyl, etc.), an aryloxycarbonyl group (e.g., phenoxycarbonyl, naphthoxycarbonyl, etc.), an aralkyloxycarbonyl group (e.g., benzyloxycarbonyl, etc.), an alkoxy group (e
  • ethylcarbamoyl dimethylcarbamoyl, N-methylphenyl- carbamoyl, N-phenylcarbamoyl, etc.
  • a sulfamoyl group e.g., N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N-arylsulfamoyl, N-alkyl-N-arylsulfamoyl, N,N-diarylsulfamo y l, etc.
  • a cyano group e.g., N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N-arylsulfamoyl, N-alkyl-N-arylsulfamoyl, N,N-diarylsulfamo y l, etc.
  • a cyano group e.g., N-alky
  • R 17 in general formula (VA) represents a hydrogen atom, or a C 1 to C 32 , preferably C 1 to C 22 , straight chain or branched chain alkyl, alkenyl, cycloalkyl, aralkyl or cyclic alkenyl group, which each may have one of the substituents set forth as an example for the above-described substituent R 15 .
  • R 17 may represent an aryl group or a heterocyclic residue, which each may have one of the substituents set forth as examples for the above-described substituent R 15 .
  • R 17 mav represent a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-arylanilno group, an N-alkylanilino group, an N-acylanilino group, a hydroxy group or a mercapto group.
  • Substituents R 18 , R 19 and R 20 include groups which have been employed in conventional 4-equivalent type phenol or a-naphthol couplers.
  • substituent R 18 represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon residue, an acylamino group, an -O-R 21 group or an -S-R 21 group (wherein R 21 is an aliphatic hydrocarbon residue).
  • R 21 is an aliphatic hydrocarbon residue.
  • Substituents R 19 and R 20 include aliphatic hydrocarbon residues, aryl groups and heterocyclic ring residues. Either of then may be a hydrogen atom. The above-described substituents may further have certain substituents. Furthermore, R 19 and R 20 may combine with each other and form a nitrogen-containing heterocyclic nucleus. l represents an integer of 1 to 4, m'represents an integer of 1 to 3, and n represents an integer of 1 to 5.
  • the above-described aliphatic hydrocarbon residues include both saturated and unsaturated ones, which each may have a straight chain form, a branched chain form or a cyclic form, with preferable examples including an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.) and an alkenyl group (e.g., allyl, octenyl, etc.).
  • an alkyl group e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.
  • an alkenyl group e.g
  • aryl group is a phenyl group, a naphthyl group or the like.
  • Representatives of the above-described heterocyclic ring residues are pyridinyl, quinolyl, thienyl, piperidyl, imidazolyl and the like.
  • aliphatic hydrocarbon residues, aryl groups and hetero ring residues each may be substituted by a halogen atom, a nitro group, a hydroxy group, a carboxy group, an amino group, a substituted amino group, a sulfo group, an alkyl group, an alkenyl group, an aryl group, a hetero ring residue, an alkoxy group, an aryloxy group, an arylthio group, an arylazo group, an acylamino group, a carbamoyl group, an ester residue, an acyl group, an acyloxy group, a sulfonamido group, a sulfamoyl group, a sulfonyl group, a morpholino group, etc.
  • Substituents R 11 , R 12 , R 13 , R 14 , R 15 , R 17' R 18 , R 19 and R 20 in the couplers represented by general formulae (IA) to (VIIIA) may combine with their respective corresponding substituents, or one of them may become a divalent group to form a symmetric or an asymmetric complex coupler.
  • DIR couplers which can be effectively used in the present invention are illustrated below.
  • the diffusibilities of the DIR couplers employed in the present invention are preferably about 0.4 or more. More preferably, the diffusibilities are not higher than about 1.0. When the diffusibilities are extremely heightened, the visual sharpness tends to decrease.
  • a known method such as the method as described in U.S. Patent 2,322,027, etc., may be used.
  • a high-boiling organic solvent such as a phthalic acid alkyl ester (e.g., dibutyl phthalate, dioctyl phthalate, etc.), a phosphoric acid ester (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctylbutyl phosphate, etc.), a citric acid ester (e.g., tributyl acetylcitrate, etc.), a benzoic acid ester (e.g., octyl benzoate, etc.), an alkylamide (e.g., diethyllaurylamide, etc.), a fatty acid ester (
  • a dispersion method by a polymer as described in Japanese Patent Publication No. 39,853/'76 and Japanese Patent Application (OPI) No. 59,943/'76 can be used for the incorporation of the coupler.
  • the coupler has an acid group such as a carboxylic acid and sulfonic acid
  • the coupler is introduced into a hydrophilic colloid as an alkaline aqueous solution thereof.
  • Binders or protective colloids which can be used to advantage in preparing photographic emulsions include conventional gelatins. However, other conventional hydrophilic colloids can be also used herein.
  • hydrophilic colloids examples include proteins such as gelatin derivatives, graft polymers obtained by grafting other high polymers onto gelatin, albumin, casein, etc.; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates and the like; sugar derivatives such as sodium alginate, starch derivatives, etc.; and synthetic hydrophilic high molecular weight polymers such as polyvinyl alcohol, partially acetylated polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl- imidazole, polyvinylpyrazole, copolymers containing repeating units which constitute the above-described polymers, and so on.
  • proteins such as gelatin derivatives, graft polymers obtained by grafting other high polymers onto gelatin, albumin, casein, etc.
  • cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose,
  • gelatins which can be used are not only lime-processed gelatin, but also acid-processed gelatin, enzyme-processed gelatin as described in Bull. Soc. Sci. Phot Japan, No. 16, p. 30 (1966) and, further- hydrolysis products and enzymatically decomposed products of gelatins.
  • Gelatin derivatives which can be used include those obtained by reacting gelatin with various kinds of compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sulfones, vinylsulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds and so on. Specific examples thereof are disclosed in U.S. Patents 2,614,928, 3,132,945, 3,186,846 and 3,312,553, British Patents 861,414, 1,033,189 and 1,005,784, Japanese Patent Publication No. 26845/67, and so on.
  • the foregoing gelatin graft polymers include the graft polymers formed by grafting homo- or copolymer of a vinyl monomer or monomers such as acrylic acid, methacrylic acid, or the derivatives thereof such as the esters, the amides, etc., acrylonitrile, styrene, etc., to gelatin.
  • the graft polymers .formed by grafting a polymer having a compatibility with gelatin to some extent, such as the polymer of acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylate, etc., to gelatin are preferred. Examples of these graft polymers are described in U.S. Patent Nos. 2,763,625, 2,831,767, 2,956,884, etc.
  • Typical examples of synthetic hydrophilic high polymers which can be used are those described in West German Patent Application (OLS) No. 2,312,708, U.S. Patents 3,620,751 and 3,879,205, and Japanese Patent Publication No. 7561/68.
  • Silver halides which can be present in photographic emulsion layers of photographic materials employed in the present invention are conventional and include silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride.
  • Preferable silver halides are silver iodobromides containing 15 mol% or less of iodide.
  • Especially preferred ones are silver iodobromides containing 2 to 12 mol% of silver iodide.
  • Silver halide grains in the photographic emulsion may have any conventional mean grain size (the grain size being defined as grain diameter if the grain has a spherical or a nearly spherical form and as a length of the edge if the grain has a cubic form, and being averaged based on projected areas of the grains).
  • the mean grain size is 3 ⁇ or less.
  • Grain size distribution may be either narrow or broad.
  • Silver halide grains in the photographic emulsion may have a regular crystal form such as that of a cube, an octahedron or so on, an irregular crystal form such as that of. a sphere, a plate or so on, or a composite form thereof. Also, silver halide grains may be a mixture of grains having various kinds of crystal forms.
  • the individual silver halide grains may comprise a core and an outer shell or may be homogeneous. In addition, they may have a surface where a latent image has been formed to an appreciable extent, or may be grains where a latent image is predominantly formed in the interior thereof.
  • Photographic emulsions employed in the present invention can be prepared using conventional methods as described in P. Glafkides, Chimie et Physique Photo- graphique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman, et al., Making and Coating Photographic Emulsion, The Focal Press, London (1964), and so on. That is, photographic emulsions can be prepared using the acid process, the neutral process, the ammonia process, or so on. Suitable methods for reacting a water-soluble silver salt with a water-soluble halide include a single jet method, a double jet method, a combination thereof, and so on.
  • a method in which silver halide grains are produced in the presence of excess silver ions can be employed.
  • the so-called controlled double jet method in which the p Ag of the liquid phase wherein silver halide grains are to be precipitated is maintained constant, may be employed.
  • Two or more silver halide emulsions prepared separately may also be employed in the form of mixture.
  • cadmium salts zinc salts, lead salts, thallium salts, iridium salts or complexes, rhodium salts or complexes, iron salts or complexes and/or the like may be present.
  • Silver halide emulsions having any grain size distribution may be employed in this invention.
  • a silver halide emulsion having a wide grain size distribution (called as "poly-dispersed emulsion) may be used or several kinds of mono-dispersed silver halide emulsion having a narrow grain size distribution (the mono-dispersed silver halide emulsion in this specification is a silver halide emulsion wherein more than 90% of the weight or number of total silver halide grains.is included in the size range within +40% of the mean grain size) may be used as a mixture of them.
  • a mixture of the mono-dispersed emulsion and the poly-dispersed emulsion may be used.
  • a mono-dispersed emulsion for a high sensitive silver halide emulsion layer may be used.
  • the mono-dispersed silver halide emulsion may having a uniform composition and property throughout the inside and the surface thereof or may be a so-called core-shell structure having different composition and property between the inside and surface thereof.
  • a silver halide emulsion layer may be a double layer type silver halide emulsion layer composed of a high-sensitive emulsion layer and a low-sensitive emulsion, or may be a triple layer type silver halide emulsion layer composed of a high-sensitive emulsion layer, an intermediate-sensitive emulsion layer and a low-sensitive emulsion layer.
  • Removel of the soluble salts from the silver halide emulsion after the formation of silver halide grains or after physical ripening can be effected using the noodle washing method (which comprises gelling the gelatin), or using a sedimentation process (thereby causing flocculation in the emulsion) using an inorganic salt, an anionic surface active agent, an anionic polymer (e.g., polystyrenesulfonic acid), or a gelatin derivative (e.g., acylated gelatin, carbamovlated gelatin, etc.).
  • the noodle washing method which comprises gelling the gelatin
  • a sedimentation process thereby causing flocculation in the emulsion
  • an inorganic salt an anionic surface active agent
  • an anionic polymer e.g., polystyrenesulfonic acid
  • a gelatin derivative e.g., acylated gelatin, carbamovlated gelatin, etc.
  • the silver halide emulsion prefferably be chemically sensitized.
  • Chemical sensitization can be carried out using processes as described in, e.g., H. Frieser, Die Gründlagen der Photographischen Sawe mit Silberhalogeniden, pp. 675-734, Akademische Verlagsgesellschaft (1968).
  • sulfur sensitization using compounds containing sulfur capable of reacting with active gelatin or silver ions e.g., thiosulfates, thioureas, mercapto compounds, rhodanines, etc.
  • reduction sensitization using reducing materials e.g., stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, etc.
  • noble metal sensitization using noble metal compounds e.g., gold complexes, and complexes of Periodic Table Group VIII metals such as Pt, Ir, Pd, etc.
  • noble metal compounds e.g., gold complexes, and complexes of Periodic Table Group VIII metals such as Pt, Ir, Pd, etc.
  • Photographic emulsions employed in the present invention can contain various conventional compounds for the purpose of preventing fog in preparation, storage or photographic processing, or for stabilizing photographic properties.
  • Specific examples of such compounds include azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles and benzimidazoles (especially nitro- or halogen-substituted ones); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole) and mercaptopyrimidines; the above-described heterocyclic mercapto compounds having water-soluble groups such as a carboxyl group, a sulfonyl group or the like; thioketo compounds such as oxazoline- thione; azaindenes such
  • Photographic emulsions or other hydrophilic colloidal layers of the light-sensitive materials of the present invention may contain various kinds of surface active agents for a wide variety of conventional purposes, for example, as a coating aid, prevention of static charges, improvement in a slipping property, emulsifying dispersions, prevention of adhesion, improvement in photographic characteristics (e.g., development acceleration, increase in contrast, sensi- tization, etc.), and so on.
  • surface active agents for a wide variety of conventional purposes, for example, as a coating aid, prevention of static charges, improvement in a slipping property, emulsifying dispersions, prevention of adhesion, improvement in photographic characteristics (e.g., development acceleration, increase in contrast, sensi- tization, etc.), and so on.
  • surface active agents which can be used include nonionic surface active agents such as saponin (steroid type), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol/ polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitol esters, polyalkylene glycol alkylamines or polyalkylene glycol alkylamides, polyethylene oxide adducts of silicone, etc.), glycidol derivatives (e.g., alkenyl- succinic polyglycerides, alkylphenyl polyglycerides, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and so on; anionic surface active agents containing acidic groups such as carboxyl, sulfo, phospho, sulfate, phosphate and like groups, e.g., alkylene
  • the photographic emulsions of the present invention may contain, for example, polyalkylene oxides and derivatives thereof such as the ethers, esters and amines thereof, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones and so on in order to increase the sensitivity and the contrast thereof, or in order to accelerate the developing rate thereof.
  • polyalkylene oxides and derivatives thereof such as the ethers, esters and amines thereof, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones and so on in order to increase the sensitivity and the contrast thereof, or in order to accelerate the developing rate thereof.
  • polyalkylene oxides and derivatives thereof such as the ethers, esters and amines thereof, thioether compounds, thiomorph
  • the photographic emulsions or other hydrophilic colloidal layers of photographic materials used in the practice of the present invention can contain dispersions of water-insoluble or slightly soluble synthetic polymers for the purpose of improving dimensional stability and so on.
  • polymers include those having as monomer components alkyl(meth)acrylate, alkoxyalkyl(meth)acrylate, glycidyl(meth)acrylate, (meth)acrylamide, vinyl ester (e.g., vinyl acetate), acrylonitrile, olefin and styrene, individually or as combinations of two or more thereof, or a combination of one of the above-described monomers and acrylic acid, methacrylic acid, an ⁇ , ⁇ -unsaturated dicarboxylic acid, a hydroxyalkyl(meth)acrylate, a sulfoalkyl(meth)acrylate, styrenesulfonic acid, or so on.
  • a method where a developing agent is contained in the light-sensitive material, e.g., in an emulsion layer, and the sensitive material is treated in an aqueous alkaline solution to effect development may be employed.
  • Developing agents which are hydrophobic can be incorporated in emulsion layers using various methods as described in, e.g., Research Disclosure, No. 169 (RD-16928), U.S. Patent 2,739,890, British Patent 813,253, West German Patent 1,547,763, and so on.
  • Such development processing may be carried out in combination with silver salt stabilizing processing using a thiocyanate.
  • a conventional fixing solution can be used.
  • fixing agents which can be used include not only thiosulfates and thiocyanates, but also organic sulfur compounds which are known to have a fixing effect.
  • the fixing solution may contain water-soluble aluminum salts as a hardener.
  • Dye images can be formed using conventional methods, for example, the negative-positive method (described in Journal of the Society of Motion Picture and Television Engineers, Vol. 61, pp. 667-701 (19 5 3) and so on).
  • the color developing solution is conventional and generally comprises an alkaline aqueous solution containing a color developing agent.
  • color developing agents include known aromatic primary amine developers such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethyl- aniline, 4-amino-3-methyl-N-ethyl-N-3-methoxyethyl- aniline, etc.).
  • aromatic primary amine developers such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amin
  • the color developing solution can additionally contain a pH buffer, a development inhibitor and an anti-foggant.
  • a pH buffer e.g., a pH buffer
  • a development inhibitor e.g., a water softener, a-preservative, an organic solvent, a development accelerator, dye forming couplers, competing couplers, a fogging agent, an assistant developer, a viscosity imparting agent, a polycarboxylic acid series chelating agent, an antioxidant, and so on.
  • bleaching agents which can be used include compounds of polyvalent metals, such as Fe (III), Co (III), Cr (VI), Cu (II) and the like; peroxy acids, quinones, nitroso compounds and so on.
  • bleaching agents which can be used include ferricyanides; bichromates; complex salts formed by Fe (III) or Co (III) and aminopolycarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetate, 1,3-diamino-2-propanol tetraacetic acid, etc., or organic acids such as citric acid, tartaric acid, malic acid, etc.; persulfates and permanganates; nitrosophenol; and so on.
  • potassium ferricyanide, sodium (ethylenediamine- tetraacetato)ferrate (III) and ammonium (ethylenediamine- tetraacetato)ferrate (III) are especially useful.
  • the (ethylenediaminetetraacetato)iron (III) complexes are useful in both an independent bleaching solution and a combined bleach-fix bath.
  • the bleaching or the bleach-fix bath can contain a bleach accelerating agent as described in U.S. Patents 3,042,520 and 3,241,966, Japanese Patent Publication Nos. 8506/70 and 8836/70, and so on, thiol compounds described in Japanese Patent Application (OPI) No. 65732/78, and other various kinds of additives.
  • a bleach accelerating agent as described in U.S. Patents 3,042,520 and 3,241,966, Japanese Patent Publication Nos. 8506/70 and 8836/70, and so on, thiol compounds described in Japanese Patent Application (OPI) No. 65732/78, and other various kinds of additives.
  • Photographic emulsions employed in the present invention may be spectrally sensitized with methine dyes and others.
  • sensitizing dyes may be employed solely or as a combination of two or more thereof. Combinations of sensitizing dyes are frequently employed for the purpose of supersensitization. Typical examples of supersensitizing combinations are described in U.S. Patents 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,814,609 and 4,026,707, British Patent 1,344,281, Japanese Patent Publication Nos. 4936/68 and 12375/83, Japanese Patent Application (OPI) Nos. 110618/77 and 109925/77, and so on.
  • OPI Japanese Patent Application
  • photographic emulsion layers and other layers are coated on a conventional flexible support such as a plastic film, paper, cloth or the like, or a rigid support such as glass, ceramic, metal or the like.
  • flexible support which can be used to advantage include films made from semi-synthetic or synthetic high molecular weight polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.; and paper coated or laminated with a baryta layer or an a-olefin polymer (e.g., polyethylene, polypropylene, an ethylene-butene copolymer, etc.).
  • a baryta layer or an a-olefin polymer e.g., polyethylene, polypropylene, an ethylene-butene copolymer, etc.
  • Supports may be colored with dyes or pigments. Further, they may be rendered black for the purpose of shielding light.
  • the surfaces of these supports are, in general, subjected to a subbing treatment to increase adhesiveness to photographic emulsion layers. Before or after receiving the subbing treatment, the surfaces of the support may be subjected to a corona discharge treatment, an ultraviolet irradiation treatment, a flame treatment, or so on.
  • photographic emulsion layers and other layers can be coated on a support or other layers using conventional coating methods.
  • coating methods include dip coating, roller coating, curtain coating, extrusion coating, and so on.
  • the methods disclosed in U.S. Patents 2,681,234, 2,761,791 and 3,526,528 can be used to advantage in coating such layers.
  • the present invention can be applied to a multilayer multicolor photographic material having layers of at least two different spectral sensitivities on the support.
  • a multilayer color photographic material usually has at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support.
  • the order of these layers can be arbitrarily selected. It is general, however, to incorporate a cyan forming coupler in a red-sensitive emulsion layer, a magenta forming coupler in a green-sensitive emulsion layer, and a yellow forming coupler in a blue-sensitive emulsion layer.
  • different combinations may be used.
  • the exposure for obtaining a photographic image is carried out in a conventional manner.
  • Any known light sources including natural light (sunlight), a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, a CRT spot and so on can be employed for exposure.
  • Suitable exposure times which can be used include not only exposure times commonly used in cameras ranging from about 1/1,000 to about 1 sec., but also exposure times shorter than 1/1,000 sec., for example, about 1/104 to about 1/10 6 sec. as with xenon flash lamps and cathode ray tubes. Exposure times longer than 1 second can also be used. The spectral distribution of the light employed for the exposure can be controlled using color filters, if desired. Laser beams can also be employed for exposure. Moreover, the emulsions of the present invention may also be exposed to light emitted from phosphors excited by electron beams, X-rays, ,-rays, a-rays and the like.
  • conventional color forming couplers that is, compounds capable of forming colors by oxidative coupling with aromatic primary amine developers (e.g., phenylenediamine derivatives, aminophenol derivatives, etc.) in color development processing may be used in combination with the high reaction rate or low reaction rate coupler, or may be used independently of the high reaction rate or low reaction rate coupler by addition to a layer not containing the high reaction rate or low reaction rate coupler.
  • aromatic primary amine developers e.g., phenylenediamine derivatives, aminophenol derivatives, etc.
  • magenta couplers examples include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcumarone couplers, open- chain acylacetonitrile couplers and so on.
  • yellow couplers examples include acylacetamide couplers (e.g., benzoyl acetanilides, pivaloyl acetanilides, etc.), and so on.
  • cyan couplers examples include naphthol couplers, phenol couplers, and so on. These couplers can provide desirable results when they have hydrophobic groups (ballast groups) in their molecules and are thereby rendered non-diffusible.
  • couplers may be 4-equivelent or 2-equivalent. Moreover, they may be colored couplers having a color correcting effect, or couplers capable of releasing development restrainers with the progress of development (conventional DIR couplers). In addition to conventional DIR couplers, conventional colorless DIR coupling compounds which yield colorless products upon coupling and release development restrainers may be used.
  • colored couplers which can be used in the present invention are described in, e.g., U.S. Patents 3,476,560, 2,521,908 and 3,034,892, Japanese Patent Publication Nos. 2016/69, 22335/63, 11304/67 and 32461/69, Japanese Patent Application (OPI) Nos. 26034/76 and 42121/77, and West German Patent Application (OLS) No. 2,418,959.
  • conventional compounds capable of releasing development restrainers with the progress of development may be incorporated in the light-sensitive materials. Specific examples thereof are described in, e.g., U.S. Patents 3,297,445 and 3,379,52.9, West German Patent Application (OLS) No. 2,417,914, and Japanese Patent Application (OPI) Nos. 15271/77 and 9116/78.
  • photographic emulsion layers and other hydrophilic colloidal layers may contain inorganic or organic hardeners.
  • specific examples thereof include chromium salts (e.g., chromium alum, chromium acetate, etc.), aldehydes (e.g., formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (e.g., dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (e.g., 2,3-dihydroxydioxane, etc.), active vinyl compounds (e.g., 1,3,5-triacryloyl-hexahydro-s-triazine, 1,3 - vinylsulfonyl-2-propanol, etc.), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen
  • hydrophilic colloidal layers of the photographic materials of the present invention contain dyes and ultraviolet absorbents
  • they may be mordanted by cationic polymers and the like.
  • Specific examples of such polymers are described in, e.g., British Patent 685,475, U.S. Patents 2,675,316, 2,839,401, 2,882,156, 3,048,487, 3,184,309 and 3,445,231, West German Patent Application (OLS) No. 1,914,362, Japanese Patent Application (OPI) Nos. 47624/75 and 71332/75, and so on.
  • the photographic materials prepared in accordance with the present invention may contain a color fo g preventing agent, such as a hydroquinone derivative, aminophenol derivative, gallic acid derivative, ascorbic acid derivative, and the like.
  • a color fo g preventing agent such as a hydroquinone derivative, aminophenol derivative, gallic acid derivative, ascorbic acid derivative, and the like.
  • the hydrophilic colloidal layers of the photographic materials prepared in accordance with the present invention may contain ultraviolet absorbents.
  • ultraviolet absorbents include benzotriazole compounds substituted with aryl groups, 4-thiazolidone compounds, benzophenone compounds, cinnamic acid esters, butadiene compounds, benzoxazole compounds, and, further, ultraviolet absorbing polymers.
  • a polymer ultraviolet absorbent in a latex form is preferably used. These ultraviolet absorbents may be fixed in the foregoing hydrophilic colloidal layers.
  • ultraviolet absorbents are described in U.S. Patents 3,533,794, 3,314,794 and 3,352,681, Japanese Patent Application (OPI) No. 2784/71, U.S. Patents 3,705,805, 3,707,375, 4,045,229, 3,700,455 and 3,499,752, West German Patent Publication 1,547,863, and so on.
  • Hydrophilic colloidal layers of the photographic materials prepared in accordance with the present invention may contain water-soluble dyes for various purposes, e.g., as filter dyes, prevention of irradiation, and so on.
  • water-soluble dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.
  • oxonol dyes, hemioxonol dyes and merocyanine dyes are used to greater advantage.
  • Known discoloration inhibitors can be used in practice of the present invention and, further, color image stabilizing agents can also be used individually or as a combination of two or more thereof.
  • Examples of known discoloration inhibitors include hydrouinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives and bisphenols.
  • hydroquinone derivatives which can be used for the above-described purpose are disclosed in U.S. Patents 2,360,290, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,765, 2,710,801 and 2,816,028, British Patent 1,363,921, and so on.
  • gallic acid derivatives which can be used for the above-described purpose are described in U.S. Patents 3,457,079 and 3,069,262, and so on; p-alkoxyphenols are disclosed in U.S. Patents 2,735,765 and 3,698,909, Japanese Patent Publication Nos. 20977/74 and 6623/77, and so on; p-oxyphenol derivatives are disclosed in U.S. Patents 3,432,300, 3,573,050, 3,574,627 and 3,764,337, Japanese Patent Application (OPI) Nos. 35633/77, 147434/77 and 152225/77, and so on; bisphenols are. disclosed in U.S. Patent 3,700,455.
  • Multilayer color photographic material sample 101 was prepared by coating the layers having the following compositions on a polyethylene terephthalate film support.
  • the 1st layer Antihalation layer (AHL):
  • the 2nd layer Interlayer (ML):
  • the 3rd layer 1st red-sensitive emulsion layer (RL 1 ):
  • the 4th layer 2nd red-sensitive emulsion layer (RL 2 ):
  • the 5th laver Interlayer (ML):
  • the 6th layer lst green-sensitive emulsion layer (GL 1 ):
  • the 8th laver Yellow filter layer (YFL):
  • the 9th layer lst blue-sensitive emulsion layer (BL 1 ):
  • the 11th layer lst protective layer (PL 1 ):
  • the 12th layer 2nd protective layer (PL 2 ):
  • This sample was prepared in the same manner as Sample 101 except that an equivalent mole of Coupler C-4 was used in place of Coupler C-1 in RL 2 and the reduction in sensitivity was compensated by increasing the mean grain size of the silver halide emulsion to 0.70 ⁇ without changing the structure of the mono-dispersed silver iodobromide emulsion.
  • This sample was prepared in the same manner as Sample 101 except that an equivalent mole of Coupler EX-2 was used in place of Coupler D-3 in RL 1 , and an equivalent mole of Coupler C-4 was used in place of Coupler C-l in RL 2 , and the reduction in sensitivity was compensated by increasing the mean grain size of the silver halide emulsion to 0.70 ⁇ without changing the structure of the mono-dispersed silver iodobromide emulsion.
  • the granularity of the cyan color image of each sample was measured by a conventional RMS (Root Mean Square) method.
  • the determination of granularity by the RMS method is well known in the art and is described in Photographic Science and Engineering, Vol. 19, No. 4 pages 235-238 (1975) as a title of "RMS Granularity: Determination of Just Noticeable Difference".
  • the aperture for measurement was 48 ⁇ . Furthermore, the MTF value of each cyan image at a spatial frequency of 7 cycles per mm was measured.
  • the development processing for the photographic material was performed as follows at 38°C.
  • compositions of the processing solution used in the above process were as follows.
  • Sample 104 having a combination of the low reaction rate coupler and the low reaction rate coupler shows a poor granularity at high-density portions.
  • Sample 102 having the low reaction rate coupler and the high reaction rate coupler for improving the granularity shows good granularity but shows a reduced MTF value, that is, sharpness is reduced.
  • the diffusible DIR coupler.of this invention is used in place of the DIR coupler in Sample 102, the MTF value can be improved (Sample 101) without being accompanied by reduction in sensitivity, that is, the granularity and sharpness can be improved at once.
  • This sample was prepared in the same manner as Sample 101 except that an equimolar mole of Coupler 14-1 was used in place of Coupler M-4 in GL 2 of the 7th layer and the increase in sensitivity was corrected by reducing the mean grain size of the silver halide emulsion from 0.60 p to 0.50 p without changing the structure of the silver halide grains.
  • This sample was prepared in the same manner as Sample 101 except that an equimolar mole of Coupler D-3 was used in place of Coupler EX-2 in GL l of the 6th layer, an equimolar mole of Coupler M-1 was used in place of Coupler M-4 in GL 2 of the 7th layer, and the increase in sensitivity was corrected by reducing the mean grain size of the silver halide emulsion in GL 2 of the 7th.layer from 0.60 to 0.50 without changing the structure of the silver halide grains.
  • the magenta image of Sample 203 has excellent granularity from a low density portion to a high density portion and also shows a good MTF value, which shows the superior effects of this invention.
  • Samples 301-304 were prepared in the same manner as Sample 203 except that an equimolar amount of DIR Coupler set forth in Table 3 was used in place of Coupler D-3 in GL 1 of the 6th layer of Sample 203 prepared in
  • each of the samples of this invention has excellent granularity and sharpness.
EP83109820A 1982-09-30 1983-09-30 Matériels photographiques couleurs à l'halogénure d'argent sensibles à la lumière Expired EP0107112B1 (fr)

Applications Claiming Priority (2)

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JP171193/82 1982-09-30
JP17119382A JPS5960437A (ja) 1982-09-30 1982-09-30 ハロゲン化銀カラ−写真感光材料

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EP0107112A3 EP0107112A3 (en) 1984-07-04
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0192199A2 (fr) * 1985-02-16 1986-08-27 Konica Corporation Matériau photographique sensible à la lumière
EP0204416A2 (fr) * 1985-04-24 1986-12-10 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0208502A2 (fr) * 1985-07-01 1987-01-14 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0233641A2 (fr) * 1986-02-20 1987-08-26 Konica Corporation Matériaux photographiques à l'halogénure d'argent sensibles à la lumière
EP0327274A2 (fr) * 1988-01-30 1989-08-09 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière
EP0329016A2 (fr) * 1988-02-19 1989-08-23 Agfa-Gevaert AG Matériau de reproduction photographique couleur
US4963465A (en) * 1989-01-12 1990-10-16 Agfa-Gevaert Aktiengesellschaft Color photographic negative recording material
US5545513A (en) * 1992-05-20 1996-08-13 Eastman Kodak Company Photographic material with improved granularity
EP0898199A1 (fr) * 1997-08-18 1999-02-24 Konica Corporation Produit photographique à l'halogénure d'argent sensible a la lumière
EP1485687A2 (fr) * 2002-02-04 2004-12-15 Ortho-McNeil Pharmaceutical Corporation Technique permettant de se procurer des donnees moleculaires a partir d'un echantillon de produit pharmaceutique et appareil a cet effet

Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
DE3346621A1 (de) * 1983-12-23 1985-07-04 Agfa-Gevaert Ag, 5090 Leverkusen Farbfotografisches aufzeichnungsmaterial und entwicklungsverfahren
US4980267A (en) * 1988-08-30 1990-12-25 Eastman Kodak Company Photographic element and process comprising a development inhibitor releasing coupler and a yellow dye-forming coupler

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DE2018341A1 (fr) * 1969-04-17 1970-11-05
US3726681A (en) * 1969-11-22 1973-04-10 Agfa Gevaert Ag Multilayered color photographic material
DE2600524A1 (de) * 1975-01-08 1976-07-15 Fuji Photo Film Co Ltd Farbphotographisches mehrschichten- aufzeichnungsmaterial
EP0045427A2 (fr) * 1980-08-01 1982-02-10 Agfa-Gevaert AG Matériau d'enregistrement photographique sensible à la lumière et son utilisation pour la production d'images photographiques
DE3209996A1 (de) * 1981-03-20 1982-10-14 Konishiroku Photo Industry Co., Ltd., Tokyo Farbphotographisches silberhalogenid-aufzeichnungsmaterial

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CA1134818A (fr) * 1977-12-23 1982-11-02 Philip T.S. Lau Copulants et emulsions, et elements et procedes photographiques utilisant ceux-ci

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DE2018341A1 (fr) * 1969-04-17 1970-11-05
US3726681A (en) * 1969-11-22 1973-04-10 Agfa Gevaert Ag Multilayered color photographic material
DE2600524A1 (de) * 1975-01-08 1976-07-15 Fuji Photo Film Co Ltd Farbphotographisches mehrschichten- aufzeichnungsmaterial
EP0045427A2 (fr) * 1980-08-01 1982-02-10 Agfa-Gevaert AG Matériau d'enregistrement photographique sensible à la lumière et son utilisation pour la production d'images photographiques
DE3209996A1 (de) * 1981-03-20 1982-10-14 Konishiroku Photo Industry Co., Ltd., Tokyo Farbphotographisches silberhalogenid-aufzeichnungsmaterial

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5051346A (en) * 1985-02-16 1991-09-24 Konishiroku Photo Industry Co., Ltd. Light-sensitive photographic material comprising lipophilic coupler hydrophilic coupler and diffusion inhibitor releasing
EP0192199A3 (en) * 1985-02-16 1989-02-01 Konishiroku Photo Industry Co. Ltd. Light-sensitive photographic material
EP0192199A2 (fr) * 1985-02-16 1986-08-27 Konica Corporation Matériau photographique sensible à la lumière
EP0204416A2 (fr) * 1985-04-24 1986-12-10 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0204416A3 (en) * 1985-04-24 1989-02-01 Konishiroku Photo Industry Co. Ltd. Light-sensitive silver halide color photographic material
EP0208502A2 (fr) * 1985-07-01 1987-01-14 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0208502A3 (en) * 1985-07-01 1988-08-17 Konishiroku Photo Industry Co. Ltd. Light-sensitive silver halide color photographic material
EP0233641A2 (fr) * 1986-02-20 1987-08-26 Konica Corporation Matériaux photographiques à l'halogénure d'argent sensibles à la lumière
EP0233641A3 (en) * 1986-02-20 1989-06-07 Konishiroku Photo Industry Co. Ltd. Silver halide photographic lightsensitive materials
EP0327274A2 (fr) * 1988-01-30 1989-08-09 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière
EP0327274A3 (en) * 1988-01-30 1990-03-21 Konica Corporation Light-sensitive silver halide photographic material
EP0329016A3 (en) * 1988-02-19 1990-08-16 Agfa-Gevaert Ag Colour-photographic recording material
EP0329016A2 (fr) * 1988-02-19 1989-08-23 Agfa-Gevaert AG Matériau de reproduction photographique couleur
US4963465A (en) * 1989-01-12 1990-10-16 Agfa-Gevaert Aktiengesellschaft Color photographic negative recording material
US5545513A (en) * 1992-05-20 1996-08-13 Eastman Kodak Company Photographic material with improved granularity
EP0898199A1 (fr) * 1997-08-18 1999-02-24 Konica Corporation Produit photographique à l'halogénure d'argent sensible a la lumière
US6030758A (en) * 1997-08-18 2000-02-29 Konica Corporation Silver halide light sensitive photographic material
EP1485687A2 (fr) * 2002-02-04 2004-12-15 Ortho-McNeil Pharmaceutical Corporation Technique permettant de se procurer des donnees moleculaires a partir d'un echantillon de produit pharmaceutique et appareil a cet effet
EP1485687A4 (fr) * 2002-02-04 2009-01-14 Ortho Mcneil Pharmaceutical Co Technique permettant de se procurer des donnees moleculaires a partir d'un echantillon de produit pharmaceutique et appareil a cet effet

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Publication number Publication date
JPS5960437A (ja) 1984-04-06
JPH0375852B2 (fr) 1991-12-03
EP0107112A3 (en) 1984-07-04
EP0107112B1 (fr) 1988-01-07
DE3375228D1 (en) 1988-02-11

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