EP0384668A2 - Lichtempfindliches farbphotographisches Silberhalogenidmaterial - Google Patents

Lichtempfindliches farbphotographisches Silberhalogenidmaterial Download PDF

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Publication number
EP0384668A2
EP0384668A2 EP90301709A EP90301709A EP0384668A2 EP 0384668 A2 EP0384668 A2 EP 0384668A2 EP 90301709 A EP90301709 A EP 90301709A EP 90301709 A EP90301709 A EP 90301709A EP 0384668 A2 EP0384668 A2 EP 0384668A2
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EP
European Patent Office
Prior art keywords
group
formula
silver halide
light
photographic material
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EP90301709A
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English (en)
French (fr)
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EP0384668A3 (de
Inventor
Hirofumi Konica Corporation Ohtani
Yukio Konica Corporation Ohya
Syoji Konica Corporation Matsuzaka
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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
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30—Hardeners
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • 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
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group

Definitions

  • This invention relates to a light-sensitive color photographic material suitable for full color photographing, particularly to a negative-type light-sensitive silver halide color photographic material of which at least one color sensitive layer is a single layer.
  • color photography widely spread is the so-called negative-positive system in which photographing is practiced with a color negative film and color print is effected by enlarging onto a color paper.
  • a color negative film has very broad exposure latitude, with very little probability of failure during photographing, and even users in general having no special knowledge can take color photographs without any particular concern.
  • Having broad exposure latitude refers to the fact that the gradation is good over wide exposure amount range from the shadow portion with little exposure amount to the highlight portion with much exposure amount in the so-called characteristic curve in which the exposure amount is taken on the axis of abscissa and the color formed density on the axis of ordinate. If the gradation is inferior, color reproducibility, tone reproducibility will be deteriorated.
  • Color negative film as different from color reversal film or color paper, is a light-sensitive material for which gradation is demanded to be strictly controlled over wider range of exposure amount, and for this reason, color negative films for photography commercially available at the present time are made to have an overlaid constitution comprising a plurality of emulsion layers of higher sensitivity layer containing greater grain sizes and lower sensitivity layer containing smaller grain sizes for the respective color sensitive layers to the light of blue color, green color and red color. Further, the so-called DIR compound for forming consequently a developing inhibitor through the reaction with the oxidized product of the developing agent is employed.
  • Such technique is inherent in color negative film, and particularly the DIR compound improves not only gradation but also sharpness, graininess and color reproducibility, and is essential in color negative film.
  • An object of the present invention is to provide a light-sensitive silver halide color photographic material having high color formed density stable to storage after preparation of the light-sensitive material and excellent in gradation, color reproduction and tone reproducibility.
  • hydrophilic colloid such as gelatin, etc. is used as the binder, and recently in order to stand damages of the film which are liable to be generated by the rapid processing by means of an automatic developing machine at high temperature and high pH, or based on the demands from aspect of productivity, film hardening treatment is generally applied.
  • film hardener treatment is good or not is indispensable for ensuring the quality from aspect of physical properties except for special cases, and investigations have been made, including primitive inorganic film hardeners such as potassium alum, chromium alum, etc. to organic film hardeners adapted more highly to photographic characteristics.
  • primitive inorganic film hardeners such as potassium alum, chromium alum, etc.
  • film hardeners such as chlorotriazine type film hardeners disclosed in U.S. Patents 3,325,287 and 3,645,743 and Japanese Unexamined Patent Publication No. 40244/1982 and vinyl sulfone type film hardeners disclosed in U.S. Patent 3,490,911 and German Patent (OLS) No. 2,749,260, other aldehyde type, epoxy type, etc. may be included.
  • the film as the result of film hardening should have luster, film attachment should be good, film hardening should proceed rapidly, scratching strength should be great, it should be harmless to photographic characteristics, and there should be otherwise no problem in labour hygiene, no fear of environmental pollution, etc.
  • the s-triazine type has the drawback of lacking rapid film hardenability
  • the vinyl sulfone type various drawbacks such as lacking luster, film attachment, scratching strength, etc.
  • the film hardener which acts through activation of carboxyl groups and the chlorotriazine type film hardener have characteristics at least satisfactory for the above-mentioned items of physical properties, and are described in Japanese Patent Publication No. 6151/1972 and Japanese Unexamined Patent Publications Nos. 19220/1973, 78788/1976, 128130/1977, 130326/1977 and 1043/1981.
  • a light-sensitive silver halide color photographic material comprising a support, and silver halide emulsion layers which are respectively blue-sensitive, green-sensitive or red-sensitive and provided on the support, wherein said material contains a DIR compound and at least one selected from the group consisting of a film hardner which acts through activation of carboxyl groups, a chlorotriazine type film hardener and a bis(vinylsulfonylalkyl)ether type film hardener, and at least two of said blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers have single layer constitutions.
  • the DIR compound refers to a compound which eliminates a developing inhibitor or a compound capable of releasing a developing inhibitor through the reaction with the oxidized product of the color developing agent.
  • the above-mentioned compound capable of releasing a developing inhibitor may be one which releases the developing inhibitor either imagewise or non-imagewise.
  • Imagewise release may be effected by, for example, the reaction with the oxidized product of the developing agent, while non-imagewise release by utilizing, for example, the TIME group as described below.
  • Rd 1 represents hydrogen atom, a halogen atom or an alkyl, alkoxy, acylamino, alkoxycarbonyl, thiazolidinylideneamino, aryloxycarbonyl, acyloxy, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, nitro, amino, N-arylcarbamoyloxy, sulfamoyl, N-alkylcarbamoyloxy, hydroxy, alkoxycarbonylamino, alkylthio, arylthio, aryl, heterocyclic, cyano, alkylsulfonyl or aryloxycarbonylamino group.
  • n 0, 1 or 2
  • the respective Rdi's may be either the same or different.
  • the total carbon atoms contained in n Rd 1 's may be 0 to 10.
  • the total number of the carbon atoms contained in Rd 1 in the formula (D-6) may be 0 to 15.
  • X represents oxygen atom or sulfur atom.
  • Rd 2 represents an alkyl group, an aryl group or a heterocyclic group.
  • Rd 3 represents hydrogen atom, or an alkyl, cycloalkyl, aryl or heterocyclic group
  • Rd 4 represents hydrogen atom, a halogen atom or an alkyl, cycloalkyl, aryl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkanesulfonamide, cyano, heterocyclic, alkylthio or amino group.
  • Rd 1 , Rd 2 , Rd 3 or Rd 4 represents an alkyl group
  • the alkyl group may include those having substituents, and may be either straight or branched.
  • Rd 1 , Rd 2 , Rd 3 or Rd4 represents an aryl group
  • the aryl group may include those having substituents.
  • the heterocyclic group may include those having substituents, preferably 5- or 6-membered monocyclic or fused rings containing at least one selected from nitrogen atom, oxygen atom and sulfur atom as the hetero atom, that may be selected from the groups of, for example, pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imide, oxazine.
  • the carbon atoms contained in Rd 2 in the formula (D-8) may be 0 to 15.
  • the -TIME group may be typically represented by the formulae (D-11) to (D-19) set forth below.
  • Rds represents hydrogen atom, a halogen atom or an alkyl, cycloalkyl, alkenyl, aralkyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano, nitro, sulfonamide, sulfamoyl, carbamoyl, aryl, carboxy, sulfo, hydroxy or alkanesulfonyl group.
  • Rds's may be mutually bonded together to form a fused ring.
  • Rd 6 represents an alkyl, alkenyl, aralkyl, cycloalkyl, heterocyclic or aryl group.
  • Rd 7 represents a hydrogen atom or an alkyl, alkenyl, aralkyl, cycloalkyl, heterocyclic or aryl group.
  • Each of Rds and Rd 9 in the formulae (D-19) represents hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms), k in the formulae (D-11) and (D-15) to (D-18) represents an integer of 0, 1 or 2, 1 in the formulae (D-11) to (D-13). (D-15) and (D-18) represents an integer of 1 to 4, m in the formula (D-16) represents an integer of 1 or 2. When 1 and m are 2 or more, the respective Rds and Rd 7 may be either the same or different. n in the formula (D-19) represents an integer of 2 to 4, and Rd s and Rd 9 in number of n may be each the same or different.
  • B in the formulae (D-16) to (D-18) represents oxygen atom or (Rd s represents the same meaning as already defined), and in the formula (D-16) may be either a single bond or a double bond, and m is 2 in the case of the single bond and m is 1 in the case of the double bond.
  • the component represented by SR may be one which can form the component as mentioned above through the reaction with the oxidized product of the developing agent, and may include, for example, a coupler component which undergoes the coupling reaction with the oxidized product of the developing agent or a redox component which undergoes the redox reaction with the oxidized product of the developing agent.
  • coupler component there may be included yellow couplers, magenta couplers, cyan couplers such as acylacetanilides, 5-pyrazolones, pyrazoloazoles, phenols, naphthols, acetophenones, indanones, carbamoylacetanilides, 2(5H)-imidazolones, 5-isoxazolones, uracils, homophthalimides, oxazolones, 2,5-thiadiazoline-1,1-dioxides, triazolothiadiazines, indoles, etc., and otherwise those which form various dyes or form no dye.
  • yellow couplers such as acylacetanilides, 5-pyrazolones, pyrazoloazoles, phenols, naphthols, acetophenones, indanones, carbamoylacetanilides, 2(5H)-imidazolones, 5-isoxazolones,
  • the (T 1 ) e - SR(T 2 ) m INHIBIT should be preferably bonded to the active site of the component A of the formula (D-1).
  • SR is a coupler component
  • SR is bonded to (T 1 ) e - and (T 2 ) m INHIBIT so as to function for the first time as the coupler after cleavage from (T 1 ) e .
  • the coupler component is a phenol or a naphthol and the oxygen atom of hydroxyl group is a 5-pyrazolone
  • the oxygen atom at the 5-position, or the nitrogen atom at the 2-position of the enantiomer, and also the oxygen atom of hydroxyl group of the enantiomer in acetophenones or indanones should be preferably bonded to (T 1 ) e , and (T 2 ) m -INHIBIT to the active site of the coupler.
  • SR is a redox component
  • its examples may include hydroquinones, catechols, pyrogallols, aminophenols (e.g. p-aminophenols, o-aminophenols), naphthalenediols (e.g. 1,2-naphthalenediols, 1,4-naphthalenediols, 2,6-naphthalenediols), or aminonaphthols (e.g. 1,2-aminonaphthols, 1,4-aminonaphthols, 2,6-aminonaphthols), etc.
  • aminophenols e.g. p-aminophenols, o-aminophenols
  • naphthalenediols e.g. 1,2-naphthalenediols, 1,4-naphthalenediols, 2,6-naphthalenediols
  • aminonaphthols e.g. 1,2-
  • SR is a redox component
  • SR is bonded to (T 1 ) e - and (T 2 ) m INHIBIT so as to function for the first time as the redox component after cleavage from (T 1 ) 2 .
  • T, and T 2 may include those represented by the formulae (D-11) to (D-19) as described above.
  • DIR compounds preferable are those wherein Y is represented by the formula (D-2), (D-3), (D-8), (D-10) or (D-20), and among (D-10) and (D-20), those wherein INHIBIT is represented by the formula (D-2), (D-3), (D-6) (particularly when X of (D-6) is oxygen atom), or (D-8) are preferred.
  • yellow color image forming coupler residues As the coupler component represented by A in the formula (D-1), yellow color image forming coupler residues, magenta color image forming coupler residues, cyan color image forming coupler residues and no color exhibiting coupler residues may be included.
  • DIR compounds to be used in the present invention the compounds as shown below may be included, but these are not limitative of the invention.
  • DIR compounds which can be used in the present invention, including these are described in U.S. Patents 4,234,678, 3,227,554, 3,617,291, 3,958,993, 4,i49,886, 3,933,500, Japanese Unexamined Patent Publications Nos. 56837/1982 and 13239/1976, U.S. Patents 2,072,363 and 2,070,266, Research Disclosure (hereinafter abbreviated to RD) No. 21228, December, 1981, etc.
  • RD Research Disclosure
  • the DIR compound should be preferably used in an amount of 0.0001 to 0.1 mole, particularly 0.001 to 0.05 mole, per mole of silver halide.
  • the place in which the DIR compound to be used in the present invention is added may be any place which can affect developing of the silver halide in the emulsion layer of single layer constitution, preferably in a silver halide emulsion layer, more preferably in an emulsion layer having a single layer constitution.
  • the hardener which acts through activation of carboxyl groups refers to a hardener which reacts with the carboxyl groups in the binder.
  • R 1 and R 2 each represent an alkyl group (e.g. methyl, ethyl, benzyl, phenethyl, 2-ethylhexyl group, etc.) or an aryl group (e.g. phenyl, naphthyl group, etc.), and it is also preferable that the both are bonded to form a heterocyclic ring together with nitrogen atom.
  • alkyl group e.g. methyl, ethyl, benzyl, phenethyl, 2-ethylhexyl group, etc.
  • aryl group e.g. phenyl, naphthyl group, etc.
  • R 3 represents, for example, -NR 4 R 5 (R 4 and R 5 have the same meanings as R 1 and R 2 ), a halogen atom, a carbamoyl group, a sulfo group, a ureido group, an alkoxy group, an alkyl group, etc.
  • R 3 is inclusive of those having substituents, and examples of substituents may include halogen atoms, an alkyl group, a carbamoyl group, a sulfo group, a sulfooxy group, a ureido group, etc.
  • n 0 to 5
  • R 3 ' S the plural number of R 3 ' S may be either the same or different from each other.
  • X e represents an anion, and preferable examples may include halide ions, sulfate ion, sulfonate ion, CIO 4 e , BF 4 ⁇ , PF 6 ⁇ , etc. 1 represents 0 or 1, n represents 0 to 2, and when an intramolecular salt is formed, n is 0.
  • R 1 and R 2 each represent a cycloalkyl group (e.g. cyclohexyl group, etc.) or an alkyl group (e.g. methyl, ethyl, 2-ethylhexyl, etc.), or otherwise an alkoxy alkyl group such as methoxyethyl group, an aralkyl group such as benzyl group, phenethyl group, etc. or an group represented by the formula:
  • R 3 represents an alkylene group (e.g. ethylene, propylene and trimethylene group, etc.)
  • R 4 , R 5 and R 6 each represent an alkyl group (e.g. methyl and ethyl group, etc.), including the case wherein two of the R 4 to R 6 are bonded to form a heterocyclic ring (e.g. pyrrolidine ring, piperazine ring, morpholine ring, etc.) together with nitrogen atom and the case of having substituents.
  • a heterocyclic ring e.g. pyrrolidine ring, piperazine ring, morpholine ring, etc.
  • substituents may be preferably carbamoyl groups such as diethylcarbamoyl, piperidinocarbonyl, etc., sulfo group, etc.
  • m represents 0 or 1
  • X 9 represents an anion, preferably a halide ion, sulfonate ion, sulfate ion, CIO 4 ⁇ , BF 4 ⁇ , PF s e , etc.
  • m is 0.
  • R 1 represents an alkyl group (e.g. methyl, ethyl, butyl group, etc. or otherwise, an aralkyl group such as benzyl, and phenethyl group, etc.) or an aryl group (e.g. phenyl group, naphthyl group, etc.).
  • alkyl group e.g. methyl, ethyl, butyl group, etc. or otherwise, an aralkyl group such as benzyl, and phenethyl group, etc.
  • aryl group e.g. phenyl group, naphthyl group, etc.
  • R 2 and R 3 represent, for example, hydrogen atom or substituents such as halogen atoms, acylamido, nitro, carbamoyl, ureido, alkoxy, alkyl, alkenyl, aryl, aralkyl groups, etc., and it is also preferable that R 2 and R 3 may be bonded to form a fused ring together with the pyridinium ring skelton.
  • X represents a group eliminable when the compound represented by the formula (H-III) reacts with a nucleophilic reagent.
  • Preferable examples may include halogen atoms, sulfonyloxy group, sulfoalkyl group or a group represented by -OP (OR4)2 O
  • X represents a sulfonyloxyl group
  • R 1 may be bonded to each other.
  • Y e represents an anion, preferably a halide ion, sulfonate ion, sulfate ion, CIO 4 ⁇ , BF 4 ⁇ , PF 6 ⁇ , etc.
  • n 0 or 1
  • m 1
  • R 1 and R 2 are entirely the same as R 1 and R 2 in the formula (H-I), and R 3 represents an alkyl group (e.g. methyl, ethyl, butyl group, or otherwise an aralkyl group such as benzyl and phenethyl group, etc.), or an aryl group (e.g. phenyl and naphthyl group, etc.).
  • R 3 represents an alkyl group (e.g. methyl, ethyl, butyl group, or otherwise an aralkyl group such as benzyl and phenethyl group, etc.), or an aryl group (e.g. phenyl and naphthyl group, etc.).
  • X ⁇ represents an anion, preferably a halide ion, sulfonate ion, sulfate ion, CIO 4 ⁇ , BF 4 ⁇ , PF 6 ⁇ , etc.
  • R 1 , R 2 , and R 3 , R 4 are entirely the same as R 1 , R 2 in the formula (H-I), and further R 1 and R 3 may form a ring.
  • X represents a group eliminable during the reaction with a nucleophilic reagent, preferably a halogen atom, a sulfonyloxy group (preferably alkylsulfonyloxy and arylsulfonyloxy), 1-pyridium group, an imidyloxy group (e.g. phthalimidyloxy, succinimidyloxy and glutarimidyloxy), an azoyloxy group and an ammonio group.
  • a nucleophilic reagent preferably a halogen atom, a sulfonyloxy group (preferably alkylsulfonyloxy and arylsulfonyloxy), 1-pyridium group, an imidyloxy group (e.g. phthalimidyloxy, succinimidyloxy and glutarimidyloxy), an azoyloxy group and an ammonio group.
  • the anion represented by Y 1 ⁇ may include, for example, a halide ion, sulofnate ion, sulfate ion, CI0 4 e , BF 4 ⁇ , PF 6 ⁇ , phosphonate ion, phosphate ion.
  • R 1 and R 2 each represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group or -NR 3 R 4 (R 3 and R 4 each represent an alkyl, alkenyl, cycloalkyl, aryl or aromatic heterocyclic group, and also include one having a ring formed through bonding of R 3 and R 4 ).
  • X 1 is the same as the definition of X 1 in the formula (H-V).
  • R 1 , R 2 , and R 3 , R 4 , and R 5 , R 6 are the same as the definitions of R 1 , R 2 in the formula (H-I), X 1 is the same as the definition of X, in the formula (H-V), and Y 1 ⁇ the same as the definition as Y, e in the formula (H-V).
  • R 1 represents an aryl group
  • Z represents a group of non-metallic atoms necessary for formation of an aromatic heterocyclic ring
  • the ring formed by R 1 and Z is inclusive of those having substituents.
  • Y e represents an anion
  • m represents 0 or 1
  • m is 0.
  • the carboxyl activation type hardener to be used in the present invention other than the compounds represented by the above formulae (H-I) through (H-VIII), the compounds described in Japanese Unexamined Patent Publications Nos. 38540/1975, 93470/1977, 43353/1981, 113929/1983, U.S. Patent 3,321,313, etc. are also preferable.
  • specific examples of the compounds to be used in the present invention are set forth as classified, but the present invention is not limited at all to these.
  • Compounds of the formula (H-I) these compounds and their synthetic methods are described in detail in Japanese Unexamined Patent Publications Nos.
  • the amount of the carboxyl group activation type hardener to be used in the present invention can be selected as desired depending on the purpose. Generally, it can be used at a ratio of 0.01 to 10 % by weight based on dry gelatin. Particularly, preferable ratio is 0.05 to 5 % by weight.
  • the carboxyl group activation type hardener and other hardeners can be also used at any desired ratio, but when the carboxyl group activation type hardener is made 1, other hardeners may be used preferably within the range from 0.01 to 1 by weight ratio.
  • hydrophilic colloidal layer is to be described.
  • the hydrophilic colloidal layer in the present invention may be preferably a binder having amino groups and carboxyl groups, and may be a binder which undergoes hardening reaction with the carboxyl group activation type hardening agent, but generally gelatin may be advantageously used.
  • Gelatin may include, in addition to lime-treated gelatin, acid-treated gelatin, the enzyme-treated gelatin as described in Bull. Soc. Sci. Phot, Japan, No. 16, p. 30 (1966), gelatin derivatives (those obtained by reacting various compounds such as acid halide, acid anhydride, isocyanates, bromoacetic acid, alkanesultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, epoxy compounds, etc. with gelatin).
  • gelatin derivatives obtained by reacting various compounds such as acid halide, acid anhydride, isocyanates, bromoacetic acid, alkanesultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, epoxy compounds, etc. with gelatin).
  • the emulsion layer and other hydrophilic colloid layers can incorporate plasticizers, dispersions of synthetic polymers insoluble or difficultly soluble in water (latices).
  • chlorotriazine type film hardner Preferable as the chlorotriazine type film hardner are those represented by the formula (H-1) or (H-2) shown below.
  • Z represents chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, -OM group (M represents a monovalent metal atom) or -NR R , -NHCOR''' (R , R , R'' each represent hydrogen atom, an alkyl group or an aryl group), and Z 2 has the same meaning as Z, excluding chlorine atom.
  • Z 3 and Z 4 each represent chlorine atom, hydroxy group, an alkyl group, an alkoxy group or -OM group (M represents a monovalent metal atom).
  • Q and Q are each linking group representing -O-, -S-, -NH-, L represents an alkylene group or an arylene group. 1 and m each represent 0 or 1.
  • the alkyl group represented by Z, and Z 2 in the above formula (H-1) may be exemplified by a methyl, ethyl and butyl groups, etc., the alkylthio group by a methylthio, ethylthio and butylthio groups, etc., and alkoxy group by a methoxy, ethoxy and butoxy groups, etc.
  • M of the -OM group represented by Z 1 or Z 2 may be, for example, sodium atom or potassium atom.
  • the chlorotriazine type film hardener shown by the above formula (H-2) is described in U.S. Patents 3,645,743, Japanese Patent Publications Nos. 6151/1972, 33380/1972 and 9607/1976, and Japanese Unexamined Patent Publications Nos. 19220/1973, 78788/1976, 60612/1977, 128130/1977, 130326/1977 and 1043/1981.
  • the alkyl group represented by R 3 and R4 may be, for example, a methyl, ethyl or butyl groups, etc.
  • the alkoxy group may be, for example, a methoxy, ethoxy or butoxy groups, etc.
  • the M of -OM group for example, sodium atom or potassium atom.
  • the alkylene group represented by L in the formula (H-2) may be the group of ,for example, -CH 2 -, --(CH 2 ) 2 -, -(CH 2 ) 3 -, etc., the arylene group, for example, p-, o- or m-phenylene group, etc.
  • the chlorotriazine type film hardener represented by the above formula (H-2) is described in Canadian Patent 895,808, Japanese Patent Publication No. 33542/1983 and Japanese Unexamined Patent Publication No. 40244/1982.
  • the compound represented by the above formula (H-1) or (H-2) is generally diffused into all the layers provided by coating, and therefore it may be added in at least one layer or a plurality of layers selected from among the emulsion layers according to the present invention or the auxiliary layers. Said addition may be performed by dissolving the compound in water or an alcohol (e.g. methyl alcohol, ethyl alcohol, etc.) and adding the solution in an amount of 1 to 100 mg, preferably 5 to 50 mg per 1 g of gelatin.
  • the addition method may be either the batch system or the inline system.
  • chlorotriazine type film hardeners are set forth, but the present invention is not limited at all to these.
  • the bis(vinylsulfonylalkyl)ether type hardners to be used in the present invention will be described bellow.
  • Preferred Bis(vinylsulfonylalkyl)ether type hardner is represented by the following formula (H-a): In the formula; L denotes a divalent organic group, m and n denote positive integers, and p denotes 0 or 1.
  • the hardener represented by the formula (H-a) As the divalent organic group represented by L in the formula (H-a), preferred is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a divalent heterocyclic group, a divalent group represented by or a divalent groups prepared by combining plural number of these divalent groups.
  • the both ends of the divalent groups represented by L should preferably be carbon atoms.
  • n and m should preferably be an integer of 1 to 6, particularly preferably 1.
  • the amount of the bis(vinylsulfonylalkyl)ether type hardners can be selected depending on the purpose. It may be generally used in the rage of 0.01 to 20 % by weight, particularly preferably, in the range of 0.05 to 15 % by weight based on a dry gelatin.
  • the constitution that the color sensitive layer defined in the present invention is a single layer is also inclusive of the case when a plurality of emulsion layers which are the same in color sensitivity, being the same in the kind of the couplers contained in the emulsion layers, grain sizes of the silver halide grains, the halogen compositions and crystal habits, and also the ratio of the coupler to the silver halide, are arranged as continuous layers.
  • the same in color sensitivity or “the same color sensitivity” may be the same in the point of, for example, blue sensitivity, green sensitivity, red sensitivity, and is not required to be totally the same in spectral sensitivity characteristics.
  • the blue-sensitive layer should be preferably a single layer, and further preferably, both the blue-sensitive layer and the green-sensitive layer should be single layers. Particularly, all of the blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers should be preferably single layers, respectively.
  • the same color sensitive layer has a single layer constitution
  • the number of the layers coated of the light-sensitive layer can be reduced as compared with the overlaid constitution of the prior art, whereby the film can be made thinner. Therefore, production efficiency, sharpness are improved, and graininess is also improved.
  • the film thickness should be preferably 20 to 3 ⁇ m, particularly 15 to 5 ⁇ m, after drying.
  • the exposure latitude is the width of light received at which the exposure effect with a significant difference can be exhibited, particularly the exposure region from the highlight to the deep shadow in the characteristic curve, and is determined by the method defined in "Shashin no Kagaku” (Chemistry of Photography), p. 393 (Shashin Kogyo Shuppansha, 1982).
  • the light-sensitive material should be preferably one having an exposure latitude measured according to the method as described above of 3.0 or more, particularly 3.0 to 8.0.
  • the means for making the exposure latitude of the silver halide emulsion layer which is a single layer wide, e.g. 3.0 or more, it is possible to use the method in which silver halide grains with different sensitivities are used as a mixture.
  • the method in which silver halide grains with different grain sizes are used as a mixture may be included, for example, the method in which silver halide grains with different grain sizes are used as a mixture, and the method in which the desensitizer is contained in at least a part of the silver halide grains.
  • the grain group having a larger mean grain size should preferably be in the range of 0.2 to 2.0 nm and the grain group having a smaller mean grain size, 0.05 to 1.0 u.m, and the mean grain size of the latter group is smaller than that of the former group.
  • one or more of silver halide grains having an intermediate mean grain size may be combined.
  • the combination of silver halide grains having a maximum mean grain size of 0.2 to 2.0 u.m and silver halide grains having a minimum mean grain size of 0.05 to 1.0 nm may be preferable, and further one or more of silver halide grains having an intermediate mean grain size may be also combined.
  • the mean grain size of the silver halide grains with the maximum mean grain size should be preferably 1.5 to 40 times as that of the silver halide grain with the minimum mean grain size.
  • silver halide grains with different mean grain sizes can be also used as a mixture, but by using silver halide grains containing a desensitizer in place of the low sensitivity silver halide grains with small grain sizes, the mean grain size difference can be made smaller without changing the sensitivity of the silver halide grains, and further it becomes possible to use silver halide grains with equal mean grain size and different sensitivities.
  • the exposure latitude can be obtained even if the fluctuation coefficient of the grains as a whole may be made smaller.
  • these silver halide grains with small fluctuation coefficient exposed to the same environment are preferably stabilized in photographic performances relative to changes with lapse of time and fluctuations in developing processing. Further, in aspect of production technique, it becomes also possible to sensitize chemically a mixed system of silver halide grains with different sensitivities in the same batch.
  • desensitizer in addition to metal ions, various ones such as antifoggants, stabilizers, desensitizing dyes, etc. can be used.
  • the metal ion doping method is preferred.
  • the metal ion to be used for doping there may be included the metal ions of the groups Ib, Ilb, Illa, Illb, iVb, Va, VIII in the periodic table of elements.
  • Preferable metal ions may include Au, Zn, Cd, TI, Sc, Y, Bi, Fe, Ru, Os, Rh, Ir, Pd, Pr, Sm and Yb. Particularly, Rh, Ru, Os and Ir are preferred.
  • metal ions can be used as, for example, halogeno complexes, etc., and the pH of the AgX system during doping should be preferably 5 or less.
  • the amount of these metal ions doped will differ variously depending on the kind of the metal ion, the grain size of the silver halide grains, the doping position of the metal ion, the desired sensitivity, etc., but may be preferably 10- 17 to 10- 2 mole, further 10- 12 to 10- 3 mole, particularly 10- 9 to 10- 4 mole, per mole of AgX.
  • the silver halide grains with different doping conditions are adjusted in conditions to be provided for practical application, these can be also made up in the same batch by mixing at a predetermined ratio and subjected to chemical sensitization.
  • the respective silver halide gains receive the sensitizing effects based on their qualities, whereby an emulsion having a broad exposure latitude depending on the sensitivity difference and the mixing ratio can be obtained.
  • azoles e.g. benzothiazolium salt, indazoles, triazoles, benztriazoles, benzimidazoles, etc.
  • heterocyclic mercapto compounds e.g. mercaptotetrazoles, mercaptothiazoles, mercaptothiadiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptopyrimidines, etc.
  • azaindenes e.g. tetraazaindenes, pentaazaindenes, etc.
  • decomposed products of nucleic acids e.g. adenine, guanine, etc.
  • benzenethiosulfonates thioketo compounds, and others.
  • cyanine dyes there may be included cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes, etc.
  • the position where the desensitizer exists it should be preferably mixed internally of the silver halide grains, and its distribution may be either uniform, localized at the central portion of grain or the intermediate positions, etc., or also gradually reduced from the central portion of grain toward outside, in viewpoint of storability of the light-sensitive material, digenstion stability of the coating liquid, etc.
  • the desensitizer exists as localized at the central portion of grain is preferable, and by use of the system in which seed grains with small fluctuation coefficient are used, the steps of grain growth et seq can be proceeded in the same batch.
  • the light-sensitive material of the present invention should desirably have at least one color sensitive layer (e.g. blue-sensitive layer) containing AgX grains containing a desensitizer.
  • a color sensitive layer e.g. blue-sensitive layer
  • the blue-sensitive layer contains AgX grains containing a desensitizer, more preferably when the blue-sensitive layer and the green-sensitive layer contain them, most preferably when all of the color sensitive layers contain them.
  • the fluctuation coefficient defined by the ratio S/ r of the standard deviation of grain size (S) as the silver halide grains contained in the respective silver halide emulsion layers and the mean grain size ( r should be preferably 0.4 or less, more preferably 0.33 or less, further preferably 0.25 or less, particularly preferably 0.20 or less.
  • the mean grain size ( r ) is defined by the following formula when the number of grains with a grain size ri (in the case of a cubic silver halide grain, its length of one side, or in the case of a grain with other shape than cubic, the length of one side of the cube calculated to have the same volume) is ni:
  • grain size distribution can be determined according to the method described in the essay of Tribel and Smith in “Empirical Relationship between Sensitometry Distribution and Grain Size Distribution in Photography", The Photographic Journal, Vol. LXXIX (1949), p.p. 330 - 338.
  • any of conventional silver halide emulsions can be used, but a silver halide containing substantially iodine in the halogen composition (e.g. silver iodobromide, silver iodochlorobromide) may be preferable, particularly preferably silver iodobromide with respect to sensitivity.
  • the amount of iodine may be preferably 1 mole % or more and 20 mole % or less, particularly 3.5 mole % or more 12 mole % or less.
  • a core/shell type silver halide emulsion to be used in the present invention preferably has a grain structure comprising two or more phases different in silver iodide content and comprises silver halide grains in which a phase containing a maximum silver iodide content (referred to as "core”) is other than the outermost surface layer (referred to as "shell").
  • core a phase containing a maximum silver iodide content
  • shell the outermost surface layer
  • the content of silver iodide in an inner phase (core) having the maximum silver iodide content is preferably 6 to 40 mole %, more preferably 8 to 40 mole %, particularly preferably 10 to 40 mole %.
  • the content of silver iodide in the outermost surface layer is preferably less than 6 mole %, more preferably 0 to 4.0 mole %.
  • a ratio of the shell portion in the core/shell type silver halide grains is preferably 10 to 80 %, more preferably 15 to 70 %, particularly preferably 20 to 60 % in terms of volume.
  • a ratio of the core portion is preferably, in terms of volume, 10 to 80 %, more preferably 20 to 50 % based on the whole grains.
  • Difference of silver iodide content between the core portion having higher silver iodide content and the shell portion having less silver iodide content of the silver halide grains may be clear with sharp boundary or may be hazy where boundary is not clear and the content continu ously changes. Also, those having an intermediate phase with silver iodide content between those of the core portion and the shell portion, between the core and the shell, may be preferably used.
  • a volume of the intermediate phase is preferably 5 to 60 %, more preferably 20 to 55 % based on the whole grain.
  • Differences of the silver iodide content between the shell and the intermediate phase, and between the intermediate phase and the core are each preferably 3 mole % or more and the difference of the silver iodide content between the shell and the core is preferably 6 mole % or more.
  • the core/shell type silver halide emulsion can be prepared according to the known methods as disclosed in Japanese Provisional Patent Publications No. 177535/1984, No. 138538/1985, No. 52238/1984, No. 143331/1985, No. 35726/1985 and No. 258536/1985.
  • soluble silver salt and soluble halide are generally used, but as clear from the examples mentioned below, iodide salts are preferably used in the form of silver iodide fine crystals in the point of preservability and processing stability of the light-sensitive material.
  • silver iodobromide fine crystals having high Agl content are similarly and preferably used as the silver iodide fine crystals.
  • Distribution condition of the silver iodide in the above core/shell type silver halide grains can be determined by various physical measuring method and, for example, it can be examined by the measurement of luminescence at low temperature or X-ray diffraction method as described in Lecture Summary of Annual Meeting, Japanese Photographic Association, 1981.
  • the core/shell type silver halide grain may be any shape of normal crystal such as cubic, tetradecahedral and octahedral, or twinned crystal, or mixtures thereof, but preferably normal crystal grains.
  • Said emulsion can be chemically sensitized in conventional manner, and optically sensitized to a desired wavelength region by use of a sensitizing dye.
  • silver halide emulsion antifoggants, stabilizers, etc. can be added.
  • gelatin can be advantageously used as the binder for said emulsion.
  • the emulsion layer and other hydrophilic colloid layers can be hardened, and also a plasticizer and a dispersion (latex) of a water-soluble or difficultly soluble synthetic polymer can be contained therein.
  • couplers are used.
  • colored couplers having the effect of color correction, competitive couplers and compounds releasing photographically useful fragments such as developer, silver halide solvent, toning agents, film hardeners, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers through the coupling with the oxidized product of the developing agent.
  • auxiliary layers such as filter layer, antihalation layer, anti-irradiation layer, etc. can be provided.
  • a dye which flows out from the light-sensitive material or bleached during developing processing may be also contained.
  • formalin scavenger fluorescent brightener, matte agent, lubricant, image stabilizer, surfactant, color fog preventive, developing accelerator, developing retarder, bleaching accelerator, etc. can be added.
  • papers laminated with polyethylene, etc., polyethylene terephthalate film, baryta film, cellulose triacetate, etc. can be used.
  • the light-sensitive material of the present invention is particularly useful as the negative-type light-sensitive material.
  • aqueous gelatin Into a reaction vessel in which an aqueous gelatin had been thrown, while controlling the pAg and the pH in the reaction vessel and also controlling the addition time, were added at the same time an aqueous silver nitrate solution, an aqueous potassium iodide solution and an aqueous potassium bromide solution, and then precipitation and desalting were practiced by use of a pH coagulatable gelatin, followed by addition of gelatin to prepare a seed emulsion.
  • the emulsion obtained is called NE-1.
  • a seed emulsion was prepared in the same manner as described above except for adding K 3 RhCl s in the reaction vessel (NE-2). The emulsions and their contents are shown in Table 1.
  • gelatin was added to effect re-dispersion to give an emulsion of pAg 7.8, pH 6.0.
  • the amounts coated are indicated in the amount represented in g/m 2 unit calculated on silver for silver halide and colloidal silver, the amount represented in g/m 2 unit for the additive and gelatin, and further in moles per mole of silver within the same layer for sensitizing dye, coupler and DIR compound.
  • each color sensitive emulsion layer was applied with optimum sensitization with sodium thiosulfate and chloroauric acid.
  • surfactants were added as the coating aid.
  • Samples No. 102 to 106 were prepared in the same manner as Sample No. 101 except for adding those indicated in Table 3 in place of the film hardener HH-1 contained in Pro-2.
  • Sample No 107 was prepared in the same manner as Sample No. 101 except for omitting G-2 and B-2 in Sample No. 101, changing the emulsion contained in G-1 and B-1 to a mixture of equal moles of EM-1 and EM-2.
  • Samples No. 108 to No. 112 were prepared in the same manner as Sample No. 107 except for adding those shown in Table 3 in place of the film hardener HH-1 contained in Pro-2.
  • the samples Nos. 101 to 112 thus obtained were divided into two, one of which was provided as the standard sample, while the other subjected to storage stability test of the light-sensitive material by leaving it to stand under the conditions of 25 C, RH of 80 % for 15 days.
  • wedge exposure was effected in conventional manner, and then color developing was performed with the processing liquors and processing steps shown below.
  • storage stability of gradation is represented by the value E which is a product of 1,000 with the standard deviation a of the absolute value ⁇ of the difference between the point gamma values at the respective exposure points of the characteristic curve which is the standard and the characteristic curve to be evaluated.
  • the gradation change is not uniform, and the storage stability of the gradation is not excellent as the value of ⁇ is greater.
  • the samples of the present invention were found to have excellent storage stability of gradation with little fluctuation of gradation from the highlight to the shadow of the characteristic curve in storage of light-sensitive material.
  • the effects of the present invention are not limited to the film hardeners used in the examples, but could be observed in all the compounds in the film hardeners shown by the exemplary compounds.
  • Sample No. 201 was prepared in the same manner as in Sample No. 101 of Example 1.
  • H-a-1 was added in place of the hardner HH-1 contained in the Pro-2 layer of Sample No. 201.
  • Sample No. 204 was a multi-layer light-sensitive color material entirely the same as Sample No. 201.
  • Sample Nos. 202 and 205 were prepared in the same manner as in Sample No. 201 excepting for removing the G-2 and B-2 layers in Sample No. 201, changing the emulsions contained in the G-1 and B-1 layers in Sample No. 201 to Em-3 in an equimolar amount with Em-2 and changing the hardner contained in the Pro-2 layer of Sample No. 201 as described above.
  • Sample Nos. 203 and 206 were prepared in the same manner as in Sample No. 202 excepting for removing the R-2 layer in Sample No. 202, changing the emulsions contained in the R-2 layer in Sample No. 202 to Em-3 in an equimolar amount with Em-2 and changing the hardner contained in the Pro-2 layer of Sample No. 202 as described above.
  • the samples of the present invention show small variation in gradation from the highlight thorough the shadow of the characteristic curve and good storability of gradation. It is also realized that the samples of the present invention has a wide exposure latitude as the exposure latitude represented by log H was 3.0 or more. Further, when the blue-sensitive and red-sensitive layers comprise a single layer constitution and when the green-sensitive and red-sensitive layers comprise a single layer constitution in place of Sample No. 205, the same effect as in Sample No. 205 could be recognized.
  • the effect of the present invention was mostly shown when the hardner of the present invention was used and all of the three color sensitive layers were composed of a single layer constitution.

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EP19900301709 1989-02-21 1990-02-16 Lichtempfindliches farbphotographisches Silberhalogenidmaterial Withdrawn EP0384668A3 (de)

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