Classifications

• • 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

• the present invention relates to a color photographic material excellent in sharpness and color reproduction quality.
• DIR couplers capable of releasing a development retarder
• DIR couplers described, for example, in U.S. Patent Nos. 3,227,554, 3,701,783, 3,615,506, and 3,617,291, and JP-A ("JP-A" means unexamined published Japanese patent application) No. 82423/1987 are known.
• JP-A means unexamined published Japanese patent application
• No. 82423/1987 are known.
• the development retarder released at the time of color development diffuses from the photographic material into the processing solution and accumulates in the processing solution, which brings about a problem that the processing solution exhibits a development-retarding effect.
• DIR couplers are required that can be decomposed into a substantially photographically noninfluential compound after flowing into the color-­ development processing solution.
• Examples of such DIR couplers are described, for example, in U.S. Patent No. 4,477,563. These couplers were couplers that indeed did not contaminate a color-developing solution and were suitable for a process wherein the color-development processing solution was continuously used repeatedly.
• malondianilide couplers described in U.S. Patent No. 4,477,563 mentioned above, have been used as DIR couplers because their coupling activity is high.
• the object of the present invention is to provide a highly sensitive color photographic material excellent in sharpness and color reproduction quality which contains a novel DIR coupler, whose dye produced by coupling with the oxidized product of a color-­developing agent is sufficiently fast, and which will not contaminate development processing solutions.
• a silver halide color photographic material wherein a compound represented by the formula (I) given below is contained in at least one hydrophilic colloid layer formed on a support.
• R1 represents a group of non-metallic atoms required to form a heterocyclic group together with the residue
• R2 represents an organic residue
• X represents a group of such a nature that when the compound reacts with the oxidized product of an aromatic primary amine developing agent, X splits off to act as a development retarder or a development retarder precursor that will be decomposed into a substantially photographically noninfluential compound after flowing into the color-developing solution.
• Couplers represented by formula (I) used in the present invention will now be described further in detail.
• the heterocyclic group represented by contains at least one nitrogen atom, with all the remaining atoms forming the ring being carbon atoms, several (for example one or two) of which may be replaced with hetero atoms, such as nitrogen atoms, oxygen atoms, or sulfur atoms.
• the thus formed basic heterocyclic group is preferably a 5- to 7-membered group.
• the heterocyclic group may have substituents or other condensed ring. These condensed rings may further be substituted.
• W represents N, O, or S
• R0 represents a substituent
• n is an integer of 0 to 2
• at least one of Y0 and Z0 represents N, otherwise being C
• V1 and V2 each represent N or C
• two R0's each may be the same or different, including either to form a ring together or not to form a ring.
• the substituent represented by R0 can be mentioned include, for example, a halogen atom, an acyloxy group, a sulfonyloxy group, an alkyl group, a nitro group, a cyano group, an acylamino group, and sulfonamido group.
• a halogen atom an acyloxy group, a sulfonyloxy group, an alkyl group, a nitro group, a cyano group, an acylamino group, and sulfonamido group.
• rings represented by formula (III), (IV), (V), (VI), (VII), and (VIII): wherein Q0 represents an substituted or unsubstituted 1,2-condensed benzene ring, A represents a hydrogen atom, a monovalent group e.g., ⁇ alkyl, alkoxyalkyl (e.g., methoxyethyl and propoxyethyl) or halogenoalkyl (e.g., chloroethyl and bromopropyl) having preferably 1 to 20 carbon atoms, aralkyl (e.g., benzyl and phenethyl) having preferably 7 to 20 carbon atoms; or an aryl (e.g., phenyl, and a substituted phenyl, such as tosyl and chlorophenyl) having preferably 6 to 20 carbon atoms ⁇ , and R represents a hydrogen atom, or a substituent, such as an alky
• R2 in formula (I) represents an organic residue, which herein stands for a straight-chain or branched, or chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group (preferably having 1 to 30 carbon atoms, e.g., methyl, propyl, t-butyl, trifluoromethyl, tridecyl, 3-(2,4-di-t-amylphenoxy)propyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexylsulfonylethyl, cyclopentyl and benzyl), an aryl group (preferably having 6 to 30 carbon atoms, e.g., phenyl, 4-t-butylphenyl and 4-­tetradecaneamidophenyl), a heterocyclic group (preferably a 5- to 7-membered ring, e.g., 2-furyl, 2-thienyl, 2-­
• the aliphatic group represented by R3 and R4 may be straight-chain or branched, or chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group preferably having 1 to 30 carbon atoms, such as methyl, propyl, isoamyl, trifluoromethyl, 3-(2,4-di-t-amylphenoxy)propyl, 2-dodecyloxyethyl, 3-phenoxypropyl, and benzyl.
• the aromatic group represented by R3 and R4 includes a substituted or unsubstituted phenyl group, whose substituent includes a halogen atom (e.g., fluorine, chlorine and bromine), a straight-chain or branched, or chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group (e.g., methyl, propyl, t-­butyl, trifluoromethyl, tridecyl, 3-(2,4-di-t-­amylphenoxy)propyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-­hexylsulfonylethyl, cyclopentyl, and benzyl), an aryl group (e.g., phenyl, 4-t-butylphenyl, and 4-­tetradecaneamidophenyl), a heterocyclic group (e.g., 2-­furyl,
• the heterocyclic group represented by R3 and R4 is preferably a 5- to 6-membered ring whose hetero atom is, for example, nitrogen, oxygen, or sulfur, and which preferably contains 1 to 25 carbon atoms and may have a substituent (e.g., an alkyl, such as methyl, isopropyl, and octyl; alkoxy, such as methoxy, isopropoxy and, octoxy; and an alkoxycarbonyl, such as methoxycarbonyl, ethoxycarbonyl, and octoxycarbonyl).
• a substituent e.g., an alkyl, such as methyl, isopropyl, and octyl
• alkoxy such as methoxy, isopropoxy and, octoxy
• an alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, and octoxycarbonyl
• the compound represented by formula (IX) will release ⁇ Z-(L2-Y) b or ⁇ L1-Z-(L2-Y) b after it is coupled with the oxidized product of a color-developing agent.
• L1 in the ⁇ L1-Z-(L2-Y) b will immediately split off, and ⁇ Z-(L2-Y) b is formed.
• the ⁇ Z-(L2-Y) b diffuses in the photosensitive layer while exhibiting a development-­retarding effect, and part of it flows into the color-­development processing solution.
• the ⁇ Z-(L2-Y) that has flowed into the processing solution decomposes quickly at the chemical bond part in L2, that is, the linkage between Z and Y is cleaved, leaving in the developing solution a compound wherein a water-soluble group is attached to Z and whose developing-retarding property is low. Hence the development-retarding effect substantially disappears.
• a divalent nitrogen-­containing heterocyclic group or nitrogen-containing heterocyclic thio group such as a tetrazolylthio group, a benzthiazolylthio group, a benzimidazolylthio group, a thiadiazolylthio group, an oxadiazolylthio group, a triazolylthio group, and an imidazolylthio group. Examples are shown below in the formulae connecting with A-(L1) a - group and -(L2-Y) b group.
• a substituent represented by X1 is included in the part of Z in formula (IX), and it preferably represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkaneamido group, an alkeneamido group, an alkoxy group, a sulfonamido group, or an aryl group.
• Examples of the group represented by Y in formula (IX) include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an aralkyl group, or a heterocyclic group.
• R21 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 cycloalkyl group, an alkanesulfonyl group, an arylsulfonyl group, or an acyl group;
• R22 represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, or an aryl
• the linking group represented by L2 in formula (IX) includes a chemical bond that will cleave in a developing solution.
• Examples of such a chemical bond include those listed in the following Table. Since those may be cleaved by a nucleophilic reagent, such as a hydroxy ion or hydroxylamine, the effect of the present invention can be obtained.
• a nucleophilic reagent such as a hydroxy ion or hydroxylamine
• the divalent linking group shown in the above Table is attached to Z, directly or through an alkylene group and/or a phenylene group, and to Y directly. If the divalent linking group is attached to Z through an alkylene group or a phenylene group, the divalent group may contain, for example, an ether linkage, an amido linkage, a carbonyl group, a thioether bond, a sulfone group, a sulfonamido linkage, and a urea bond.
• substitution position of Z and the substitution position of Y are also shown.
• d is an integer of 0 to 10, preferably 0 to 5
• W1 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, an alkaneamido group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, an aryloxycarbonyl group, an alkanesulfonamido group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, an aryl group, a carbamoyl group, an N-alkylcarbamoyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atom
• the alkyl group or alkenyl group represented by X1 and Y more particularly represents a straight-chain, branched or cyclic alkyl group or alkenyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, which preferably has a substituent, such as a halogen atom, a nitro group, an alkoxy group having 1 to 4 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an alkanesulfonyl group having 1 to 4 carbon atoms, an arylsulfonyl group having 6 to 10 carbon atoms, an alkaneamido group having 1 to 5 carbon atoms, an anilino group, a benzamido group, an alkyl-substituted carbamoyl group having 1 to 6 carbon atoms, a carbamoyl group, an aryl-substituted carbamoyl group having 6 to 10 carbon atoms, an alkyl
• the alkaneamido group or alkeneamido group represented by X1 more particularly represents a straight-­chain, branched or cyclic alkaneamido group or alkeneamido group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, which may have a substituent, such as those mentioned for the above alkyl group and alkenyl group.
• the alkoxy group represented by X1 more particularly represents a straight-chain, branched, or cyclic alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, which may have a substituent, such as those mentioned for the above alkyl group and alkenyl group.
• the aryl group represented by Y preferably represents a phenyl group or a naphthyl group whose substituent is selected, for example, from such substituents as those mentioned for the above alkyl group or alkenyl group, and an alkyl group having 1 to 4 carbon atoms.
• the heterocylic group represented by Y is preferably a 5- to 7-membered heterocylic group, such as a diazolyl group (e.g., 2-imidazolyl and 4-pyrazolyl), a triazolyl group (e.g., 1,2,4-triazol-3-yl), a thiazolyl group (e.g., 2-benzothiazolyl), an oxazolyl group (e.g., 1,3-oxazol-2-yl), a pyrrolyl group, a pyridyl group, a diazonyl group (e.g., 1,4-diazin-2-yl), a triazinyl group (e.g., 1,2,4-triazin-5-yl), a furyl group, a diazolinyl (e.g., imidazolin-2-yl), a pyrrolinyl group, and a thienyl group.
• Couplers represented by formula (IX) useful ones are those represented by the following formulae (X), (XI), (XII), (XIII), (XIV), (XV), and (XVI). These couplers are preferable because their split development retarders are high in development-retarding effect.
• couplers that are used in the present invention, the following compounds can be mentioned, but the present invention is not limited to them.
• the amount of the compound represented by formula (I) of the present invention to be added varies depending on the structure of the compound or the application of the compound, the amount preferably is 1 x 10 ⁇ 7 to 0.5 mol, more preferably 1 x 10 ⁇ 6 to 1 x 10 ⁇ 1 mol, per mol of silver present in the same layer or in the adjacent layer.
• the compound represented by formula (I) of the present invention may be used alone or in combination with a known coupler in a certain layer. If the compound represented by formula (I) of the present invention is used in combination with another color image-forming coupler, the molar ratio of the present compound to the other color image-forming coupler is from 0.1/99.9 to 90/10, preferably from 1/99 to 50/50.
• the photographic material of the present invention may be one having, on a support, at least one silver halide emulsion layer of at least a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and there is no limit to the number and order of the silver halide emulsion layers and the nonsensitive layers.
• a silver halide photographic material having on the support at least one photosensitive layer consisting of several silver halide emulsion layers, whose color sensitivites are substantially the same and whose photographic sensitivities are different, the photosensitive layer being a unit photosensitive layer having a color sensitivity to any one of blue light, green light, and red light, and in the case of a multilayer silver halide color photographic material, the unit photosensitive layers are arranged in such a manner that there are, on the support, a red-sensitive layer, a green-sensitive layer, and then a blue-sensitive layer, in the order stated. However, the order may be reversed according to the purpose, or the same color-sensitive layers may have a different color-­sensitive layer between them.
• Nonsensitive layers such as various intermediate layers, may be placed between said silver halide photosensitive layers, or on the top or bottom layer of said silver halide photosensitive layers.
• Such intermediate layers may contain couplers, DIR compounds, etc., as described in JP-A Nos. 43748/1986, 113438/1984, 113440/1984, 20037/1986, and 20038/1986, and also color-mix inhibitors as used usually.
• each of the silver halide emulsion layers constituting respective unit photosensitive layers preferably use can be made of a two-layer constitution consisting of a high-speed emulsion layer and a slow-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045.
• the emulsion layers are arranged in such an order that the sensitivities lower successively toward the support, and it also is possible to provide a nonsensitive layer between the halogen emulsion layers.
• JP-A No. 112751/1982, 200350/1987, 206541/1987, and 206543/1987 it is possible to provide a slow-speed emulsion layer away from the support and a high-speed emulsion layer near the support.
• BL slow-speed blue-sensitive layer
• BH high-speed blue-sensitive layer
• GH high-speed green-sensitive layer
• GL high-speed red-sensitive layer
• RH low-speed red-sensitive layer
• RL slow-speed blue-­sensitive layer
• JP-B means examined Japanese patent publication
• JP-B means examined Japanese patent publication
• JP-A Nos. 25738/1981 and 63936/1987 an arrangement of a blue-sensitive layer/GL/RL/GH/RH with the blue sensitive layer being furthest from the support is also possible.
• an arrangement of three layers having different sensitivities on a support with the sensitivities being lowered toward the support that is, an arrangement including, on the support, a silver halide emulsion layer highest in sensitivity as an upper layer, a silver halide emulsion layer as an intermediate layer lower in sensitivity than that of the upper layer, and a silver halide emulsion layer as a lower layer lower in sensitivity than that of the intermediate layer, in the stated order, can be mentioned.
• a preferable silver halide contained in the photographic emulsion of the photographic material used in the present invention is silver bromoiodide, silver chloroiodide, or silver bromochloroiodide containing about up to 30 mol % of silver iodide, with silver bromoiodide or silver bromochloroiodide containing about 2 mol % to about 25 mol % of silver iodide particularly preferred.
• the silver halide grains in the photographic emulsions may have a regular crystal structure such as cubic, octahedral, or tetradecanhedral, an irregular crystal such as spherical or tabular, a crystal having crystal defects such as twin planes, or a thereof composite crystal structure.
• the grain size of the silver halide may be fine grains having a diameter of about 0.2 ⁇ m or less, or coarse grains with the diameter of the projected area being down to 10 ⁇ m, and a polydisperse emulsion or a monodisperse emulsion can be used.
• the silver halide photographic emulsion for use in the present invention can be prepared by the process described, for example, in Research Disclosure (RD) No. 17343 (December, 1987), pp. 22 - 23, " I. Emulsion Preparation and Types” ; ibid. No. 18716 (November, 1979), p. 648; P.Glafkides, Chemie et Phisique Photographique (Paul Montel, 1967); G.F. Duffin, Photographic Emulsion Chemistry (Focal Press, 1966); or V.L. Zelikman, et al., Making and Coating Photographic Emulsion (Focal Press, 1964).
• a monodisperse emulsion described, for example, in U.S. Patent Nos. 3,574,628 and 3,655,394, and British Patent No. 1,413,748 is also preferably.
• Tabular grains having an aspect ratio of 5 or more can be used in the present invention.
• Tabular grains may be easily prepared by suitably using the methods described, for example, in Gutoff : Photographic Science and Engineering , Vol. 14, pp. 248 - 257 (1970) : U.S. Patent Nos. 4,434,226, 4,414,310, 4,433,048, and 4,439,520; and British Patent No. 2,112,157.
• the crystal structure may be uniform, the outer halogen composition may be different from the inner halogen composition, or the crystal structure may be layered.
• the halide composition may be joined by the epitaxial joint to a different silver halide composition or a compound other than silver halides, for example, silver rhodanide or lead oxide, is jointed.
• the emulsion to be used in the present invention may be physically ripened, chemically ripened, and spectrally sensitized. Additives to be used in these steps are described in Research Disclosure Nos. 17643 and 18716, and the involved sections are listed in the Table below.
• Additive RD 17643 RD 18716 1 Chemical sensitizer p. 23 p. 648 (right column) 2 Sensitivity-enhancing agents ditto ditto 3 Spectral sensitizers, Supersensitizers pp. 23-24 pp. 648 (right column) -649 (right column) 4 Brightening agents p. 24 - 5 Antifogging agents and Stabilizers pp. 24-25 p. 648 (right column) 6 Light absorbers, Filter dyes and UV absorbers pp. 25-26 pp.
• yellow couplers those described, for example, in U.S. Patent Nos. 3,933,501, 4,022,620, 4,326,024, and 4,401,452, JP-B No. 10793/1983, British Patent Nos. 1,425,020 and 1,476,460, U.S. Patent Nos. 3,973,968, 4,314,023 and 4,511,649, and European Patent No. 249,473A may be used preferably.
• the 5-pyrazolone type and pyrazoloazole type are preferable, and those described, for example, in U.S. Patent Nos. 4,310,619 and 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A No. 33552/1985, Research Disclosure No. 24230 (June 1984), JP-A Nos. 43659/1985, 72238/1986, 35730/1985, 118034/1980, 118034/1980, and 18595/1985, U.S. Patent Nos. 4,500,630 4,540,654, and 4,556,630 are particularly preferable.
• cyan couplers can be mentioned phenol couplers and naphthol couplers, and those described, for example, in U.S. Patent Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, and 4,327,173, West German Patent Application (OLS) No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent Nos. 3,446,622, 4,333,999, 4,451,559, 4,427,767, 4,690,889, 4,254,212, and 4,296,199, and JP-A Nos. 42658/1986 are preferable.
• OLS West German Patent Application
• a coupler that releases a photographically useful residue can be used favorably in this invention.
• a DIR coupler that releases a development retarder those described in patents cited in paragraph VII-F of the above-mentioned Research Disclosure No. 17643, JP-A Nos.151944/1982, 145234/1982, and 184248/1985, and U.S. Patent No. 4,248,962 are preferable.
• Couplers for use in the present invention can be introduced into a photographic material by any one of various known dispersing methods.
• high boiling organic solvents having a boiling point of 175 °C or higher at the normal pressure examples include phthalic esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl)phthalate, bis(2,4-di-­t-amylphenyl)isophthalate, and bis(1,1-diethylpropyl) phthalate), phosphoric or phosphonic esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldi­phenyl phosphate, tricyclohexyl phosphate, tri-2-ethyl­hexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, and di
• the auxiliary solvents are organic solvents hhaving a boiling point higher than about 30 °C, preferably from about 50 °C to below about 160 °C.
• these solvents include ethyl acetate, butyl acetate, ethyl propionate, methylethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.
• various antiseptics or mildewproofing agent such as, for example, benzoisothiazolone, n-butyl p-hydroxybenzoate, phenols, and 2-(4-thiazolyl)benzimidazole, described in JP-A Nos. 257747/1988 and 272248/1987, and Japanese Patent Application No. 238096/1987.
• the present invention can be applied to various color photographic materials. Examples may be mentioned include color negative film for general use or movie, color reversal film for slide or television, color paper, color positive film, and color reversal paper.
• Suitable bases that can be used in the present invention are described, for example, on p. 28 of the above-mentioned RD No. 17643, and on the right column of p. 627 to the left column of p. 648 in ibid . No. 18716.
• the color photographic material according to the present invention can be subjected to development processing as described in pp. 28 - 29 of the above-­mentioned RD No. 17643, and on the left to right columns of p. 651 in ibid . No. 18716.
• the color-developing solution to be used in the developing process of the photographic material of the present invention is preferably an aqueous alkaline solution whose major component is an aromatic primary amine-type color developing agent.
• the color developing agent aminophenol-type compounds are useful, and p-phenylenediamine-type compounds are preferably used, typical examples thereof being 3-methyl-4-amino-N,N-­diethylaniline, 3-metyl-4-amino-N-ethyl-N- ⁇ -­hydroxylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -­methanesulfonamidoethylaniline, and 3-methyl-4-amino-N-­ethyl-N- ⁇ -methoxyethylaniline and their sulfates, and hydrochlorides or p-toluenesulfonates. These compounds may be used in combination according to the purpose.
• the color-developing solution contains pH buffers such as carbonates, borates, or phosphates of alkali metals; antifoggants or development retarders, such as mercapto compounds, benzothiazoles, benzimidazoles, iodides or bromides; and if required, preservatives such as hydroxylamines, diethylhydroxylamines, sulfites, hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, and triethylenediamines(1,4-­diazabicyclo[2,2,2]octane); organic solvents such as ethylene glycol and diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines; dye-forming couplers; competing couplers; fogging agents such as sodium boron hydride; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; thickening
• black-and-white developing solution known black-­and-white-developing agents such as dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-­pyrazolidone), and aminophenols (e.g., N-methyl-p-­aminophenol) may be used alone or in combination with others.
• dihydroxybenzenes e.g., hydroquinone
• 3-pyrazolidones e.g., 1-phenyl-3-­pyrazolidone
• aminophenols e.g., N-methyl-p-­aminophenol
• the color-developing solution has a pH of 9 to 12.
• the replenishing amount of the developing solution varies depending on the color photographic material to be processed, generally the replenishing amount is 3 l or below per m2 of the photographic material, and the replenishing amount can be lowered to 500 ml or below if the bromide ion concentration of the replenishing solution is lowered. If it is required to lower the replenishing amount, it is preferable that the area of the processing tank in contact with air is minimized to prevent the solution from evaporating or being oxidized by air.
• the replenishing amount can also be lowered by suppressing the accumulation of bromide ions in the developing solution.
• the processing time of color-­development is set between 2 and 5 minutes, but the processing time can be shortened by using a processing solution of high temperature and high pH, as well as with a high concentration of color developing agent.
• the photographic emulsion layers are generally subjected to a bleaching process after color development.
• the bleaching process can be carried out together with the fixing process (bleach-fixing process), or it can be carried out separately from the fixing process. Further, to quicken the process bleach-fixing may be carried out after the bleaching process. In accordance with the purpose, the process may be arbitrarily carried out using a bleach-fixing bath having two successive tanks, or a fixing process may be carried out before the bleach-fixing process, or a bleaching process may be carried out after the bleach-fixing process.
• the bleaching agent use can be made of, for example, compounds of polyvalent metals, such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitro compounds.
• ferricyanides As typical bleaching agents, use can be made of ferricyanides; dichromates; organic complex salts of iron (II) or cobalt (III), such as complex salts of aminopolycarboxylic acids, for example ethylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycolether­ diaminetetraacetic acid, citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; and nitrobenzenes.
• iron iron
• cobalt cobalt
• aminopolycarboxylic acids for example ethylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropa
• aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and persulfates are preferable in view of rapid processing and the prevention of environmental pollution.
• aminopolycarboxylic acid iron (III) complex salts are particularly useful in a bleaching solution as well as a bleach-fix solution.
• the pH of the bleaching solution or the bleach-fix solution using these aminopolycarboxylic acid iron (III) complex salts is generally 5.5 to 8, but if it is required to quicken the process, the process can be effected at a lower pH.
• bleach-accelerating agents are compounds having a mercapto group or a disulfide linkage, described in U.S. Patent No. 3,893,858, West German Patent Nos. 1,290,812 and 2,059,988, JP-A Nos. 32736/1978, 57831/1978, 37418/1978, 72623/1978, 95630/1978, 95631/1978, 104322/1978, 124424/1978, 141623/1978, and 28426/1978, and Research Disclosure No. 17129 (July. 1978); thiazolidine derivatives, described in U.S. Patent No.
• thiosulfates As a fixing agent can be mentioned thiosulfates, thiocyanates, thioether-type compounds, thioureas, and large amounts of iodide salts, although thiosulfate is used usually, and in particular ammoniun thiosulfate is widely used.
• thiosulfate is used usually, and in particular ammoniun thiosulfate is widely used.
• sulfite salt As the preservative for bleach-fix solution sulfite salt, bisulfite salt, or carbonyl-bisulfite adduct is preferable.
• the silver halide color photographic material of the present invention undergoes, after a desilvering process such as fixing or bleach-fix, a washing step and/or a stabilizing step.
• the amount of washing water may be set within a wide range depending on the characteristics (e.g., due to the materials used, such as couplers), the application of the photographic material, the washing temperature, the number of washing tanks (the number of steps), the type of replenishing system, including, for example, the counter-current system and the direct flow system, and other various conditions.
• the relationship between the number of water-­washing tanks and the amount of washing water in the multi-­stage counter-current system can be found according to the method described in Journal of Society of Motion Picture and Television Engineers , Vol. 64, pages 248 to 253( May 1955).
• the pH of the washing water used in processing the present photographic material is 4 to 9, preferably 5 to 8.
• the washing water temperature and the washing time to be set may vary depending, for example, on the characteristics and the application of the photographic material, and they are generally selected in the range of 15 to 45 °C for 20 sec. to 10 min., and preferably in the range of 25 to 40 °C for 30 sec. to 5 min.
• the photographic material of the present invention can be processed derectly with a stabilizing solution instead of the above washing.
• a stabilizing process any of known processes, for example, a multi-step counter-current stabilizing process or its low-replenishing-amount process, described in JP-A Nos. 8543/1982, 14834/1983, and 220345/1985.
• the above washing process is further followed by a stabilizing process, and as an example thereof can be mentioned a stabilizing bath that is used as a final bath for color photographic materials for photography, which contains formalin and a surface-­active agent.
• a stabilizing bath that is used as a final bath for color photographic materials for photography, which contains formalin and a surface-­active agent.
• each kind of the chelating agents and bactericides may be added.
• the over-flowed solution due to the replenishing of washing solution and/or stabilizing solution may be reused in other steps, such as a desilvering step.
• the silver halide color photographic material of the present invention may contain therein a color-­developing agent for the purpose of simplifying and quickening the process.
• a color-­developing agent for the purpose of simplifying and quickening the process.
• a precursor for a color-developing agent for example, indoaniline-type compounds described in U.S. Patent No. 3,342,597, Schiff base-type compounds described in U.S. Patent No. 3,342,599 and Research Disclosure Nos. 14850 and 15159, aldol compounds described in Research Disclosure No. 13924, metal salt complexes described in U.S. Patent No. 3,719,492, and urethane-type compounds described in JP-A No. 135628/1978 can be mentioned.
• the present silver halide color photographic material may contain, if necessary, various 1-phenyl-3-­pyrazolidones. Typical compounds are described in JP-A No. 64339/1981, 144547/1982, and 115438/1983.
• the various processing solutions used for the present invention are used at 10 to 50 °C. Although generally a temperature of 33 to38 °C is standard, a higher temperature can be used to accelerate the process to reduce the processing time, or a lower temperature can be used to improve the image quality or the stability of the processing solutions. Also, to save the silver of the photographic material, a process using hydrogen peroxide intensification or cobalt intensification described in West German Patent No. 2,226,770 and U.S. Patent No. 3,674,499 may be carried out.
• the photographic material of the present invention can be applied to the heat development-type photographic material as described in U.S. Patent No. 4,500,626, JP-A Nos. 133449/1985 and 218443/1984, and European Patent No. 210,660A2.
• the silver halide color photographic material of the present invention has the effects of a dye produced by coupling with the oxidized product of a color developing agent being sufficiently fast, of not contaminating a development processing solution, and providing a highly sensitive color photographic image excellent in sharpness and color reproduction.
• a multilayer color photosensitive material (Sample 101) consisting of layers of the following composition was prepared on an undercoated triacetate cellulose film support.
• the coating amount of silver halide and colloidal silver are each indicated in g/m2 in terms of silver
• the coating amount of the coupler, additive, and gelatin are each indicated in g/m2
• the coating amount of the sensitizing dye is indicated in mol per mol of silver halide.
• Symbols showing additives have meanings as shown below, but when having plural effects, one of them is shown as a representative: UV : ultraviolet absorbent, Solv : high-boiling organic solvent, ExS : sensitizing dye, ExC : cyan coupler, ExM : magenta coupler, ExY : yellow coupler, Cpd : additive,
• Silver iodobromide emulsion (AgI : 14 mol%, uniform AgI-type, diameter corresponding to sphere : 0.5 ⁇ m, deviation coefficient of diameter : 20 %, tabular grains, diameter/thickness : 3.0) silver 1.2 Silver iodobromide emulsion (AgI : 13 mol%, uniform AgI-type, diameter corresponding to sphere : 0.3 ⁇ m, deviation coefficient of diameter : 15 %, cubic grains, diameter/thickness : 1.0) silver 0.6 Gelatin 1.0 ExS-1 4 x 10 ⁇ 4 ExS-2 5 x 10 ⁇ 5 ExC-1 0.05 ExC-2 0.05 ExC-3 0.03 ExC-4 0.12 ExC-5 0.01
• Silver iodobromide emulsion (AgI : 16 mol%, inner higher AgI-type of core/shell ratio 1:1, diameter corresponding to sphere : 0.7 ⁇ m, deviation coefficient of diameter : 15 %, tabular grains, diameter/thickness : 5) silver 0.7 Gelatin 1.0 ExS-1 3 x 10 ⁇ 4 ExS-2 2.3 x 10 ⁇ 5 ExC-6 0.11 ExC-7 0.05 ExC-4 0.05 Solv-1 0.05 Solv-3 0.05
• Silver iodobromide emulsion (AgI : 14 mol%, surface higher AgI-type of core/shell ratio 1:1, diameter corresponding to sphere : 0.5 ⁇ m, deviation coefficient of diameter : 15 %, tabular grains, diameter/thickness : 4.0) silver 0.35 Silver iodobromide emulsion (AgI : 3 mol%, uniform AgI-type, diameter corresponding to sphere : 0.3 ⁇ m, deviation coefficient of diameter : 25 %, cubic grains, diameter/thickness : 1.0) silver 0.20 Gelatin 1.0 ExS-3 5 x 10 ⁇ 4 ExS-4 3 x 10 ⁇ 4 ExS-5 1 x 10 ⁇ 4 ExM-8 0.4 ExM-9 0.07 ExM-10 0.02 ExY-11 0.03 Solv-1 0.3 Solv-4 0.05
• Silver iodobromide emulsion (AgI : 14 mol%, inner higher HgI-type of core/shell ratio 1:3, diameter corresponding to sphere : 0.7 ⁇ m, deviation coefficient of diameter : 20 %, tabular grains, diameter/thickness : 5.0) silver 0.8 Gelatin 0.5 Exs-3 5 x 10 ⁇ 4 ExS-4 3 x 10 ⁇ 4 ExS-5 1 x 10 ⁇ 4 ExM-8 0.1 ExM-9 0.02 ExY-11 0.03 ExC-2 0.03 ExM-14 0.01 Solv-1 0.2 Solv-4 0.01
• Silver iodobromide emulsion (AgI : 12 mol%, inner higher AgI-type of core/shell ratio 2:1, diameter corresponding to sphere : 1.0 ⁇ m, deviation coefficient of diameter : 15 %, tabular grains, diameter/thickness : 6.0) silver 0.35
• Silver iodobromide emulsion (AgI : 12 mol%, inner higher AgI-type of core/shell ratio 1:1, diameter corresponding to sphere : 0.4 ⁇ m, deviation coefficient of diameter : 20 %, tabular grains, diameter/thickness : 6.0) silver 0.20 Gelatin 0.5 ExS-3 8 x 10 ⁇ 4 ExY-13 0.11 ExM-12 0.03 ExM-14 0.10 Solv-1 0.20
• Silver iodobromide emulsion (AgI : 14.5 mol%, uniform AgI-type, diameter corresponding to sphere : 0.7 ⁇ m, deviation coefficient of diameter 15 %, tabular grains, diameter/­thickness : 7.0) silver 0.3 Silver iodobromide emulsion (AgI : 13 mol%, uniform AgI-type, diameter corresponding to sphere : 0.3 ⁇ m, deviation coefficient of diameter 25 %, tabular grains, diameter/­thickness : 7.0) silver 0.15 Gelatin 1.6 ExS-6 2 x 10 ⁇ ExC-16 0.05 ExC-2 0.10 ExC-3 0.02 ExY-13 0.3 ExY-15 1.0 Solv-1 0.20
• Twelfth layer High-speed blue-sensitive emulsion layer
• Silver iodobromide emulsion (AgI : 10 mol%, inner higher AgI-type, diameter corresponding to sphere : 1.0 ⁇ m, deviation coefficient of diameter : 25 %, multiple twinned crystal tabular grains, diameter/thickness : 2.0) silver 0.5 Gelatin 0.5 ExS-6 1 x 10 ExY-15 0.20 ExY-13 0.05 Solv-1 0.10
• Second protective layer
• Fine-grain silver bromide emulsion (AgI : 12 mol%, uniform AgI-type, diameter corresponding to sphere : 0.07 ⁇ m) silver 0.5 Gelatin 0.45 Poly(methyl methacrylate) particles (particle diameter : 1.5 ⁇ m) 0.2 H-1 0.4 Cpd-5 0.5 Cpd-6 0.5
• Samples 102 to 114 were prepared with the same procedure as Sample 101, except that couplers shown in Table 1 were respectively added to the 11th layer and to the 12th layer in place of ExY-13 in such amount that the gradation when wedge-exposed by a blue light is to be equal.
• Sample 120 was prepared with the same procedure as Sample 101, except that ExY-15 was added to the 11th and to the 12th layer, respectively, in place of ExY-13 in the amount of equal mol to ExY-13.
• the thus-prepared Samples 101 to 114 and 120 were evaluated for 1) sharpness, 2) interlayer effect, 3) stability of dye-image, and 4) sensitivity change after running processing according to the folowing procedures.
• each sample was subjected to processing process I described below to evaluate a sharpness by the measurement of MFT.
• Each sample was subjected to an wedge exposure to a yellow light after a uniform exposure to a green light and then a development process according to processing process I described below.
• the thus-processed samples were evaluated as to density and the degree of interlayer effect by a green-density D G at the portion of yellow density of 1.5.
• each sample was subjected to a wedge exposure to a white light and then to a development process according to the following processing process I. Then, each sample was subjected to a humidity and heat stability test by leaving samples in the atmosphere of 60°C and 70 % RH. The density after the test for the portion having yellow density of 1.0 before test was shown.
• the sensitivities (at the portion having density of fogging + 0.2) of a processed sample immediately after starting an automatic developer (processing process I shown below) and a processed sample after 20 days from starting (after running processing 800 meter for 35 mm film) were measured to evaluate the sensitivity change (as sample for the running test, film that had taken a photograph of a standard object was used).
• the development processing was carried out in accordance with the following procedure by an automatic developer (until the accumulated replenishing amount reached 3 times the tank volume of the mother solution). Processing procedure Step Time (min.:sec.) Temp. (°C) Replenisher Amount(ml)* Tank Volume(l) Color developing 3 : 15 38 45 10 Bleaching 1 : 00 38 20 4 Bleach-fixing 3 : 15 38 30 8 Water-washing(1) : 40 35 ** 4 Water-washing(2) 1 : 00 35 30 4 Stabilizing : 40 38 20 4 Drying 1 : 15 55 Note: * replenisher amount per 35 mm width 1 m length ** counter current piping system from washing (2) to (1)
• compositions of the processing solutions were as follows: Color-developing solution Mother solution(g) Replenisher (g) Diethylenetriaminepentaacetate 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonate 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg - Hydroxylamine sulfate 2.4 2.8 4-(N-ethyl-N- ⁇ -hydroxyethylamino)-2-methylaniline sulfate 4.5 5.5 Water to make 1.0 l 1.0 l pH 10.05 10.10
• Tap water was treated by passage through a hybrid-type column filled with an H-type strong acidic cation-exchange resin (Amberlite IR-120B, made by Rohm & Haas) and an OH-type strong alkaline anion-exchange resin (Amberlite IRA-400, made by the same company) to obtain water containing calcium and magnesium ions of each below 3mg/l.
• H-type strong acidic cation-exchange resin Amberlite IR-120B, made by Rohm & Haas
• Amberlite IRA-400 OH-type strong alkaline anion-exchange resin
• Comparative couplers used are as follows: Table 1 Sample No. Coupler in the 11th and the 12th layers MTF-value* D G ** Fastness of Image Sensitivity Change 101(Comparative Example) ExY-13 + 0.15 - 0.23 0.73 ⁇ 0 102( " ) Comparative Coupler (1) + 0.12 - 0.15 0.97 - 0.18 103( " ) " (2) + 0.13 - 0.16 0.97 - 0.16 104( " ) " (3) + 0.14 - 0.19 0.82 - 0.10 105(This Invention) Exemplified Coupler (1) + 0.15 - 0.24 0.96 ⁇ 0 106( " ) " (2) + 0.16 - 0.23 0.97 ⁇ 0 107( " ) " (3) + 0.16 - 0.24 0.98 ⁇ 0 108( " ) “ (6) + 0.15 - 0.23 0.97 - 0.01 109( " ) “ (10) + 0.15 - 0.23 0.97 ⁇ 0 110( “ ) “ (21)
• Sample 101 which employed a coupler described in U.S. Patent No. 4,477,563, has a problem of image-dye fastness, although a change of sensitivity is not observed.
• Samples 102 and 104 which employed couplers described in JP-A Nos. 82423/1972 and 261262/1988, have a problem such that the sensitivity lowers during the running processing, although there is no problem with image-dye fastness.
• Samples 105 to 114 solved these problems, being excellent in sharpness and color reproduction.
• Example 2 The same evaluation as in Example 1 was carried out, except that the processing process was changed to the following processing process II.
• compositions of the processing solutions were as follows: Color-developing solution Mother solution(g) Replenisher (g) Diethylenetriaminepentaacetate 5.0 6.0 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.3 0.9 Potassium iodide 1.2 mg - Hydroxylamine sulfate 2.0 2.8 4-(N-ethyl-N- ⁇ -hydroxyethylamino)-2-methylaniline sulfate 4.7 5.3 Water to make 1.0 l 1.0 l pH 10.00 10.05

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• 1989
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