EP0175311B1 - Matériau photographique couleur à l'halogénure d'argent sensible à la lumière - Google Patents

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

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Publication number
EP0175311B1
EP0175311B1 EP19850111632 EP85111632A EP0175311B1 EP 0175311 B1 EP0175311 B1 EP 0175311B1 EP 19850111632 EP19850111632 EP 19850111632 EP 85111632 A EP85111632 A EP 85111632A EP 0175311 B1 EP0175311 B1 EP 0175311B1
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EP
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Prior art keywords
silver halide
group
light
sensitive
halide emulsion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19850111632
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German (de)
English (en)
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EP0175311A3 (en
EP0175311A2 (fr
Inventor
Shigeto Hirabayashi
Yukio Ohya
Syoji Matsuzaka
Yoshiyuki Nonaka
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0175311A2 publication Critical patent/EP0175311A2/fr
Publication of EP0175311A3 publication Critical patent/EP0175311A3/en
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Publication of EP0175311B1 publication Critical patent/EP0175311B1/fr
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3041—Materials with specific sensitometric characteristics, e.g. gamma, density
    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • 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
    • G03C2200/00—Details
    • G03C2200/23—Filter dye
    • 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 silver halide color photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material for color printing paper use in which the image sharpness is improved.
  • a silver halide color photographic light-sensitive material is coated on the support thereof with three kinds of silver halide emulsion layers for photographic use which are spectrally sensitized selectively so as to have the sensitivity to blue-light, green-light, and red-light, respectively.
  • a silver halide color photographic light-sensitive material for color-negative use a blue-light-sensitive silver halide emulsion layer, a green-light-sensitive silver halide emulsion layer and a red-light-sensitive.
  • silver halide emulsion layer are generally coated thereon in order from the side to be exposed, and between the blue-light-sensitive silver halide emulsion and the green-light-sensitive silver halide emulsion layer there is provided with a yellow filter layer capable of bleaching itself for absorbing blue-light transmitting through the blue-light-sensitive silver halide emulsion layer, and further, each of the emulsion layers is provided with other interlayers with a variety of special purposes and a protective layer as the outermost layer, and still further, in a silver halide photographic light-sensitive material for color printing paper use, a red-light-sensitive silver halide emulsion layer, a green-light-sensitive silver halide emulsion layer and a blue-light-sensitive silver halide emulsion layer are generally coated thereon in order from the side to be exposed, and similar to the case of the silver halide photographic light-sensitive material for color negative use, the interlayers with the particular purposes including a ultraviolet ray absorbing layer
  • each of these silver halide emulsion layers is provided in different arrangements, and that a double-layered light-sensitive silver halide emulsion layer sensitive to each color rays in the substantially same wavelength region may be used for the respective silver halide emulsion layers.
  • a color developing agent such as an aromatic primary amine developing agent is used to develop the exposed silver halide grains and a dye image is formed by the reaction of the oxidation products produced of the color developing agent with a dye formable coupler.
  • a phenol or naphthol cyan coupler in order to form the dye image in cyan, magenta and yellow, a phenol or naphthol cyan coupler, a 5-pyrazolone, pyrazolinobenzimidazole, pyrazolotriazole, indazolone or cyanoacetyl magenta coupler, or an acylacetamide yellow coupler are used, respectively.
  • the above-mentioned dye forming couplers are contained in a light-sensitive silver halide emulsion layer or a developer.
  • This invention relates to a silver halide photographic light-sensitive material for color printing paper use, in which the above-mentioned couplers are contained in advance in the silver halide emulsion layers.
  • the reasons why the silver halide photographic light-sensitive materials for color printing paper use are low in image sharpness are assumedly as follows: Namely, the most serious cause of the low sharpness is attributed to a large halation or irradiation caused by diffusing a light in a reflective support or by reflecting from the surface of the reflective support when exposing to light, because the reflective support used is in white.
  • a well known technique among the techniques for preventing the deterioration of image sharpness caused by such halation or irradiation is that such a colored layer as an antihalation layer or a filter layer is provided, and a technique is also well known in which a coloring agent such as colloidal silver is added in an alkaline soluble resin or a hydrophilic colloid to use as a coloured layer. It is not only a matter of course that such coloring agent of the above-mentioned colored layers shall completely be decolored in a process after exposing a silver halide color photographic light-sensitive material to light, such as in a developing process or the like, but also that the coloring agent is required to be excellent in spectral absorption and inert in photographic chemistry.
  • This invention has been achieved by taking the above-mentioned problems into consideration.
  • an object of the invention to provide a silver halide color photographic light-sensitive material having a high image sharpness, as a technical target thereof.
  • a silver halide color photographic light-sensitive material of the invention capable of achieving the above-mentioned technical target comprises a reflective support bearing thereon photographic component layers including at least a blue-light-sensitive silver halide emulsion layer, a green-light-sensitive silver halide emulsion layer and a red-light-sensitive silver halide emulsion layer each being associated with a complementary coupler, at least one layer of the photographic component layers containing at least one dye which is either water-soluble or capable of being decolorized by a development processing liquid, such silver halide color photographic light-sensitive material of the invention being characterized in that at least one of the photographic component layers comprises a compound capable of releasing a development inhibitive substance or the precursor thereof through a reaction with the oxidation product of a color developing agent and the optical reflection density of the silver halide color photographic light-sensitive material in 470 nm, 550 nm or 680 nm is not less than 0.5.
  • the photographic component layer described herein means any of the hydrophilic colloidal layers taking part in forming an image. They include, for example, a silver halide emulsion layer, a subbing layer, an interlayer such as a simple interlayer, a filter layer, an ultraviolet ray absorbing layer, an antihalation layer, etc., a protective layer, and the like.
  • the typical examples of the DIR compounds include a DIR coupler having introduced into the coupling position thereof a group capable of forming a compound having a development inhibiting function when splitting off from the coupling position.
  • Such couplers are described, for example, in British Patent No. 935,454 and U.S. Patent No. 3,227,554, 4,095,984, and 4,149,886, Japanese Patent O.P.I. Publication No. 151944/1982, and the like.
  • the above-mentioned DIR couplers have the functions that the parent nucleus forms a dye when the coupler makes a coupling reaction to the oxidation product of a color developing agent, and on the other hand, the DIR couplers also have the function to release development inhibitor.
  • the DIR couplers include such a compound as described in U.S. Patent No. 3,652,345, 3,928,041, 3,958,993, 3,961,959, and 4,052,213, and Japanese Patent O.P:I. Publication No. 110529/1978,13333/1979 and 161237/1980, and the like, in which a development inhibitor is released but a dye is not formed when the compound makes a coupling reaction to the oxidation product of a color developing agent.
  • timing DIR compounds that is, a compound that the parent nucleus forms a dye or a colorless compound when coupling to the oxidation product of a color developing agent and on the other hand the timing group which was splitted off releases a development inhibitor through an intramolecular nuclephilic substitution reaction or an elimination reaction, such as described in Japanese Patent O.P.I. Publication Nos. 145135/1979, 114946/1981 and 154234/1982.
  • the invention also makes use of such a timing DIR compound that such a timing group as mentioned above is coupled to the parent nucleus of a coupler capable of producing a completely diffusible dye when making a reaction with the oxidation product of a development agent, such as described in Japanese Patent O.P.I. Publication Nos. 160954/1983 and 162949/1983.
  • the more preferable DIR compounds may be represented by the following Formulas (I) and (II), and among them, in particular, the most preferable DIR compound is a compound represented by the following Formula (II):
  • the inhibitors represented in the abovegiven formulas are a component of a compound (i.e., the residual group of the compound) capable of splitting off through a reaction with a color developing agent so as to inhibit a development of a silver halide.
  • the preferable compounds thereof include, for example, such a heterocyclic compound as benztriazole, 3-octylthio-1,2,4-triazole and the like, a heterocyclic mercapto compound.
  • heterocyclic groups include, for example, a tetrazolyl group, thiadiazolyl group, oxadiazolyl group, thiazolyl group, oxazolyl group, imidazolyl group, triazolyl group and the like; and typically include 1-phenyltetrazolyl group, 1-ethyltetrazolyl group, 1-(4-hydroxyphenyl)tetrazolyl group, 1,3,4-thiazolyl group, 5-methyl-1,3,4-oxadiazolyl group, benzthiazolyl group, benzoxazolyl group, benzimidazolyl group, 4H-1,2,4-triazolyl group and the like.
  • the inhibitor couples to the coupling point of the Coup.
  • Formula (V) gives an example of the timing groups each releasing an inhibitor through an intramolecular nucleophilic substitution reaction; wherein Nu represents a nucleophilic group having oxygen, sulfur or nitrogen atom having abundant electrons and is coupled to the coupling position of Coup; E represents an electrophilic group having a carbonyl group, thiocarbonyl group, a phosphinyl group or a thiophosphinyl group having inabundant electrons, and is coupled to the hetero atom of an inhibitor; and V represents a coupling group which is subjected to an intramolar nucleophilic substitution reaction which is followed by forming a three- membered ring or a seven-membered ring after releasing Nu from Coup because V relates Nu to E in three dimensions, and thereby V is capable of releasing an inhibitor.
  • Coup and Inhibitor are synonymous with the above.
  • Optical reflection density (D R ) according to the invention is well known in the skilled in the art and defined as follows: wherein Ps is the radiant flux reflected by the sample, and Po is the radiant flux incident on the sample.
  • the DIR compounds may be added into a light-sensitive silver halide emulsion layer and/or a non-light-sensitive photographic component layer, and preferably into the blue-, green-, or red-light-sensitive silver halide emulsion layer.
  • the above-mentioned DIR compounds are ordinarily added in an amount of 2 x 10- 4 to 5 x 10- 1 mol per mol of silver in an emulsion layer, and more preferably 1 x 10- 3 to 1 x 10- 1 mol.
  • DIR compounds In order to contain the above-mentioned DIR compounds into a silver halide emulsion layer or the coating solutions of other photographic component layers relating to the invention, they may be added after they are changed into an alkaline solution when the DIR compounds are alkali-soluble, and when they are oil-soluble, it is preferred that the DIR compounds are dissolved in a high boiling solvent and, if necessary, a low boiling solvent in combination, and are then added in a silver halide emulsion after dispersing in the forms of fine particles in such a process as described in U.S. Patent Nos. 2,322,027, 2,801,170, 2,801,171, 2,272,191 and 2,304,940.
  • hydroquinone derivatives ultraviolet absorption agent, anti-discoloring agent and the like in combination. It is also allowed to use two or more kinds of the DIR compounds mixed together. More detailed description of how to add the preferred DIR compounds in the invention is that one or no less than two kinds of the DIR compounds are dissolved together with, if necessary, other couplers, a hydroquinone derivative, an anti-discoloring agent, a ultraviolet absorbing agent and the like are dissolved in an organic amide, a carbamate, an ester, a ketone, a urea derivative, an ether, a hydrocarbon, and in particular, a high boiling solvent such as di-n-butylphthalate, tricresylphosphate, triphenyl phosphate, di-isooctylazelate, di-n-butyl- sebacate, tri-n-hexylphosphate, N,N-di-ethyl-capryl
  • the above couplers may also be dispersed in a latex dispersing method.
  • Such latex dispersing method and the effects thereof are described in Japanese Patent O.P.I. Publication Nos. 74538/1974, 59943/1976 and 32552/1979, and Research Disclosure No. 14850, pp. 77-79.
  • the suitable latexes include, for example, a homopolymer, copolymer and terpolymer each of such a monomer as styrene, acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetacetoxy ethyl methacrylate, 2-(methacryloyloxy)ethyltrimethyl ammonium methosulfate, 3-(methacryloyloxy)propane-1-sodium sulfonate, N-isopropyl acrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, 2-acrylamido-2-methylropane sulfonic acid, and the like.
  • a homopolymer, copolymer and terpolymer each of such a monomer as styrene, acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetacetoxy
  • DIR compounds can be synthesized in the processes described respectively in U.S. Patent Nos. 3,227,554, 3,615,506, 3,617,291, 3,632,345, 3,928,041, 3,933,500, 3,938,996, 3,958,993, 3,961,959, 4,046,574, 4,052,213, 4,063,950, 4,095,984, 4,149,886, and 4,234,678; British Patent Nos. 2,072,363 and 2,070,266; Research Disclosure No. 21228, 1981; Japanese Patent O.P.I. Publication Nos.
  • a development inhibitor being released when developing from the DIR compounds corresponding to the density of an image are able to obtain two kinds of image effects;
  • the one effect is the so-called intraimage effect in which the development inhibitor inhibits a development corresponding to an image density and improves the image sharpness in a layer when the layer is a light-sensitive emulsion layer
  • the other effect is the so-called interimage effect such as a masking effect in which the development inhibitor inhibits the developments of other layers corresponding to the image density of a layer being the source of diffusion, when the released development inhibitor diffuses to the other layers.
  • the DIR compounds may be added to a light-sensitive silver halide emulsion layer and/or a non-light-sensitive photographic component layer. It is good enough that, preferably, at least one of silver halide emulsion layers contains such DIR compound.
  • a DIR compound for example, in the case of adding such a DIR compound to an ordinary multilayered color photographic light-sensitive material comprising a blue-light-sensitive silver halide emulsion layer, a green-light-sensitive silver halide emulsion layer and a red-light-sensitive silver halide emulsion layer, it is good enough to contain in one or not less than two layers thereof.
  • Water-soluble dyestuffs or those decolorized by a developing liquid, (AI dyes) which are to be used in the photographic component layers of a silver halide color photographic light-sensitive material of the invention include an oxonal dye, a merocyanine dye, a hemioxonol dye and an azo dye. Among them, the oxonol, hemioxonol and merocyanine dyes and the like are useful. The examples of such dyes capable of being used may be given in British Patent Nos. 584,609 and 1,277,429; Japanese Patent O.P.I. Publication Nos.
  • the AI dyes of the invention may be added into a light-sensitive silver halide emulsion layer and/or a non-light-sensitive photographic component layer.
  • No less than two of the AI dyes of the invention are allowed to be contained in one and the same layer. And, the same AI dye is allowed to be contained in not less than two different layers.
  • the quantity of these AI dyes added is preferably from 2 x 10- 4 to 5 x 10- 1 mol per mol of a silver halide being contained in every blue-, green- and red-light-sensitive silver halide emulsion layer, and more preferably from 2 x 10- 3 to 5 x 10- 1 mol.
  • the silver halide color photographic light-sensitive materials of the invention are to be so contained with the AI dyes as to indicate a value of not less than 0.5 in at least one of the optical reflective densities of 470 nm, 550 nm or 680 nm.
  • the every optical reflective density thereof is lower than 0.5, not only the effect is not expected on improving an image sharpness, but also the color reproductivity is deteriorated.
  • the upper limit of the optical reflective density is not limitative, however, it is preferred to be not more than 2.0 from the view point of the sensitivity, decolorization property thereof and the like.
  • an amount of silver (i.e., a coating weight of silver) to be contained in the silver halide emulsion layer thereof is preferably from 0.3 to 1 g per sq. meter in the total of the light-sensitive silver halide emulsion layers.
  • the amount of silver is not more than 1 g per sq. meter to obtain an excellent image quality, and is not less than 0.3 g per sq. meter to obtain a relatively higher maximum density and a higher sensitivity.
  • a silver halide composition preferably used in the invention is silver chlorobromide or silver chloroiodobromide. Further, it is also allowed to use such a combined mixture of silver chloride and silver bromide. That is to say, for the purpose of realizing a high speed development, it is preferred to contain chlorine atoms in the halide composition of a silver halide, and more preferred that the silver halide is silver chlorobromide or silver chloroiodobromide each containing at least 1 mol% silver chloride.
  • the crystals of these silver halide particles may be of normal or twin type.
  • the ratio of [100] plane to [111 ] plane is arbitrary to use.
  • the crystal structures of these silver halide particles may be either uniform from the interior through the exterior thereof or of the layered structure (a core-shell type) in which the interior and the exterior are heterogeneous.
  • These silver halides may be of either a type of forming a latent image mainly on the surface thereof or a type of forming a latent image inside the particles thereof.
  • tabular silver halide particles (described in Japanese Patent Application No. 170070/1984) may be used.
  • the silver halide particles which are preferably used in the invention are of the monodispersion type which may be obtained any one of the preparation processes such as an acidic process, neutral process, ammoniacal process, which have so far been known in the art.
  • compositions containing the above-mentioned silver halide particles are hereby called a silver halide emulsion.
  • silver halide emulsions may also be chemically sensitized with an active gelatin; a sulfur sensitizer such as alylthiocarbamide, thiourea, cystine and the like; a selenium sensitizer; a reduction sensitizer such as a stannous salt, thiourea dioxide, polyamine and the like; a noble metal sensitizer such as gold sensitizer including typically potassium aurothiacyanate, potassium chloroaurate, 2-aurothio-3-methyl benzothiazolium chloride and the like, or a sensitizer of a water-soluble salt of, for example, ruthenium, palladium, platinum, rhodium, iridium and the like including typically ammonium chloropalladate, potassium chloroplatinate, sodium chloropalladate (some kinds thereof function as a sensitizer, an antifoggant and the like, depending upon the quantity thereof); which are used independently or in combination suitably (for example, in combination of gold sensit
  • the silver halide emulsions relating to the invention may be chemically ripened by adding thereto a sulfur-containing compound, and may be contained thereto at least one kind of hydroxytetrazaindenes and at least one kind of nitrogen-containing heterocyclic compounds having a mercapto group before, during or after the chemical ripening.
  • Silver halide to be used in the invention can also be optically sensitized by adding thereto a suitable sensitizing dye in an amount of 5 x 10- 8 to 3 x 10- 3 mol per mol of the silver halide so as to endow each of the regions of desired photospectral wavelengths with photosensitivity.
  • a suitable sensitizing dye in an amount of 5 x 10- 8 to 3 x 10- 3 mol per mol of the silver halide so as to endow each of the regions of desired photospectral wavelengths with photosensitivity.
  • sensitizing dyes may be used, and each of them may be used independently or in combination with two or more kinds thereof.
  • Such sensitizing dyes which may be advantageously used in the invention may be given below, for example.
  • the sensitizing dyes to be used in a blue-light-sensitive silver halide emulsion include, for example, those described in West German Patent No. 929,080; U.S. Patent Nos. 2,231,658, 2,493,748, 2,503,776,2,519,001, 2,912,329, 3,656,959, 3,672,897, 3,694,217, 4,025,349 and 4,046,572; British Patent No. 1,242,588; and Japanese Patent Examined Publication Nos. 14030/1969 and 24844/1977; and the like.
  • the sensitizing dyes to be used in a green-light-sensitive silver halide emulsion typically include, for example, a canine dye, a merocyanine dye or a compound cyanine dye such as described in U.S. Patent Nos. 1,939,210, 2,072,908, 2,739,149, and 2,945,763; British Patent No. 505979; and the like.
  • the sensitizing dyes to be used in a red-light-sensitive silver halide emulsion include typically a cyanine dye, a merocyanine dye and a compound cyanine dye such as described in U.S. Patent Nos.
  • cyanine dyes, merocyanine dyes or the compound cyanine dyes such as described in U.S. Patent Nos. 2,213,995, 2,493,748, and 2,519,001; West German Patent No. 929,080; and the like may also advantageously be used in a green or red-light-sensitive silver halide emulsion.
  • sensitizing dyes may be used independently or in combination. Such combination of sensitizing dyes is frequently used especially for the purpose of color-hypersensitizing.
  • the typical examples thereof are described in U.S. Patent Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862, and 4,026,707; Japanese Patent Examined Publication Nos. 4936/1968 and 12375/1978; Japanese Patent O.P.I. Publication Nos. 110618/ 1977 and 109925/1977.
  • the silver halide emulsion layers relating to the invention it is allowed to contain the other couplers than the DIR compounds of the invention, i.e., a compound capable of forming a dye through a reaction thereof with the oxidation products of a color developing agent.
  • a yellow coupler, a magenta coupler and a cyan coupler may be used without any special limitation.
  • These couplers may be of the so-called two-equivalent type or four-equivalent type, and a diffusible dye releasing coupler and the like may also be used when combining with the above-mentioned couplers.
  • Such yellow couplers which are useful include, for example, an open-chained ketomethylene compound and further the so-called two-equivalent type couplers such as an active point-o-aryl substituted coupler, an active point-o-acyl substituted coupler, an active point-hydantoin compound substituted coupler, an active point-urazol compound substituted coupler and an active point-succinic acid imide compound substituted coupler, an active point-fluorine substituted coupler, an active point-chlorine or bromine substituted coupler, an active point-o-sulfonyl substituted coupler, and the like.
  • the typical examples of the useful yellow couplers include those described in U.S. Patent Nos.
  • Magenta couplers which may be used in the invention include, for example, such a compound of a pyraxolone, a pyrazolotriazole, a pyrazolinobenzimidazole, an indazolone.
  • the above-mentioned magenta couplers may include not only four-equivalent type couplers but also two-equivalent type couplers, similar to the case of the yellow couplers.
  • the typical examples of such magenta couplers include, for example, those described in U.S. Patent Nos.
  • Cyan couplers which are useful in the invention include, for example, a phenol coupler, a naphthol coupler and the like. These cyan couplers may be of not only the four-equivalent type but also the two-equivalent type, similar to the case of the yellow couplers.
  • the typical cyan couplers include, for example, those described in U.S. Patent Nos. 2,369,929, 2,434,272, 2,474,293, 2,521,908, 2,895,826, 3,034,892, 3,311,476, 3,458,315, 3,476,563, 3,583,971, 3,591,383, 3,767,411, and 4,004,929; West German OLS Patent Nos.
  • the amount of the couplers added is not limitative, however, it is preferably from 1 x 10- 3 to 5 mol per mol of silver, and more preferably from 1 x 10- 2 to 5 x 10- 1 mol per mole of silver.
  • a variety of photographic additives may be contained in the silver halide color photographic light-sensitive materials of the invention.
  • an antifoggant for example, there may be used an antifoggant, a stabilizer, an ultraviolet ray absorbing agent, an anti-color contamination agent, an optical brightening agent, an anti-fading agent for a color image, an antielectrostatic agent, a hardener, a surface active agent, a plasticizer, a wetting agent and the like.
  • a hydrophilic colloid which is used for preparing an emulsion include anyone out of a protein such as gelatin, a derivative gelatin, a graft polymer of gelatin and other macromolecules, albumin, caseii, and the like; a cellulose derivative such as a hydroxyethylene cellulose derivative, carboxymethylene cellulose, and the like; a starch derivative, a synthetic hydrophilic macromolecule of a single or the polymer of polyvinyl alcohol, polyvinyl imidazole, polyacrylamide and the like.
  • a protein such as gelatin, a derivative gelatin, a graft polymer of gelatin and other macromolecules, albumin, caseii, and the like
  • a cellulose derivative such as a hydroxyethylene cellulose derivative, carboxymethylene cellulose, and the like
  • a starch derivative a synthetic hydrophilic macromolecule of a single or the polymer of polyvinyl alcohol, polyvinyl imidazole, polyacrylamide and the like.
  • Supports of the silver halide color photographic light-sensitive materials of the invention may be anyone of the reflective type.
  • such supports include, for example, baryta paper; polyethylene coated paper; polypropylene synthetic paper; a transparent support provided with a reflective layer or a reflector, such as a glass plate, a polyester film, e.g., cellulose acetate film, cellulose nitrate film or a poly- ethyleneterephthalate film; a polyamide film; a polycarbonate film; a polystyrene film; and the like.
  • These supports may suitably be selected to use according to the purpose of using a light-sensitive material.
  • a variety of coating methods such as a dipping method, an air-doctor method, a curtain coating method, a hopper coating method and the like may be applied.
  • a simultaneous coating method for not less than two layers may also be applied, such as described in U.S. Patent No. Nos. 2,761,791 and 2,941,898.
  • each emulsion layer may be determined arbitrarily.
  • a blue-light-sensitive silver halide emulsion layer it is preferred to arrange a green-light-sensitive silver halide emulsion layer and a red-light-sensitive silver halide emulsion layer in order from the support side.
  • These light-sensitive silver halide emulsion layers each may comprise two or more layers.
  • the light-sensitive materials of the invention it is arbitrary to provide an interlayer in a suitable thickness according to the purpose of using the sensitive material.
  • a variety of layers such as a filter layer, an anticurling layer, a protective layer and an antihalation layer may be suitably combined to use as the compound layers of the light-sensitive material.
  • a hydrophilic colloid capable of being used in such an emulsion layer as mentioned above may similarly be used as a bonding agent.
  • various photographic additives capable of being contained in such an emulsion layer as mentioned above may be contained.
  • the processes of a photographic light-sensitive material using the silver halide emulsions relating to the invention are not specially limited, but any of the processes may be applied.
  • the typical examples of the processes include a process in which, after color developing, a bleach-fixing is carried out, and, if necessary, a washing and/or a stabilizing are further carried out; a process in which, after color developing, a bleaching and a fixing are separately carried out, and, if necessary, a washing and/or stabilizing are further carried out; a process in which a prehardening, neutralizing, color developing, stopping and fixing, washing, bleaching, fixing washing, posthardening, and washing are carried out in order; a process in which a color developing, washing, supplementary color developing, stopping, bleaching, fixing, washing, and stabilizing are carried out in order; a developing process in which, after halogenation-bleaching a developed silver produced by a color development, an amount of dyes produced is increased by carrying out another color development again; that is
  • Color developers capable of being used in processing a silver halide emulsion of the invention are an alkaline solution each of which the pH value is preferably no less than 8 and more preferably from 9 to 12 when they contain a color developing agent.
  • An aromatic primary amine which may be served as the above-mentioned developing agent is a compound having amino group on the aromatic ring and is capable of developing an exposed silver halide, and. in addition, may be added if necessary with a precursor capable of forming such a compound.
  • Typical examples of the above-mentioned color developing agents include those of p-phenylenediamine type, and the preferable examples include the following:
  • An amount of the above-mentioned aromatic primary amine compound to be used depends upon what degree the activity of a developer is to be determined to. It is desired to increase the amount thereof if the activity should be raised.
  • the amount thereof to be used is within the range of from 0.0002 mol per liter to 0.7 mol per liter. No less than two kinds of the compounds may also be used in combination according to silver halide purposes.
  • any arbitrary combination may freely be used purposively, such as a combination of 3-methyl-4-amino-N,N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-(3-methanesulfon- amidoethylaniline, a combination of 3-methyl-4-amino-N-ethyl-N-)3-methanesulfonamido ethylaniline and 3-methyl-4-amino-N-ethyl-N-(i-hydroxyethylaniline, and the like.
  • Color developers capable of being used in the invention are allowed to contain arbitrarily a variety of ingredients which are popularly added, such as an alkaline agent including, for example, sodium hydroxide, sodium carbonate and the like, an alkali metal sulfite, an alkali metal hydrogen sulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener, a thickening agent, a development accelerator, and the like.
  • an alkaline agent including, for example, sodium hydroxide, sodium carbonate and the like
  • an alkali metal sulfite an alkali metal hydrogen sulfite
  • an alkali metal thiocyanate an alkali metal halide
  • benzyl alcohol benzyl alcohol
  • a water softener a thickening agent
  • a development accelerator and the like.
  • a stain preventive a sludge preventive, a preservative, an interlayer effect accelerator, a chelating agent and the like
  • a bromide such as potassium bromide, ammonium bromide and the like
  • a compound for rapid processing liquid use such as an alkali iodide, nitrobenzoimidazole, mercapto- benzoimidazole, 5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole and the like.
  • the bleaching agents for the bleaching liquids or bleaching-fixing liquids used in a bleaching process there may be used generally known compounds coordinated a metallic ion such as that of iron, cobalt, copper or the like by an organic acid such as aminopolycarboxylic acid oxalic acid, citric acid or the like.
  • an organic acid such as aminopolycarboxylic acid oxalic acid, citric acid or the like.
  • aminopolycarboxylic acid include the following:
  • Such bleaching liquids may contain a variety if additives as well as the above-mentioned bleaching agents.
  • a bleaching-fixing liquid When a bleaching-fixing liquid is used in a bleaching process, a composite liquid containing a silver halide fixing agent is applied, besides the above-mentioned bleaching agents.
  • a halogen compound such as potassium bromide may further be contained in the bleaching-fixing liquid, and similar to the case of the above-mentioned bleaching liquid, it is allowed to contain or add various other additives such as a pH buffer, an optical brightening agent, an anti-foaming agent, a surface active agent, a preserving agent, a chelating agent, a stabilizing agent, an organic solvent and the like.
  • Such silver halide fixing agents include, for example, a compound capable of forming a water-soluble silver salt through a reaction with a silver halide and capable of being used in an ordinary fixing process, such as sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate or thiourea, thioether and the like.
  • the processing temperature is desirably at no lower than 30°C from the viewpoint of rapid process.
  • Any silver halide color photographic light-sensitive material of the invention is also allowed to be processed in such a washing-substitutable stabilizing process as described in Japanese Patent O.P.I. Publication Nos. 14834/1983,105145/1983,134634/1983 and 18631/1983, and Japanese Patent Application Nos. 2709/1983 and 89288/1984, and the like.
  • At least one layer of the photographic component layers contains both DIR compounds and AI dyes and the optical reflection density of the silver halide color photographic light-sensitive material is not less than 0.5 at 470 nm, 550 nm or 680 nm, therefore, it is endowed with a high image-sharpness and capable of obtaining an excellent color-reproductive image.
  • Sample No. 1 of a silver halide color photographic light-sensitive material was prepared in such a manner that each of the undermentioned layers was coated over to a paper support laminated on the both sides thereof with polyethylene, in order from the support side.
  • Samples No. 2 through 8 were prepared in the same manner applied to the above-mentioned Sample No. 1, except that the amount of the AI dye (Al-26) contained in Layer 2 and the DIR compound containing in Layer 3 of the Sample No. 1 were changed as shown in Table 1.
  • composition of each processing liquid is as follows:
  • the MTF Modulation Transfer Function
  • the MTF values thereof were compared with each other in terms of 5 lines/mm of the spatial frequency.
  • the judgements of image sharpness by making use of such MTF have well known in the skilled in the art, and are described in T. H. James, 'The Theory of the Photographic Process', 3rd Edition, Macmillan Co. The results thereof are shown in Table 1.

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Claims (9)

1. Matériau photographique couleur photosensible à base d'halogénure d'argent comprenant un support réflecteur portant des couches de constituants photographiques incluant au moins une couche d'émulsion d'halogénure d'argent cyanophotosensible, une couche d'émulsion d'halogénure d'argent chlorophotosensible et une couche d'émulsion d'halogénure d'argent érythrophotosensible, associées chacune à un copulant complémentaire, au moins une couche desdites couches de constituants photographiques contenant au moins un colorant qui est soit soluble dans l'eau, soit susceptible d'être décoloré par un liquide de traitement de développement, caractérisé en ce qu'au moins une couche desdites couches de constituants photographiques comprend un composé capable de libérer un substance inhibitrice de développement ou un précurseur de celle-ci par une réaction avec le produit d'oxydation d'un agent de développement couleur et en ce que la densité optique par réflexion de ladite matière photographique couleur photosensible à base d'halogénure d'argent à 470 nm, 550 nm ou 680 nm n'est pas inférieure à 0,5.
2. Matériau photographique couleur photosensible à base d'halogénure d'argent selon la revendication 1, dans lequel ledit composé est un composé représenté par les formules (I) ou (II);
Figure imgb0152
dans lesquelles Cop représente un copulant capable de copuler avec le produit d'oxydation d'un agent de développement en couleur;
Inhibiteur représente un groupe qui copule dans une position de copulation de Cop et s'élimine par le réaction de celui-ci avec le produit d'oxydation d'un agent de développement en couleur de manière à devenir un composé capable d'inhiber le développement d'un halogénure d'argent; et TEMPS représente un groupe représenté par les formules (III), (IV), (V) ou (VI) suivantes:
Figure imgb0153
dans lesquelles X représente un groupe d'atomes nécessaire pour compléter un noyau benzènique ou un noyau naphtalènique; Y représente -0-, -S-,
Figure imgb0154
où R3 est un atome d'hydrogène, un groupe alkyle ou aryle, et Y est couplé dans un position de copulation, et R1 et R2 représentent chacun respectivement les groupes synonymes de R3, et le groupe
Figure imgb0155
est substitué en position ortho ou para par rapport à Y et est couplé à un hétéro-atome contenu dans l'inhibiteur
Figure imgb0156
dan laquelle W représente un groupe synonyme d'Y dans la formule (III) ci-dessus; et R4 et R5 sont chacun les groupes synonymes de R, et R2 dans la formule (III); R6 représente un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe acyle, un groupe sulfone, un groupe alkoxycarbonyle ou un groupe résiduel hétérocyclique; et R7 représente un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe résiduel hétérocyclique, un groupe alcoxy, un groupe amino, un groupe acylamide, un groupe sulfonamide, un groupe carboxy, un groupe alcoxycarbonyle, un groupe carbamoyle, ou un groupe cyano; et ce groupe de synchronisation (timing) est couplé dans une position de copulation par W et est couplé à un hétéro-atome de l'inhibiteur par
Figure imgb0157
dans laquelle Nu représente un groupe nucléophile comportant un atome d'oxygène, de soufre ou d'azote ayant une grande quantité d'électrons et est couplé dans la position de copulation de Cop; E représente un groupe électrophile portant un groupe carbonyle, un groupe thiocarbonyle, un groupe phosphinyle ou un groupe thiophosphinyle déficient en électrons, et est couplé à l'hétéro-atome d'un inhibiteur; et V répresente un groupe de copulation qui est soumis à une réaction de substitution nucléophile intramoléculaire qui est suivie par la formation d'un cycle à trois maillons ou d'un cycle à sept maillons après élimination de Nu de Cop parce que V relie Nu à E en trois dimensions, et par conséquent V est capable de libérer un inhibiteur.
Figure imgb0158
dans laquelle Cop et Inhibiteur sont synonymes et ont les mêmes définitions que ci-dessus.
3. Matériau photographique couleur photosensible à base d'halogénure d'argent selon la revendication 1, dans lequel au moins une desdites couches d'émulsion d'halogénure d'argent cyanophotosensible, d'émulsion d'halogénure d'argent chlorophotosensible et d'émulsion d'halogénure d'argent érythrophotosensible contient ledit composé.
4. Matériau photographique couleur photosensible à base d'halogénure d'argent selon la revendication 3, dans lequel la teneur dudit composé est dans l'intervalle de 2 x 10-4 à 5 x 10-1 moles par mole de l'halogénure d'argent contenu dans la couche d'émulsion d'halogénure d'argent cyanophotosensible, chlorophotosensible ou érythrophotosensible contenant ledit composé.
5. Matériau photographique couleur photosensible à base d'halogénure d'argent selon la revendication 1, dans lequel ledit colorant est choisi dans le groupe constitué d'un colorant oxonol, d'un colorant hémioxonol, d'un colorant de merocyanine et d'un colorant azoïque.
6. Matériau photographique couleur photosensible à base d'halogénure d'argent selon la revendication 1, dans lequel la teneur dudit colorant est dans l'intervalle de 2 x 10-4 à 5 x 10-1 moles par mole des halogénures d'argent dans le total contenu dans lesdites couches d'émulsion d'halogénure d'argent cyanophotosensible, d'émulsion d'halogénure d'argent chlorophotosensible et d'émulsion d'halogénure d'argent érythrophotosensible.
7. Matériau photographique couleur photosensible à base d'halogénure d'argent selon la revendication 1, dans lequel ladite densité optique par réflexion à 470 nm, 550 nm ou 680 nm n'est pas supérieure à 2,0.
8. Matériau photographique couleur photosensible à base d'halogénure d'argent selon la revendication 1, dans lequel la teneur totale en argent desdites couche d'émulsion d'halogénure d'argent cyanophotosensible, couche d'émulsion d'halogénure d'argent chlorophotosensible et couche d'émulsion d'halogénure d'argent érythrophotosensible est dans l'intervalle de 0,3 à 1 g/m2.
9. Matériau photographique couleur photosensible à base d'halogénure d'argent selon la revendication 1, dans lequel l'halogénure d'argent de ladite couche d'émulsion d'halogénure d'argent cyanophotosensible, de ladite couche d'émulsion d'halogénure d'argent chlorophotosensible et de ladite couche d'émulsion d'halogénure d'argent érythrophotosensible comprend du chlorure d'argent ou du chloroiodobromure d'argent contenant au moins 1 mole % de chlorure d'argent.
EP19850111632 1984-09-18 1985-09-14 Matériau photographique couleur à l'halogénure d'argent sensible à la lumière Expired EP0175311B1 (fr)

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AU590557B2 (en) * 1985-04-25 1989-11-09 Konishiroku Photo Industry Co., Ltd. Processing method of light-sensitive silver halide color photographic material
EP0264788A3 (fr) * 1986-10-18 1989-07-12 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière à surface unique
DE3751199T2 (de) * 1986-12-09 1995-08-03 Fuji Photo Film Co Ltd Farbphotographisches Silberhalogenidmaterial und Verfahren zu dessen Behandlung.
JPH0810322B2 (ja) * 1987-05-19 1996-01-31 コニカ株式会社 ハロゲン化銀カラ−写真感光材料
JPH0820716B2 (ja) * 1987-05-19 1996-03-04 コニカ株式会社 ハロゲン化銀カラ−写真感光材料
JPH01145654A (ja) * 1987-12-02 1989-06-07 Konica Corp ハロゲン化銀カラー写真感光材料
JPH0264630A (ja) * 1988-08-31 1990-03-05 Konica Corp ハロゲン化銀カラー写真感光材料
JPH02157753A (ja) * 1988-12-09 1990-06-18 Konica Corp カラー画像形成方法
JP2665615B2 (ja) * 1989-11-14 1997-10-22 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
JP2877870B2 (ja) * 1990-02-01 1999-04-05 コニカ株式会社 ハロゲン化銀写真感光材料
JPH04241349A (ja) * 1991-01-14 1992-08-28 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
US5399465A (en) * 1993-01-15 1995-03-21 Eastman Kodak Company Method of processing reversal elements comprising selected development inhibitors and absorber dyes

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DE3564045D1 (en) 1988-09-01

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