JPH0548898B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material, and particularly to a silver halide color photographic light-sensitive material having excellent sharpness and graininess. (Prior Art) In recent years, with the spread of small cameras, there has been a demand for image quality enlarged from a small size screen to be equivalent to image quality enlarged from a larger normal size screen. In order to satisfy these needs, it is necessary to develop a color photographic material that has enough graininess and sharpness that the printed image quality is not impaired even when the enlargement magnification is increased. Various methods have been known to improve the sharpness of images, but it is widely known that great effects can be obtained by increasing the edge effect and reducing light scattering in photographic materials. . Among these, the edge effect utilizes the concentration gradient of a development inhibiting substance present during development. In this case, known development inhibiting substances include, for example, iodide ions and bromide ions released when silver halide is developed in a developer, or substances produced by oxidation of a developing agent. Effects similar to those of these development inhibitors are described in U.S. Patent No.
Compounds described in No. 3227554, No. 3615506, No. 3617291, No. 3701783, etc., or
It is also known that it can be actively enhanced by using further improved so-called DIR compounds and DIR couplers as described in US Pat. No. 34933 (including DIR couplers with so-called timing groups as described in US Pat. ing. However, even when using the above-mentioned DIR couplers, if a strong edge effect is required, a large amount of DIR couplers must be used, which inevitably greatly inhibits development. Therefore, there is a limit to the amount of DIR coupler that can be used, and there is also a limit to the edge effect caused by the above-mentioned DIR coupler. The drawback was that there was no. Increasing the coating amount of silver to solve this problem not only increases the product cost, but also increases the light scattering caused by silver halide, which reduces the DIR addition layer and This results in deterioration of the sharpness of the lower layer as well. A DIR coupler was proposed that could improve the conventional drawbacks, maintain a constant maximum image density, and particularly enhance the edge effect. (Special application 1982-
No. 7150). This invention is a diffusible development inhibitor-releasing coupler (hereinafter referred to as a diffusible DIR coupler) that can react with the oxidation product of a developing agent during development and release a development inhibitor with a diffusivity of 0.4 or more.
The invention relates to a silver halide color photographic light-sensitive material characterized by containing. Furthermore, in order to improve the above invention and obtain a silver halide color photographic light-sensitive material with excellent sharpness and color reproduction, a cyan color-forming diffusive DIR compound was added to the red-sensitive layer, and a magenta color-forming DIR compound and a blue color-forming DIR compound were added to the green-sensitive layer. An application has been filed for a method in which a yellow color-forming DIR compound is used in each of the sensitive layers (Japanese Patent Application No. 58-237069). In order to increase the multilayer effect and improve the sharpness by using a diffusive DIR compound that develops the same color in the emulsion layer for the purpose of improving sharpness, the diffusive DIR compound needs to be more active than the main coupler. be. However, when a large amount of such highly active couplers is used, a large dye cloud is generated particularly in a low concentration area, resulting in a major drawback of worsening graininess. In this way, it has not been possible to simultaneously achieve excellent color reproduction, extremely high sharpness, and fine graininess using conventional techniques. (Object of the Invention) Therefore, the first object of the present invention is to provide a silver halide color photographic light-sensitive material having extremely excellent graininess and image sharpness. A second object of the present invention is to provide a silver halide color photographic material with extremely excellent color reproducibility. (Structure of the Invention) The object of the present invention is to print one of the three subtractive primary colors on a support.
at least one silver halide emulsion layer containing a coupler that develops a color (hereinafter referred to as a main coupler) and a diffusible DIR coupler that develops a hue that is substantially the same as the main coupler; This is achieved by a silver halide color photographic light-sensitive material characterized by having at least one non-photosensitive layer containing a diffusive DIR compound represented by the following general formula []. Containing a diffusive DIR compound that develops the same hue as the main coupler not only improves color reproduction, but also greatly improves sharpness by reducing film thickness and enhancing the edge effect. have.
Furthermore, by including a DIR compound in the adjacent non-photosensitive layer, it was discovered that not only the graininess was greatly improved, but also the sharpness was actually improved, which was a surprising effect, which was considered difficult to achieve in the past. Sharpness,
It has become possible to improve graininess and color reproducibility at the same time. Furthermore, in order to increase the effect of improving color reproducibility, it is preferable that the diffusive DIR compound used in the non-photosensitive layer also develops a color having substantially the same hue as the coupler in the adjacent emulsion layer. The diffusible DIR compound referred to in the present invention is a compound that causes a coupling reaction with an oxidized form of a developing agent during development.
It means a compound capable of releasing a diffusible development-inhibiting compound or development-inhibiting precursor. A diffusible DIR coupler refers to one that releases a diffusible development-inhibiting compound or its precursor through a coupling reaction and simultaneously forms a dye. In the present invention, it is preferable to use a DIR compound with a diffusivity of 0.4 or more (the measurement method and the diffusible DIR compound are described in European Patent No. 101621) and which can release a highly diffusive development inhibitor.
DIR couplers are preferred. Such a DIR coupler is represented by the following general formula []. General formula [] A(-Y) _n In the formula, A represents a coupler component, and m is 1 or 2
Y represents a group that binds to the coupling position of the coupler component A and leaves upon reaction with the oxidized product of the color developing agent, and represents a highly diffusible development inhibitor or a compound capable of releasing a development inhibitor. In the general formula [], Y is the following general formula [
Represents a] to []. General formula [a] General formula [b] General formula [] General formula []

【formula】 General formula []

[Formula] In the general formulas [a], [b] and [],
R ₁ represents an alkoxycarbonyl group or an aryloxycarbonyl group. In general formula [a], general formula [b] and [], n is 1 or 2
and when n is 2, R ₁ may be the same or different, and the total number of carbons contained in n R ₁ is 2 to 10. In the general formula [], R ₂ represents an alkyl group, an aryl group or a heterocyclic group. In the general formula [], R ₃ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,
R ₄ represents an alkyl group or an aryl group substituted with an alkoxycarbonyl group or an aryloxycarbonyl group. In the general formula [], the number of carbon atoms contained in R ₂ is 2 to 15. In the general formula [], the total number of carbon atoms contained in R ₃ and R ₄ is 2 to 15. General formula [] -TIME-INHIBIT In the formula, the TIME group is a group that is bonded to the coupling position of the coupler and can be cleaved by reaction with a color developing agent, and after being cleaved by the coupler,
Represents a group that can release an INHIBIT group in a moderately controlled manner. The INHIBIT group has the above general formula [a] ~ []
It is expressed as In the above formula, the -TIME-INHIBIT group is preferably the general formula [] to general formula [] described in European Patent No. 101621. The yellow image-forming coupler residue represented by A includes pivaloylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malone ester monoamide type, Coupler residues of benzothiazolylacetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, malon diester type, benzimidazolylacetamide type or benzimitazolylacetate type, heterozygous compounds included in U.S. Pat. No. 3,841,880 Coupler residues derived from ring-substituted acetamides or heterocycle-substituted acetates, or U.S. Pat.
Examples include coupler residues derived from acylacetamides described in JP-A No. 50-139738 or Research Disclosure No. 15737, and heterocyclic coupler residues described in US Pat. No. 4,046,574. The magenta image-forming coupler residue represented by A includes a coupler residue having a 5-oxo-2-pyrazoline nucleus, a pyrazolo-[1,5-a]benzimidazole nucleus, or a cyanoacetophenone type coupler residue. is preferred. The cyan image-forming coupler residue represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus. In the general formula [], A is the general formula [A], [A], [A], [A] described in European Patent No. 101621.
,
Those represented by [A], [A], [A], [A], and [A] are preferred. Specific examples of diffusive DIR couplers are shown below. D-1 to D-14 below are cyan coloring diffusivity
DIR couplers D-15 to D-28 are specific examples of magenta coloring diffusive DIR couplers, and D-29 to D-46 are yellow coloring diffusive DIR couplers. D-3 D-7 D-14 D-15 D-19 D-21 D-22 D-26 D-27 D-29 D-31 D-33 D-45 The above-mentioned diffusing DIR compounds according to the present invention are disclosed in U.S. Pat. No. 3,227,554, U.S. Pat.
Same No. 3958993, Same No. 4149886, Same No. 4234678,
JP 51-13239, JP 57-56837, British Patent No.
It can be easily synthesized by the method described in No. 2070266, No. 2072363, Research Disclosure No. 212, December 1981, No. 21228, etc. In the present invention, the effect of the present invention itself is not affected whether silver halide is contained in the non-photosensitive layer or not at all. When photosensitive silver halide is contained, it accounts for at least 50%, preferably at least 70%, of the total molar amount of compounds that can cause a coupling reaction with the oxidation product of the developing agent contained in the non-photosensitive layer. Preferably, 90% or more (100% is very advantageous) of the DIR compound significantly inhibits the development of the photosensitive silver halide in the layer and renders it substantially non-photosensitive. Because it can be said. The amount of the diffusible DIR compound added is preferably 0.00001 to 0.002 mol/m ² , more preferably 0.00002 to 0.001 mol/m ² in both the non-photosensitive layer and the photosensitive layer. The thickness of the non-photosensitive layer is preferably 0.1 to 5μ, and 0.3 to 5μ.
3μ is more preferred. In the present invention, the diffusible DIR compound and other couplers described below can be introduced into the silver halide emulsion layer or the non-light-sensitive layer using known methods, such as the U.S. Pat.
The method described in No. 2322027 is used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, etc.)
dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate),
benzoic acid esters (e.g. octyl benzoate) alkyl amides (e.g. diethyl laurylamide),
Fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesate esters (e.g. tributyl trimesate), etc., or organic solvents with a boiling point of about 30°C to 150°C, such as lower alkyl acetate, butyl acetate, etc. After being dissolved in acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. As the binder or protective colloid that can be used in the emulsion layer or non-photosensitive layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. In addition to lime-processed gelatin, acid-processed gelatin, Bull.Soc.Scl.Phot.Japan.No.16,
Enzyme-treated gelatin as described in P30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Gelatin derivatives include gelatin with acid halides,
Those obtained by reacting various compounds such as acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be used. Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferable is 2
Silver iodobromide containing from mol% to 12 mol% silver iodide. The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, the ridge length in the case of cubic grains,
Expressed as an average based on projected area. ) is not particularly limited, but is preferably 3μ or less. The particle size may be narrow or wide. The silver halide grains in the photographic emulsion may have regular crystal structures such as cubic or octahedral shapes, or may have irregular crystal structures such as spherical or plate shapes, or may have irregular crystal structures such as spherical or plate shapes. It can also be a composite of shapes. It may also consist of a mixture of particles of various crystalline forms. Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area. The silver halide grains may have a layered structure in which the interior and surface layers have different phases, a bonded structure, or a uniform phase. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particle. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique (Paul
Motel Publishing, 1967), GFDuffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZelikman et al.
Making and Coating Photographic Emulsion
(The Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
One type of simultaneous mixing method is a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is,
A so-called controlled double jet method may also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, cadmium, zinc salt, lead salt, thallium salt,
An iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be coexisting. After the emulsion is precipitated or physically ripened, soluble salts are usually removed, and the long-known Nudel water washing method, which involves gelling gelatin, may be used. Inorganic salts such as sodium sulfate,
Precipitation methods using anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) ) may be used. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see for example “Die
Grundlagen der Photographischen Prozesse
mit Silberhalogeniden” (Akademische
Verlagsgesellschaft, 1968) pages 675-734 can be used. That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds) reduction sensitization method;
Noble metal compounds (e.g., gold complex salts, Pt, Ir,
A noble metal sensitization method using complex salts of metals in the periodic table group such as Pd can be used alone or in combination. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Zaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a, 7) tetraazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be added. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast , sensitization)
Various surfactants may be included for various purposes. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic interfaces such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator: Alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurine, sulfosuccinic acid Contains acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters, etc. Anionic surfactants; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts Cationic surfactants such as heterocyclic quaternary ammonium salts such as , pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)
Acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, Hydroxyalkyl (meth)
Polymers containing a combination of acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used. For the photographic processing of the layer consisting of the photographic emulsion produced using the present invention, any of the known methods and known processing solutions, such as those described in Research Disclosure No. 176, pages 28-30, can be applied. can do. This photographic processing may be carried out depending on the purpose, or photographic processing that forms a dye image (color photographic processing).
It may be either. Processing temperature is usually 18℃
to 50°C, but the temperature may be lower than 18°C or higher than 50°C. As a special type of development processing, a method may be used in which a developing agent is contained in the light-sensitive material, for example, in an emulsion layer, and the light-sensitive material is processed in an aqueous alkaline solution to perform development. Among the developing agents, hydrophobic ones are listed in Research Disc.
It can be incorporated into the emulsion layer by various methods such as those described in Japanese Patent No. 1547763. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. When forming a dye image, conventional methods can be applied.
For example, negative-positive method (e.g. “Journal of the
Society of Motion Picture and Television
Engineers, Volume 61 (1953), pp. 667-701).Color developers generally consist of an alkaline aqueous solution containing a color developing agent.The color developing agent is a known primary aromatic amine. Developers, such as phenylene diamines (e.g. 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N −
β-methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
P226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can include. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, It may also contain a fogging agent such as sodium boron hydride, an auxiliary developer such as 1-phenyl-3-pyrazolidone, a viscosity imparting agent, a polycarboxylic acid chelating agent, an antioxidant, and the like. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleach,
For example, iron (), cobalt (), chromium (),
Compounds of polyvalent metals such as copper, peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Complex salts of aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or organic acids such as citric acid, tartaric acid, and malic acid; persulfates;
Permanganate; nitrosophenol, etc. can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid () complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Bleach or bleach-fix solution has US Patent 3042520
No. 3241966, Special Publication No. 1977-8506, Special Publication No. 1973
- Bleaching accelerator described in No. 8836, etc., JP-A-53-
In addition to the thiol compound described in No. 65732, various additives can also be added. The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments,
Holopolar cyanine dye, hemicyanine dye,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these After the aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure, such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidic-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. The photographic emulsion layer and the non-light-sensitive layer of the photographic light-sensitive material prepared using the present invention contain dye-forming couplers as main couplers and other purposes. diamine derivatives, aminophenol derivatives, etc.)
A compound that can develop color by oxidative coupling with the compound may also be used. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, cyanoacetylcoumaron couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivalo Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect, or a normal DIR coupler that releases a development inhibitor that is not highly diffusive during development. In addition to DIR couplers, colorless DIR coupling compounds whose coupling reaction products are colorless and release development inhibitors, and compounds that release development inhibitors during development can be incorporated into photosensitive materials. May include. Specific examples of magenta coloring couplers are shown in U.S. Patent No.
No. 2600788, No. 2983608, No. 3062653, No. 3127269, No. 3311476, No. 3419391,
Same No. 3519429, Same No. 3558319, Same No. 3582322,
Same No. 3615506, Same No. 3834908, Same No. 3891445,
West German Patent No. 1810464, West German Patent Application (OLS) No.
No. 2408665, No. 2417945, No. 2418959, No. 2424467, Japanese Patent Publication No. 1973-6031, Japanese Patent Publication No. 1973-49-
No. 74027, No. 49-74028, No. 49-129538, No. 50
-60233, 50-159336, 51-20826, same
No. 51-26541, No. 52-42121, No. 52-58922,
This is described in No. 53-55122. A specific example of a yellow coupler is shown in U.S. Patent No.
2875057, 3265506, 3408194, 3551155, 3582322, 3725072,
West German Patent No. 3891445, West German Patent No. 1547868, West German Published Application No. 2219917, West German Patent No. 2261361, West German Patent No. 2414006
No., British Patent No. 1425020, Special Publication No. 51-10783,
JP-A-47-26133, JP-A No. 48-73147, JP-A No. 50-6341
No. 50-87650, No. 50-123342, No. 50-
No. 130442, No. 51-21827, No. 51-102636, No. 51-102636, No. 51-21827, No. 51-102636, No.
It is described in No. 52-82424, No. 52-115219, etc. A specific example of a cyan coupler is described in U.S. Patent No.
No. 2369929, No. 2434272, No. 2474293, No. 2521908, No. 2895826, No. 3034892,
Same No. 3311476, Same No. 3446622, Same No. 3458315,
Same No. 3476563, Same No. 3583971, Same No. 3591383,
Same No. 3758308, Same No. 3767411, Same No. 3880661,
OLS No. 3996253, OLS No. 4004929, West German Patent Application (OLS) No. 2414830, OLS No. 2454329, JP-A-48
−5055, No. 48-59838, No. 51-26034, No. 51
−146828, 52-69624, 52-90932, same
No. 56-65134. Examples of colored couplers include U.S. Patent Nos. 2521908, 3034892, 3476560,
Special Publication No. 38-22335, No. 42-11304, No. 44-2016
No. 44-32461, JP-A No. 51-26034, No. 52-
42121, those described in West German Patent Application (OLS) No. 2418959 can be used. Of course, two or more types of the above-mentioned couplers and the like can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers. The photographic color formers used are conveniently selected to provide intermediate scale images. The maximum absorption band of the cyan dye formed from the cyan color former is between about 600 and 720 nm, and the maximum absorption band of the magenta dye formed from the magenta color former is about 500 nm.
and 580 nm, and the maximum absorption band of the yellow dye formed from the yellow color former is preferably between about 400 and 480 nm. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,3-dihydroxydioxane, etc.), (4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. In the photosensitive material produced using the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc., they may be mordanted with a cationic polymer or the like. The photosensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifogging agent, and specific examples thereof include:
U.S. Patent No. 2360290, U.S. Patent No. 2336327, U.S. Patent No. 2403721,
Same No. 2418613, No. 2675314, No. 2701197, Same No.
No. 2704713, No. 2728659, No. 2732300, No.
No. 2735765, Japanese Patent Application Publication No. 50-92988, No. 50-92989,
No. 50-93928, No. 50-110337, No. 52-146235
No., Special Publication No. 50-23813, etc. The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (such as those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in U.S. Pat.
3314794 and 3352681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat. No. 3705805 and 3707375), butadiene Compounds such as those described in US Pat. No. 4,045,229 or benzoxide compounds (such as those described in US Pat. No. 3,700,455) can be used. Additionally, U.S. Patent 3499762
The material described in JP-A-54-48535 can also be used. UV-absorbing couplers (e.g. α
- naphthol-based cyan dye-forming couplers),
A UV-absorbing polymer or the like may also be used. These ultraviolet absorbers may be mordanted in specific layers. The photographic material produced using the present invention may contain a water-soluble dye as a hydrophilic colloid layer filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. Specific examples of hydroquinone derivatives are US patents
No. 2360290, No. 2418613, No. 2675314, No.
No. 2701197, No. 2704713, No. 2728659, No. 2701197, No. 2704713, No. 2728659, No.
No. 2732300, No. 2735765, No. 2710801, No. 2732300, No. 2735765, No. 2710801, No.
No. 2816028, British Patent No. 1363921, etc., and gallic acid derivatives are described in U.S. Patent No. 3457079,
3069262, etc., and those of p-alkoxyphenols are described in U.S. Patent No. 2735765, U.S. Pat.
3698909, Japanese Patent Publication No. 49-20977, and Japanese Patent Publication No. 52-6623, and those of p-oxyphenol derivatives are described in U.S. Pat.
No. 3574627, No. 3764337, JP-A-52-35633,
No. 52-147434 and No. 52-152225, and that of bisphenols is disclosed in U.S. Pat.
There is a description in the issue. Example 1 A color photographic light-sensitive element sample 101 was prepared on a polyethylene terephthalate support, consisting of each layer having the composition shown below. 1st layer; 1st red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 6 mol%, average grain size 0.6μ)...Silver coating amount 0.023 mol/m ² Sensitizing dye○

Claims (1)

[Scope of Claims] 1. A coupler that develops one of the three subtractive primary colors and a diffusive coupler that develops substantially the same hue as this color and is represented by the following general formula [] on a support.
It includes at least one silver halide emulsion layer containing a DIR coupler, and at least one non-photosensitive layer adjacent to the emulsion layer and containing a diffusible DIR compound represented by the following general formula []. Characteristic silver halide color photographic material. General formula [] A(-Y) _n In the formula, A represents a coupler component, and m is 1 or 2
, and Y represents the following general formula (a) to []. General formula [a] General formula [b] General formula [] General formula [] General formula [] In general formulas [a], [b] and [],
R ₁ represents an alkoxycarbonyl group or an aryloxycarbonyl group. In general formula [a], general formula [b] and [], n is 1 or 2
and when n is 2, R ₁ may be the same or different, and the total number of carbons contained in n R ₁ is 2 to 10. In the general formula [], R ₂ represents an alkyl group, an aryl group or a heterocyclic group. In the general formula [], R ₃ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,
R ₄ represents an alkyl group or an aryl group substituted with an alkoxycarbonyl group or an aryloxycarbonyl group. In the general formula [], the number of carbon atoms contained in R ₂ is 2 to 15. In the general formula [], the total number of carbon atoms contained in R ₃ and R ₄ is 2 to 15. General formula [] -TIME-INHIBIT In the formula, the TIME group is a group that is bonded to the coupling position of the coupler and can be cleaved by reaction with a color developing agent, and after being cleaved by the coupler,
Represents a group that can release an INHIBIT group in a moderately controlled manner. The INHIBITT group has the above general formula [a] ~
Represented by [ ].