JPS62195652A - Silver halide photographic sensitive material having improved sensitivity, fog restraining effect, and graininess - Google Patents

Abstract

PURPOSE:To improve the sensitivity, fog restraining effect, and graininess of a photosensitive material by incorporating a compd. which is capable of coupling with a color developing agent but does not contribute to the formation of picture image, into at least one emulsion layer. CONSTITUTION:A compd. which couples with an oxidized body of a color developing agent but does not contribute to the formation of a picture image (color non-developing coupler) is used, which is, for example, a coupler, etc., as expressed by the formula, dissolved in processing liquid due to water-soluble property of the dye formed by the coupling reaction. In the formula, COUP1 is a mother body of a coupler having a coupling site (*); BALL is a group eliminating from COUP1 by the reaction and contributing to provide resistance to diffusion; SOL is a solubilizing group contributing to discharge a product of the coupling reaction out of the system from the photosensitive material. A photosensitive material is obtd. by incorporating the compd. into a silver halide emulsion layer, incorporating also silver halide having fog centers. Since the color non-developing coupler is incorporated, fogging of the photosensitive material is restrained, and a photosensitive material having high sensitivity is obtd.

Description

[Detailed description of the invention]

[Industrial Field of Application 1] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to an Is silver halide color photographic material having high sensitivity and improved graininess. [Prior art 1] In recent years, with the miniaturization of cameras, there has been a desire for a small 7 ohm screen size for 7! Demand for improved image quality is increasing. Among them, techniques for improving graininess include reducing the grain size of silver halide grains contained in a silver halide emulsion layer, or suppressing the size of a colored dye image using an inhibitor. The demand for higher sensitivity cannot be met. There is also a method of increasing the number of coloring dye spots by increasing the number of silver halide grains contained in the silver halide emulsion layer, but latent image bleaching occurs due to excess oxidized developing agent produced during development. Even if the number of silver hemodenide grains is increased, the number of coloring dye points does not necessarily increase at the same ratio. By the way, the technology for making an internal latent image type silver halide emulsion adjoin or mix with a photosensitive silver halide emulsion is disclosed in US Patent No. 2.
, No. 996,382, but it is easily expected that the fog will be higher than that of the developing mechanism.
When this technique was applied to color photosensitive materials, it was found that the technique was beneficial in improving graininess by increasing the number of coloring points. As a result of extensive research, the inventors of the present invention surprisingly found a method that not only did not increase the fog but also improved the graininess by 6 degrees. OBJECTS OF THE INVENTION As is clear from Section L, the object of the present invention is to provide a silver halide photographic material that has high sensitivity, low fog, and improved graininess.

[Purchase of invention]

[1] The present invention has at least one photosensitive silver halide emulsion layer on a support, and the emulsion layer and/or the layer adjacent thereto contains a silver halide containing silver halide having fog nuclei inside. In a silver halide photographic light-sensitive material, a halogenated material is characterized in that it contains a compound that reacts in combination with an oxidized form of a color developing agent in combination with at least one light-sensitive silver halide emulsion layer but does not contribute to image formation. This was achieved using silver photographic materials. The present invention will be explained in detail below. In the present invention, the photosensitive silver halide emulsion layer refers to a photographic constituent layer containing photosensitive silver monoanide grains. The silver halide emulsion referred to here includes silver halide used in ordinary silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. Any silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferred. The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different. In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into consideration the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the pH and pAg in the mixing pot. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. Conversion methods may be used at any step in the formation of AgX to change the halogen composition of the particles. Known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present during the growth of silver halide grains. In the process of grain formation and/or growth, silver halide grains are produced by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts. Metal ions are added using at least one kind selected from salts (including complex salts), and metal ions are added inside the particles and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere. Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure
Closure (hereinafter abbreviated as RD)) No. 17643, Section 2 can be carried out. The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain. The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain. The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the 011) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. The size of silver halide grains is 0.05 to 30μ,
Preferably, those having a diameter of 0.1 to 20μ can be used. Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). When divided by the average grain size, the value is 0.20 or less.The grain size is the diameter in the case of spherical silver halide, and the diameter in the case of grains with a shape other than spherical. This indicates the diameter when the projected image is converted into a circular image of the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used. The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions. Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination. Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too. Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used. Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment. Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as antifoggants or stabilizers can be added. In the present invention, the photosensitive silver halide emulsion refers to one prepared by the method described above. In the present invention, the photosensitive silver halide emulsion layer and/or the layer adjacent thereto contains a silver halide emulsion having fog nuclei inside as described below. The emulsion having internal fog nuclei useful in the present invention is coated on a support to give a density of 39/@'', and after imagewise exposure, it is treated in a bleaching solution for 5 minutes at 20°C, and then in an internal developer at 20°C. It is preferable that the film is covered to such an extent that no image can be formed when developed for 5 minutes at °C, but it may be one that has the ability to form an image internally (internal latent image type).Especially Preferably, the maximum image density (I)tt of the minimum image density (Dmin) in the processing is
r a x ) (of which 11 is referred to as Takaburi degree) is 0.3 to 1.0. It is preferable that the emulsion having fog nuclei inside, which is useful in the present invention, has no fog nuclei on its surface. When measured by total application I! It is preferable that it is 20 mol% or less based on the amount of i. (Bleach solution A) Red blood salt 3g Phenosafranin 0.01259 Add water to total f.
Let it be f1l12. (Internal developer B) N-medilu p-aminophenol sulfate 2.09 Sodium sulfite 909 Hydroquinone
8.09 Sodium carbonate l hydrate 52.59 Potassium bromide
59 Sodium thiosulfate
Add 10g of water to make a total of ff1l12. (Surface developer C) N-Medilu p-aminophenol sulfate 2.5
9 Ascorbic acid 1092-diedylaminoethal 25I/potassium bromide 1° Sodium carbonate l hydrate 55.69 Add water to make the total amount IQ. In order to fog the interior of the silver halide grains, the emulsion may be irradiated with light, or other methods such as chemical fogging may be used. An emulsion with high internal fog and low surface fog can be obtained by fogging an emulsion with internal and surface sensitivity and then bleaching with a potassium ferricyanide solution. Other methods of producing emulsions having internal fog nuclei include exposing the fog-free internal latent image type emulsion to high energy radiation such as X-rays or ultraviolet or visible light. Internal latent image emulsions are described, for example, in U.S. Pat. No. 2,592,25.
No. 0, but other emulsions that do not need to contain silver iodide can also be used in the present invention. Internal latent image type silver chlorobromide emulsions and silver bromide emulsions can be used in the present invention as well as various other internal latent image type emulsions. Internal latent image type silver halide emulsions useful in the present invention include those prepared by various methods. For example, U.S. Patent No. 2,592,250, JP 52-18309
Conversion type silver halide emulsions described in US Pat. Nos. 3,206,313 and 3,31
Among those described in No. 7゜322, Specification No. 3.367.778, and Japanese Patent Publication No. 43-29I105: 1≦
Silver halide emulsions having chemically sensitized silver anodide grains, U.S. Pat. Nos. 3,271.157 and 3,4.
No. 47,927, No. 3,531゜291, No. 3,
Silver halide emulsions having silver halide grains incorporating polyvalent metal ions as described in No. 703,584, British Patent No. 1,027,146, British Patent No. 3,761,266 , 3,761,276, JP-A-49-106321, JP-A-50-8524, and JP-A-53-60222, silver halide emulsions comprising grains having a laminated structure; and U.S. Patent No. 3,511,622, JP-A-51-74
These include silver halide emulsions containing silver iodide prepared by the ammonia method described in Japanese Patent No. 062. In the silver halide emulsion preferably used in the present invention, fog nuclei are formed inside the silver halide grains by optically or chemically imparting fog nuclei to the silver halide grains, and then a silver salt aqueous solution is added to form the silver halide grains on the grains. For example, pAgl is a method of chemically applying fog.
~8, p) 16~14, 10~18 at temperature 30~80℃
A method of aging for about 0 minutes can be used. Use sulfur sensitizers, reduction sensitizers, noble metal sensitizers, etc. during ripening! By using l' alone or in combination, further (
This is preferable because it can provide fog nuclei to the f-effect. As the sulfur sensitizer, diosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are described in U.S. Pat. No. 1,574,944.
No., No. 2,410,689, No. 2,278,947, 2
, 728°668, 3,656.955-, 4,0
No. 32,928, No. 4,061,140, di-tiny salts of ureas, amines, hydrazine derivatives, porumamidine sulfinic acid, furan compounds, etc. can be used, and specific examples thereof are given in U.S. Pat. No. 487,850, 2,4
No. 19,974, No. 2,518,698, 2゜983.
No. 609, No. 2,983,610-, No. 2,694,63
No. 7, No. 3,930,867 1. I, 054, 45g. In addition to total complex salts, platinum and Iridium J are used as noble metal sensitizers.
2. Complex salts of metals in group I of the periodic table, such as Balanow 1 to 1, can be used, and a specific example thereof is disclosed in U.S. Patent No. 2.399,08.
No. 3, No. 2.4[,060, British Patent No. 618,061
It is written in the number etc. 11; “Silver halide grains that caused fog” 2.
As a method for growing silver halide, a water-soluble silver salt solution and a water-soluble silver halide solution are added to a water-soluble protective colloid solution containing silver halide grains with surface fog. In addition to the double jet method, which simultaneously injects in accordance with the growth speed of Either the neutral method or the acid method may be used. The pAg and pit in the emulsion liquid phase during emulsion preparation can be controlled as necessary. The pAg is preferably in the range of 2 to 13, and the pAg is preferably in the range of 2 to 13. I (is in the range of 2 to 13. The temperature of the emulsion during emulsion preparation is 30 to 90°C, more preferably 35 to 70°C. The silver halide composition of the silver halide emulsion includes any silver halide, such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. The silver halide The composition preferably consists essentially of silver bromide or silver chlorobromide (A gf≦5 mol %).The grain size of the silver halide with internal fog nuclei used in the present invention has special requirements. Although there is no limitation, fine particles are preferable, especially those having an average particle size of 0.
01 to 0.75 μm, more preferably 0.01 to 0.5 μm. Furthermore, there is no particular limitation on the grain shape of a silver halide emulsion having fog nuclei inside, and regular (r-egula) grain shape is not particularly limited.
r) Although the particles may be irregular, they are preferably normal crystals such as octahedrons, cubes, and tetradecahedrons. The silver halide emulsion having fog nuclei inside may be polydisperse, but it is preferably monodisperse (especially one with a coefficient of variation of grain size distribution of 20% or less). The content ratio of photosensitive silver halide grains and internally covered silver halide grains in the silver halide photographic light-sensitive material of the present invention is determined by the type of emulsion used (for example, the halogen composition).
This can be changed depending on the type of light-sensitive material used, the contrast of the emulsion used, etc., but in general, the ratio of photosensitive silver halide grains to silver halide grains having fog nuclei inside them is fTm results are obtained when the molar ratio of is equal or greater. Usually, 0.5 to 100%, especially 2 to 50%, even 5% by mole of silver halide, based on photosensitive silver halide grains.
It is preferable to use silver halide grains having internal fog nuclei in the range of 30% to 30%. The silver halide emulsion layer according to the present invention can be composed of a mixture of a light-sensitive silver halide emulsion and a silver halide emulsion provided with internal fog. Alternatively, these two types of emulsions can be coated as adjacent layers. When these two types of emulsions are coated in separate layers, it does not matter which layer is on top, since the internally fogged emulsions are sufficiently transparent to be coated with light-sensitive halogens. This is because even if the silver oxide emulsion is placed closely to the support, sufficient light can be transmitted through the emulsion which has internal fog when exposed to light. In addition, when these two types of emulsions are applied as adjacent layers, a water-permeable layer may be provided between these emulsion layers to the extent that the effects of the present invention are not impaired. In the present invention, compounds that undergo a coupling reaction with the oxidized form of a color developing agent but do not form a dye (hereinafter referred to as colorless couplers) include the following compounds. (2) Coupler that couples with the oxidized form of a color developing agent and dissolves into the processing solution because the dye formed is water-soluble (2) Coupler that couples with the oxidized form of a color developing agent but remains as a leuco form (3) ) A coupler in which the dye produced by coupling with an oxidized product of a color developing agent does not have significant visible absorption and produces a substantially colorless product.A colorless coupler according to the present invention, which belongs to the above (1). The compound can be represented by the following general formula (1): General formula (1) % formula % In the formula, C0UP+ represents a coupler core having a coupling site (asterisk *), and BAI, 1, is C0UP , a group that binds to the coupling site of C0UP and can be separated from C0UP by reaction of C0UP+ with an oxidized color developing agent.
It is a stable group having a size and shape that makes the compound of general formula ([) resistant to diffusion. SQL is a solubilizing group, which binds to the non-coupling position of COUP, and transfers the coupling product generated by the coupling between COUP and the oxidized product of the color developing agent to the photosensitive material during or after the color development process. This is a group that provides mobility to flow out of the yarn from the inside. The coupler core represented by C0tlPI changes the hue or forms a colorless reaction product through a coupling reaction with an oxidized color developing agent.
Mention may be made of any coupler cores known or used in the art. For example, the coupler core that produces a yellow dye is an acylacetanilide such as acetoacetanilide and benzoylacetanilide, and the coupler core that produces a magenta dye is a core of pyrazolones, pyrazolotriazoles, pyrazolobenzimidazoles, and indacilones. The coupler core for cyan dye formation includes phenols and naphthols. BALI is a stabilizing group having a molecular size and shape that makes the compound of general formula [I] diffusion resistant;
Useful groups represented by BALL include, but are not limited to, alkyl groups having 8 to 32 carbon atoms, aryl groups, and heterocyclic groups, as long as they impart diffusion resistance to the compound of [I]. It will be done. Although these groups do not represent unconventional or substituted groups, they can be used as substituents to increase the diffusion resistance of the compound of general formula (1), and to
It is a group that changes the reactivity of the compound f) or causes a coupling reaction and increases the diffusivity of BALL after separation. Furthermore, it is preferable that BALL is bonded to the cobbling site of the coup via a linking group. Typical linking groups include oxy (-0-), thio (-8-)
, carbonyloxy (-OCO-), sulfonyloxy (-030,-), amide (-NIICO-), sulfonamide (-NIISO*-), and the like. Preferred examples of BALL include an alkoxy group having an alkyl group and/or an aryl group having a total of 8 to 32 carbon atoms, an aryloxy group, a heterocyclic oxy group, an alkylthio group,
Arylthio group, heterocyclic thio group, arylazo group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acylamino group, alkylsulfonamide group, arylsulfonamide group, or nitrogen-containing heterocyclic group (bi[J- , pyrazole, imidazole,
triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, phthalimide, succinimide, 2.4-imidazolidinedione, 2.4-oxazolidinedione, 2.4-diγsilylinedione, triacylidine-3,5-dione, etc.) I can list the following. The solubilizing group represented by SOI is a group that imparts mobility to the coupling product generated by the coupling reaction to the extent that it can flow out of the light-sensitive material system, for example, an ionized group of 0.
hydroxyl groups, carboxyl groups, sulfonyl groups, aminosulfonyl groups, ionizable salts thereof, ester groups, ether groups, and the like. It is also preferred that one or more of these groups is bonded to a non-coupling site of COUP, or an alkyl group of an appropriate size, for example 1 to 10 carbon atoms, 6 to 12 carbon atoms. It is also advantageous to use a solubilizing group in which an aryl group having a carbon atom has one or more of the above-mentioned ionizable groups bonded to a non-coupling site of the coup. Also preferred are those bonded to the non-coupling site of the above-mentioned coup via a linking group. Typical linking groups include oxy (-0-), thio (-8-), carbonyl group, carbonyloxy group, oxycarbonyl group, amino group, carbamoyl group, aminocarbonyl group, ureido group,
Mention may be made of sulfamoyl and aminosulfonyl groups. Although the solubilizing groups for use have been listed above, particularly preferred solubilizing groups are carboxyl groups, sulfo groups, or ionizable salts thereof directly bonded to the non-coupling site of C0UP, or non-coupling groups of C0UP. an alkyl group having 1 to 10 carbon atoms containing I or more carboxy groups, sulfo groups or ionizable salts thereof bonded directly to the moiety or via an amino group or carbonyl group; Mention may be made of aryl groups having 6 to 12 carbon atoms. Furthermore, the compounds according to the present invention which can form yellow, magenta and cyan dyes preferably used in the present invention can be represented by the following general formulas (I[) to [■]. [Yellow dye-forming compound] Formula (It) where R1 is an aryl group (e.g. phenyl group) or an alkyl group (particularly a tertiary alkyl group, e.g. t-butyl group), and Rs is the above-mentioned is a stabilizing group (BALE, ),
R3 is the above-mentioned solubilizing group (SQL), R4 is a hydrogen atom or a halogen atom, an alkyl group or an alkoxy group, and n+m=5 (however, n≠0゜m≠0, and n, m When is 2 or more, they may be the same or different). [Magenta dye-forming compound] General formula (I[[) General formula (W) General formula (V) In the general formulas (III), (IV) and (V), R2
has the same meaning as Rs in general formula (n), R5 represents a solubilizing group (SQL), R6 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an amino group, and p≦5. (When p≠0 and p is 2 or more, each may be the same or different.) One of R7 and Rs represents the above-mentioned solubilizing group (SQL), and the other represents a hydrogen atom or an alkyl group. , represents an alkoxy group, an aryl group or an amino group. Rs and RIo have the same meanings as R7 and Rs in general formula (IV). [Cyan dye-forming compound] General formula (VT) General formula [■] 6 In the general formula (Vl) and [■], R2 is the general formula (l
It has the same meaning as Rs in r), at least one of R's and Rlt is the above-mentioned solubilizing group (SQL), and the remainder represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkylamido group, and q ≦3 (however, q≠0)
RI3 represents the above-mentioned solubilizing group (SQL). Unless otherwise indicated above, alkyl, alkoxy and alkylamido groups each contain 1 to 8 carbon atoms, aryl groups contain 6 to 10 carbon atoms, and amino groups contain 6 to 10 carbon atoms; Includes mono, -secondary and tertiary amino groups. These substituents and stabilizing groups (
BALL) is a halogen atom, hydroxy, carboxy,
Also included are those further substituted with groups such as amino, amido, carbamoyl, sulfamoyl, sulfonamido, alkyl, alkoxy and aryl. In the colorless coupler according to the present invention, the compound belonging to the above (2) can be represented by the following general formula [■]. General formula [■] cup. *1! '4 In the formula, C0UP has the same meaning as C0UP in the general formula (1), and R'' is bonded to the coupling site of C0UP, and the reaction between the coupler of the general formula [■] and the oxidized product of the color developing agent represents a group that cannot be separated by. Examples of the coupler nucleus represented by C0UP2 include the coupler nucleus described in general formula [1]. Examples of the group represented by RI4 include an alkyl group and a substituted alkyl group. , aryl group, substituted aryl group, alkenyl group,
Examples include cyan group. The compound represented by the general formula [■] has an alkyl group, an aryl group, and a heterocyclic group having 8 to 32 carbon atoms via a linking group at the non-coupling site of the coupler core represented by coup. Diffusion is preferred. Typical linking groups include oxy(-0-), thio(-5-), carbonyl group, carbonyloxo group, oxycarbonyl group, amino group, carbamoyl group, aminocarbonyl group, ureido group, sulfamoyl group, and amino group. Mention may be made of sulfonyl groups. In the colorless coupler according to the present invention, the compound belonging to the above (3) can be represented by the following general formula [IX]. General formula (IX) 0UP3 * IM In the formula, C0IJ P y represents a coupler core that provides a substantially colorless product by a coupling reaction with an oxidized product of a color developing agent, and R'' represents a cup of Represents a group that is bonded to the ring moiety and can be separated from C0Uh by a coupling reaction with an oxidized product of a color developing agent. Preferred examples of the group that can be separated include a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, Examples include an alkylthio group, a heterocyclic thio group, an arylazo group, an acyloxy group, an alkylsulfonyloxy group, an alkylsulfonyloxy group, a nitrogen-containing heterocyclic group, etc. In the colorless coupler represented by the general formula (IX),
More preferable ones are general formulas (X) to (X II+
). General formula [χ] 111+. In the formula, lya1'' is rt I in the general formula CIX)
%, 1z10 is a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, an acyloxy group, or a heterocycle Jλ, and X is an oxygen atom or =N-1
t". R" represents an alkyl group, an aryl group, a hydroxy group, an alkoxy group or a sulfonyl group. Z
is a non-containing compound necessary to form a 5- to 7-membered carbocyclic ring (e.g., indanone, Schiff[I-pentanone, cyclohegizanone, etc.) or a heterocycle (e.g., piperidone, pi[1-one, hydroluposdilyl, etc.]). Represents a group of metal atoms. General formula [Kari] In the formula, R + S, rt 16 and X represent the general formula (X)l
Niol II '6. It is synonymous with R" Rahi J Co Represents an anilino group. General formula [Kari] R”-CIl-R” I5 In the formula, rt+5 is -・1 or 15 in the general formula [IX]
R1'' and R20 may be the same or different, and include an alkoxycarbonyl group, a carbamoyl group, anlu group, a cyano group, a formyl group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, '''''ゞ represents an ammonylamyl group or -4fi. Δ represents a group of nonmetallic atoms necessary to form a 5- to 7-membered heterocycle (e.g., fucurimide, triazole, tetrazole, etc.) together with a nitrogen atom. General formula (XIII) υ In the formula, 1t15 has the same meaning as R'' in the general formula [IX], and R
1' represents an alkyl group, aryl group, anilino group, alkylamino group or alkoxy group, and B represents an oxygen atom, sulfur atom or nitrogen atom. Next, typical examples of the colorless coupler according to the present invention will be listed, but the invention is not limited thereto. Exemplary compounds belonging to general formula (1) H 0 ■ Cool ( II OH self 11゜0 ■ 1l II 0 ■ Exemplary compounds belonging to general formula [■] The coloring coupler is disclosed in Japanese Patent Application Laid-Open No. 59-1134.
No. 40, No. 59-171955, No. 52-82423
British Patent No. 914.145, British Patent No. 1.284,64
No. 9, U.S. Patent No. 2,742°832, U.S. Patent No. 3,227
, No. 550, No. 3,928,041, No. 3,958°993, No. 3,961,959, No. 4,046.5
No. 74, No. 4,052゜213, No. 4,149,88
It can be synthesized by the method described in No. 6, etc. The colorless coupler according to the present invention can be introduced into the silver halide emulsion layer by the same method as the dye-forming coupler etc. described later. It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used. The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. The hardener is included in the processing solution using rff! It is possible to add an amount of the photosensitive material that can be hardened to such an extent that it is not necessary to add a film agent, but this is possible by adding a hardener to the processing solution. For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-medyrol compounds (dimedy[J-lurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1 ,3,5-
Triacryloyl-hexahydro-S-triazine, 1
．． 3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-8-triazine, etc.), mucohalogen acids (muco'y
t1 chloric acid, mucophenoxychloroic acid, etc.), etc.
Can be used alone or in combination. A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in section A of rt D 17643. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer 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, olefins,
Alone or in combination with styrene, etc., or together with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid,
A polymer containing a combination of hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used. The emulsion layer of the photosensitive material contains a dye-forming agent that forms a dye through a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) during color development processing. A coupler is used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above. These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. Compounds that release photographically useful fragments such as hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used. The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valent group, and is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction in the makuuchi separated by the coupling reaction (timing DIR couplers, and timing DIR compounds). Furthermore, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination depending on the purpose. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler. As the yellow dye-forming coupler, known anruacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include, for example, U.S. Patent No. 2,87
No. 5,057, No. 3.265.506, No. 3.4
(No. 18,194, No. 3,551,155, No. 3
．． No. 582,322, No. 3.725,072, No. 3.891°445, West German Patent No. 1,547.8H,
West German Application No. 2.219.917, No. 2,261.3
No. 61, No. 2,414,006, British Patent No. 1.42
No. 5.020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 1977
-26133, 4g-73147, 50-63
No. 41, No. 50-87650, No. 50-123342
No. 50-130442, No. 51-21827,
No. 51-102636, No. 52-82424, No. 5
2-1 t5219, 5g-95346, etc. As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolopenzimidazole couplers, biracytriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used. Specific examples of magenta color-forming couplers that can be used include, for example, U.S. Pat. No. 2,600,788, U.S. Pat.
No. 3,311.476, No. 3.419,39
No. 1, No. 3.519.429, No. 3゜ssg, 3
t9, 3,582,322, 3,615,
No. 506, No. 3,834,908, No. 3.891
, 445, West German Patent Application No. 1゜810.464, West German Patent Application (OLS) No. 2.408,665, West German Patent Application No. 2゜417.
No. 945, No. 2,418,959, No. 2,424,4
No. 67, JP 40-6031, JP 49-740
No. 27, No. 49-74028, No. 49-129538
No. 50-60233, No. 50-159336,
No. 51-20826, No. 51-26541, No. 52
-42121, 52-58922, 53-55
No. 122, Japanese Patent Application No. 110943/1980, and the like. Phenol or naphthol couplers are commonly used as cyan dye-forming couplers. Specific examples of cyan color-forming couplers that can be used include, for example, U.S. Pat.
Same No. 2.801,171, Same No. 2.895,826, Same No. 3,476.563, Same No. 3,737,326
No. 3,758,308, No. 3.893.04
Specification No. 4, JP-A-47-37425, JP-A No. 50-10
No. 135, No. 50-25228, No. 50-11203
No. 8, No. 50-117422, No. 50-130441
Those described in publications, etc., and those described in Japanese Patent Application Laid-Open No. 58-987
The couplers described in Publication No. 31 are preferred. Dye-forming couplers, colored couplers, DIR couplers that do not need to be adsorbed on the silver halide crystal surface, I)
I I? Among compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc., hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc. This can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and usually a high boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low boiling point,
and/or dissolved in a water-soluble organic solvent, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, and using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. After emulsifying and dispersing the colloid, it may be added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion. Examples of high-boiling point solvents include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, and trimesic acid esters, which do not react with the oxidized form of the developing agent. A solvent is used. Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene. When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids. Anionic surfactants, nonionic surfactants, Kachina no Paku... Men's #h #Itake rK iTi Wb Ri7i Renshane can do one m short. The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable. The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer. An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in section (■) J of fl D 17643. Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good. In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material. When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer. Compounds that change the developability, such as development accelerators and development retarders, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. Compound hart D that can be preferably used as a development accelerator
No. 17643 No. A black and white developing agent and/or its precursor may be used for development acceleration and other purposes. The emulsion layer of a photographic light-sensitive material is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urea derivatives, imidazole derivatives, and the like. A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds which can preferably be used as optical brighteners are described in section 7 of fl D 17643. The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process. Examples of such dyes include oxonol dyes, hemioxonol dyes, sudyryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. In the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material, reduction of gloss of the light-sensitive material, improvement of writeability,
A matting agent can be added for the purpose of preventing photosensitive materials from sticking to each other. Any matting agent can be used, such as silicon dioxide, titanium dioxide, magnesium dioxide,
aluminum dioxide, barium sulfate, calcium carbonate,
Examples include polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resins, polycarbonates, and styrene polymers and copolymers thereof. The particle size of the matting agent is preferably O,OSμ to 10μ. The amount added is preferably 1 to 300 Ily/I11''. A lubricant can be added to the photosensitive material to reduce sliding friction. An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent is It may be used in an antistatic layer on the side of the support on which the emulsion is not laminated, and it may be used in a protective colloid layer other than the emulsion layer and/or the emulsion layer on the side on which the emulsion layer is laminated with respect to the support. Preferably used antistatic agents are the compounds described in RD 17643 No. Improvement, emulsification and dispersion,
Various surfactants can be used for the purpose of preventing adhesion and improving photographic properties (development acceleration, film hardening, sensitization, etc.). The support used in the photosensitive material of the present invention includes paper laminated with an α-olefin polymer (e.g., polyethylene, polypropylene, ethylene/butene copolymer), etc.
Flexible reflective supports such as synthetic paper, films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, and reflective layers provided on these films. flexible support, glass, metal,
Includes pottery etc. After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface.
It may be applied through one or more subbing layers to improve antihalation properties, frictional properties, and/or other properties. When coating the photosensitive material, a thickener may be used to improve coating properties. In addition, for example, hardeners, which have quick reactivity and may cause gelation before coating if added to the coating solution in advance, should be mixed at 1iη using a static mixer or the like. is preferred. As coating methods, extrusion coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected. Examples of the surfactant include, but are not limited to, natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyrinone, and others. Cationic surfactants such as heterocycles, phosphoniums or sulfoniums, carboxylic acids, sulfonic acids,
Anionic surfactants containing acidic groups such as phosphoric acid, sulfuric acid esters, and phosphoric acid esters; amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphoric acid esters of amino alcohols may be added. Moreover, it is also possible to use a fluorine-based surfactant for the same purpose. The total weight of color photosensitive materials is 30-1501g/100
cm” is preferable, more preferably 30 to 130 mg/
100 cm', most preferably 40-110
mV/100cm''.The layer structure that can particularly exhibit the effects of the present invention is a colloidal silver antihalation layer (intermediate layer), a red-sensitive layer (intermediate layer), a green-sensitive layer (intermediate layer), a colloidal silver yellow filter, and a colloidal silver yellow filter. One layer coated with a blue-sensitive layer (intermediate layer) and a protective layer, and further sequentially from the support: a colloidal silver antihalation layer (intermediate layer), a red-sensitive layer (intermediate layer), a green-sensitive layer (intermediate layer), a blue-sensitive layer (intermediate R @) Red-sensitive layer (intermediate layer) Green-sensitive layer (one layer of colloidal silver yellow filter) Blue-sensitive layer (intermediate layer) M coated with protective layer
1 configuration. Note that the layers in parentheses can be omitted. The red-sensitive layer, green-sensitive layer and blue-sensitive layer may each be divided into low-sensitivity and high-sensitivity layers. Furthermore, a layer structure in which at least one of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer is divided into three partial layers as seen in JP-A No. 49-15495, JP-A-51-4902
The layer structure that separates the high-sensitivity emulsion layer m position and the low-sensitivity emulsion layer unit as seen in No.
Examples include the layer configurations found in Japanese Patent No. 2,704,826 and Japanese Patent No. 2,704,797. To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. In addition, ■ A bleach-fixing process can be performed using a bath bleach-fixing solution, and color development, six pixel, and fixing can be performed in one bath. ■ A monobath process using a bath developing bleach-fixing solution It is possible to carry out processing steps. In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution, or an activator process may be performed in the monobath process. can be applied. Among these processes, typical processes are shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process, or a stabilization process.) Color development process - Bleach process Constant fixation process - Color development process - Bleach-fixing process Process/@Hardening process - Color development process - Stop fixing process - Washing process - Bleaching process Constant fixation process - Washing process - After F
f! Membrane treatment process/Color development treatment process - Water washing treatment process - Supplementary color development treatment process - Stop treatment process - Bleach treatment process Constant fixation treatment process/Activator treatment process - Bleach-fix treatment process/Activator treatment process - Bleaching treatment process Constant Deposition treatment step/monobath treatment step The treatment temperature is usually selected in the range of lO'C to 65°C, but it may also be a temperature exceeding 65°C. Preferably 2
Processed at 5°C to 45°C. A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenylenediamine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, such as salt bridge acids, sulfates, p-)luenesulfonates, sulfites, oxalates, benzenesulfonates, etc. I can do it. These compounds generally have a color developer IQ of about 0.
A concentration of 1 to 30 g is used, more preferably a concentration of about 1 to 15 g for color developer IQ. Q. Sufficient color density cannot be obtained if the amount added is less than that of Ig. Examples of the aminophenol-based developer include 0-aminophenol, p-aminophenol, 5-aminophenol,
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-aminol 1,4-dimethylbenzene, and the like. In particular, the primary aromatic amine color developer for (f) is N, N
' -Dialkyl-p-phenylenediamine compound, even if the alkyl group and phenyl group are substituted,
Or it may not be replaced. Among them, particularly useful compound examples include N-N-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, and N. N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethy N-β-methanesulfonamide ethy 3-methyl-4-aminoaniline Sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-medyl-N, N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-
Examples include methylaniline-p-)luenesulfonate. Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials. In this case, it is also possible to treat the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment. The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. It also contains various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfites. You may. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained. The pH of the color developing solution used in the present invention is usually 7 or more,
Preferably it is about 9-13. In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or hexose, pyrogallol-1,
3-dimethyl ether etc. may be contained. Various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution used in the present invention. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminopentaacetic acid,
-Organic phosphonic acids such as hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphonic acid, oxycarboxylic acids such as citric acid or glyconic acid, 2-phosphonobutane! , phosphonocarboxylic acids such as 2,4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds. The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately. As the bleaching agent, a metal complex salt of an organic acid is used, and for example, one in which a metal ion such as iron, cobalt, or copper is coordinated with an organic acid such as polycarboxylic acid, aminopolycarboxylic acid, oxalic acid, or citric acid is used. Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-
N,N',N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycincitric acid (or tartaric acid), ethyl etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, Examples include endylene diamine tetrabrobionic acid and phenylene diamine tetraacetic acid. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaches contain 5 to 450 g/Q, more preferably 2
Use at 0-250g/Q. In addition to the above bleaching agent, the bleaching solution may contain a sulfite as a preservative, if necessary. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetic acid iron (I) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can. The bleaching solution used in the present invention includes JP-A-46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770.910, JP-B No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added. The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.
．． It is used between 0 and 9.5, preferably between 4.5 and 8.0, and most preferably between 5.0 and 7.0. A fixer having a commonly used composition can be used. As fixing agents, compounds that react with silver halide to form water-soluble complex salts, such as those used in ordinary fixing processes, such as thiosulfates such as potassium thiosulfate, sodium diosulfate, and ammonium thiosulfate, and thiocyanic acid are used. Typical examples include thiocyanates such as potassium, sodium thiocyanate, and ammonium thiocyanate, thiourea, and thioether. These fixatives are 5
It is used in an amount of 9/Q or more, within a range where it can be dissolved, but generally it is used in an amount of 70 to 250 g/σ. Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank. The bleaching solution and/or fixing solution may contain various pH 1 buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. These agents may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, hardening agents such as water-soluble aluminum salts, methanol,
Organic solvents such as dimethylsulfamide and dimethylsulfamide can be appropriately contained. The pH of the fixer is used at 3.0 or higher, but generally it is 4.
．． 5-1O, preferably 5-9.5, most preferably 6-9. Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process. The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. Also, a bleach-fixing solution consisting of an ethylenediaminetetraacetic acid iron(II[) complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixing agent mentioned above, or conversely, a halogen such as ammonium bromide may be used. A bleach-fix solution containing a large amount of iron ethylenediaminetetraacetate (I
[) A special bleach-fix solution having a composition consisting of a combination of a complex salt bleach and a large amount of a halide such as ammonium bromide can also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can. Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution are the same as in the fixing process described above. I)H of the bleach-fix solution is used at 4.0 or more, but generally it is used at 5.0 to 9.5, preferably 6.0 to 8.
．． 5, most preferably 6.5 to 8.5. ' [Example-1] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. In all of the following examples, the amount added to the silver halide photographic material is per 1 ffi unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver. Multilayer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side. Sample-1 (comparison) No. 1, prevention of Halley's siding! (HC-1) Gelatin layer containing black colloidal silver. No. 271: Intermediate layer (1,L,) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone. 3rd layer; low sensitivity red-sensitive silver halide emulsion layer (RL-1)
Monodisperse emulsion (emulsion ■) consisting of AgBr I with an average grain size (r) of 0.30 μs and containing 6 mol% of Agl...silver coating amount 1.8 g/+a"
Sensitizing dye ■... 6 x 10-' mol sensitizing dye ■... per 1 mole of silver
- 1.0% per mole of silver. OX 10-'Morsian coupler (C-1)... 0.06 mol per mol of silver Colored cyan coupler (CG-1)... 0.003 mol DIR compound (D -1)... 0.0015 mol per mol of silver DIR compound (D-2)... 0.002 mol per mol of silver 4th layer; Highly sensitive red-sensitive silver halide emulsion layer ( RH-1)
It consists of AgBr I with an average particle size (r) of 0.5 μm and containing 7.0 mol% of Agf. Monodisperse emulsion (emulsion ■)...Silver coating 113 g/+a" Sensitizing dye I...3 x 10-' mol sensitizing dye ■... per 1 mole of silver
- t, ox to-' Morcyan coupler (C-1) for 1 mol of silver... 0.02 mol for 1 mol of silver Colored cyan coupler (CC-1)... for 1 mol of silver 0.0015 mol DIR compound (D-2)... o, oot mol per mol of silver 5th layer; Intermediate layer (1, L,) Same as the second layer, gelatin layer. 6th layer: low-sensitivity green-sensitive silver halide emulsion layer (GL-1)
Emulsion - ■... Coated silver amount 1.5 g/n' sensitizing dye ■
... 2.5X IG' mole sensitizing dye per 1 mole of silver... 1.2X 10-' mole magenta coupler (M-1) per 1 mole of silver... 0.05Q mol Colored magenta coupler (CM-1)... 0.009 mol DIR compound (D-1)... 0.0010 mol DLR compound (D- 3)... 0.0030 mol per mol of silver 7th layer: Highly sensitive green-sensitive silver halide emulsion layer (Gl+-1
) Emulsion - ■ Coated silver amount 1.4 g/m" Sensitizing dye ■... 1.5X io-' mole sensitizing dye ■ per 1 mole of silver
... 1 mole of silver. OX 10-' mol Magenta coupler (M-1)... 0.020 mol per mol of silver Colored magenta coupler (cM-1)... 0.002 mol DIR compound (D -3)... 0.0010 mol per mol of silver 8th layer; yellow filter single layer (yc-1) gelatin containing an emulsified dispersion of yellow colloidal silver and 2,5-di-t-octylhydroquinone layer. 9th layer; low-speed blue-sensitive silver halide emulsion p, q (nt,
-r) Monodispersed emulsion (emulsion 111) consisting of 8 gBrl with an average grain size of 0.48 μm and containing 6 mol% of 8 g1...trowel application! i′CO,9
g/m2 sensitizing dye ■... per mole of silver! , 3XIO5 mol Yellow coupler (Y-1)... 0□29 mol per mol of silver 10th layer: Highly sensitive blue-sensitive emulsion layer (I; 3H-1) Average grain size 0.8 μra, Agl 15 mol AgBr containing %
Monodisperse emulsion (emulsion ■) consisting of 1...Silver coating m0.5g/m'' sensitizing dye ■...1.0 x 10' mole per mole of silver Yellow coupler (Y-1)...silver o, og mol per 1 mol DIrt compound (D-2)... 0.0015 mol per 1 mol silver 11th layer; 1st protective layer (Pro-1) Silver iodobromide (Agl 1 mol) % average particle size 0.07 μm) Silver coating amount 0.5 g/m'' Gelatin layer containing UV absorbers UV-I, UV-2 12th layer: 2nd protective layer (1'ro-2) Polymethyl methacrylate particles (1.5 μm in direct view) and a gelatin layer containing a formalin scavenger (TLS-1) In addition to the above composition, each layer contains a gelatin hardener (+1-
1) and (H-2) and a surfactant were added. Next, an internal fog emulsion was prepared in the following manner. A monodisperse cubic pure silver bromide emulsion with an average grain size of 0.15μ obtained by a known method was prepared with pΔg6, p
A fog emulsion was prepared by adjusting the temperature to H7, adding diourea dioxide and an aqueous chloroauric acid solution, and aging at 60° C. for 60 minutes. Next, this emulsion was divided into parts, stirred vigorously at 60°C, and grown using the double jet method by adding a silver nitrate aqueous solution and a potassium bromide aqueous solution while maintaining the pAg of 9.1) H6 to form a cubic crystal with an average grain size of 0.25μ. A monodisperse emulsion consisting of The internal fog of this emulsion was 0.99, and the proportion of silver fog in surface development was less than 1%. The coefficient of variation of particle size was 0.17. The compounds contained in each layer of sample 1 are as follows. Sensitizing dye 1; anhydro-5,5'-dichloro-9-
Ejiru 3.3'-di(3-sulfopropyl) deacarbocyanine hydroxide sensitizing dye ■: Anhydro-9-ethyl-3,3'-di(3-sulfopropyl)-4,5°4',5'
-Dibenzothiacarbocyanine hydroxide sensitizing dye ■: Anhydro 5.5' -Diphenyl-9
-ethyl-3,3' -di(3-sulfobutyl)oxacarbocyanine hydrokid sensitizing dye IV, anhydro-9-ethyl-, l,3'
-di(3-sulfobutyl)-,5,6,5',
6'-Dibenzooxalpocyanine hydroxide sensitizing dye ■: Anhydro-3,3'-di(3-sulfopropyl)-4,5-benzo-5'-methoxydiacyanine C-1 h l1 V- 2 Js II S-I II-1 Samples 2 to 24 were prepared by changing the 6th layer, 7th FJ, and 8th layer of sample 1 as shown in Table 1. Each of the samples Nos. 1 to 24 thus prepared was subjected to wedge exposure using white light, and then subjected to the following development treatment. Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixing
Wash with water for 6 minutes and 30 seconds Stabilize for 3 minutes and 15 seconds
Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows. [Color developer] "4-amino-3medyl-N-ethyl-N-L potassium hydroxide Add 1.09 water and lf2
shall be. [Bleach solution] “Ethylenediaminetetraacetic acid iron ammonium salt glacial acetic acid
Add 10.0 ml of water to make IQ, and adjust to pH = 6.0 using aqueous ammonia. [Fixer] “Ammonium thiosulfate 175.0gL
Sodium metasulfite 2.39 Add water to tC and adjust to I)H=6.0 using acetic acid. [Stabilizer] “Formalin (37% aqueous solution) 1.5
mffL Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7
．． Add 5ml of water to make tQ. After development, the green sensitivity, minimum density, and high density value of each sample at the same exposure amount as when sample 1 obtained a density of 1.7 were determined. The sensitivity is a relative value of the reciprocal of the exposure amount that gives the lowest density +0.1, and is expressed as a value with Sample 1 as 100. Moreover, the minimum concentration and high concentration values are also shown as values with Sample 1 as 100. Further, the RMS value was used to evaluate graininess. The 1'tMS value was expressed as a value 1000 times the standard deviation of the variation in density value that occurs when scanning the minimum density + 1.2 with a microdecitometer having an aperture scanning area of 250 .mu.i. The values are expressed as relative values, with sample 1 being 100. The results are shown in Table 2. From the results in Table 2, the following conclusions can be drawn. (1) Even if internal fog emulsion is added alone to the 6th and 7th layers, a slight increase in sensitivity, improvement in maximum density, and improvement in graininess can be seen, but the minimum density increases due to the occurrence of large fog. Yes, this is a performance problem. (2) When a colorless coupler is introduced alone into the seventh layer or the eighth layer, a slight improvement in graininess is observed, but the sensitivity decreases, which is a problem in terms of performance. (3) Regarding the sample in which internal fog emulsion and colorless coupler were used in combination, the graininess was improved as expected, but the sensitivity was increased without fogging, which was a better-than-expected effect. [Example 2] In the same manner as in Example 1, each layer having the composition shown below was sequentially formed on a triacetyl cellulose film support from the support side to prepare a multilayer color photographic element sample. Sample-25 (comparison) 1st layer: Anti-halation V! J (IIC-2) Gelatin layer containing black colloidal silver. 2nd layer; middle layer (1, L,) gelatin layer. 3rd layer: low sensitivity red-sensitive silver halide emulsion layer (RL-2)
Monodisperse emulsion (emulsion V) consisting of AgBr1 containing average grain size (r) 0.80 μta and 9 mol% Agl... Silver coating amount 1.9 g/m' Sensitizing dye r... Per 1 mol of silver 2. OX 10-'molar sensitizing dye ■・
... 1 mole of silver. OX 10-'Morsian coupler (C-1)... 0.08 mol per mol of silver Colored cyan coupler (CC-1)... 0.004 mol DIR compound (D -1)... 4th layer with 5 moles of O, GO per 1 mole of silver; intermediate layer (1, L) gelatin layer. 5th ff: Low-sensitivity green-sensitive silver halide emulsion fm (GL-
2) Emulsion - ■ Coated silver amount 1.7 g/m" Sensitizing dye ■
... 1.2X 10-' mol sensitizing dye for 1 mol of silver.
... 1.2X 10-5 mole magenta coupler (M-1) for 1 mole of silver... 0.06 mole colored magenta coupler (CM-1) for 1 mole of silver... 0.012 mol for 6th layer; middle layer (1, L) gelatin layer. 7th layer: Low sensitivity blue-sensitive silver halide emulsion layer (BL-2)
Emulsion -■ Coated silver amount 1. og/I11” sensitizing dye■
... OX 10-' mole per mole of silver Yellow coupler (y-1)... 0.35 mole per mole of silver DIR compound (D-1)... per mole of silver On the other hand, o, ooi mole 8th layer: intermediate, II! (1,L) Gelatin layer comprising an emulsified dispersion of 2.5-di-octylhydroquinone. 9th layer: High sensitivity red-sensitive silver halide emulsion layer (R1!-2
) A monodisperse emulsion (emulsion ■) consisting of 8 g Brl containing 8 g 17.0 mol % with an average grain size (r) of 1.8 μm...Amount of spread silver 2.4 g/m' Sensitizing dye I... - 1.0% per mole of silver. lXl0″ molar sensitizing dye■・・
- 5.0% per mole of silver. Ox 10 'Morsian coupler (C-1)... 0.03 mol per 1 mol of silver Colored cyan coupler (CG-1)... 0.002 mol DIR compound (D- 1)... 4 moles of Q, 0QO per mole of silver 10th layer: Intermediate layer (1,L) Gelatin layer containing an emulsified dispersion of 2.5-di-L-octylhydroquinone. 11th layer; High sensitivity green-sensitive silver halide emulsion layer CGl+-
2) Emulsion - ■ Coated silver amount 2.0 g/m" Sensitizing dye I
II... 4.0XlO" mol per mol of silver Sensitizing dye ■... 4.OX 10° mol per mol of silver Magenta coupler (M-1)... per mol of silver 0.020 mol colored magenta coupler (CM-1)... Q, 0 (12 mol per mol of silver) 12th layer: A gelatin layer containing an emulsified component a of 2.5-di-L-octylhydroquinone. 13th layer: High sensitivity blue sensitive emulsion layer (I3H-2) emulsion -■
and emulsion-■ and average grain size 0.27 μm Agl
Monodispersed emulsion (emulsion-■) consisting of 2 mol% 8gI3rl... coated silver amount 2.1g/n" sensitizing dye■
...for 1 mole of silver? , QX 106 moles [1-Coupler (Y-1)... 0.08 mol per mol of silver Dlrt compound (D-1)... 0.08 mol per mol of silver. QQO 7 mol 14th layer; 1st protective layer (r'ro-3) average particle size 0.0
7 μm Agl 1 mol% AgBr1-coated silver fa0.
Gelatin layer containing 2 g/m" ultraviolet absorbers tJV-1 and UV-2. 15th layer; 2nd protective layer (Pro-4) polymethyl methacrylate particles (diameter 1.5 μm) and formalin scavenger (HS- 1) In addition to the above composition, each layer contains a gelatin hardener (H-1).
) and (1-1-2) and a surfactant were added. Samples 26 to 37 were prepared by changing the 9th layer and the 1st O layer of sample 25 to those shown in Table 3, and the 11th layer and 12th layer to those shown in Table 4. Table 3 Table 4 Exposure, development, and data processing were performed in the same manner as in Example 1. The results are shown in Table 5.6. As is clear from Table 5.6, only when an internal fogging emulsion and a colorless coupler are used simultaneously, as in the sample of the present invention,
A large improvement in graininess was seen, and higher sensitivity was achieved with no fogging problems than expected. Patent applicant Roku Konishi Photo Industry Co., Ltd. 1LE (method) % formula % 2. Name of the invention Silver halide photographic light-sensitive material with improved sensitivity, fog, and graininess 3. Amendment person's case and Relationship Patent Applicant Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Contact Publication 91 Konishiroku Photo Industry Co., Ltd., 1-Sakura-cho, Hino-shi, Tokyo (0425-83-1521)
Patent Department 5, Specification subject to amendment 6, hli correct content

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the emulsion layer and/or a layer adjacent thereto contains silver halide having fog nuclei inside. 1. A silver halide photographic light-sensitive material, comprising a compound which reacts in combination with an oxidized product of a color developing agent in combination with at least one light-sensitive silver halide emulsion layer but does not contribute to image formation.