JP2006227355A - Processing method for silver halide color photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a processing method for a silver halide color photosensitive material that is reduced in hue unevenness of a white background portion and superior in image preservability of yellow images. <P>SOLUTION: In the processing method for a silver halide color photographic sensitive material, an exposed silver halide color photographic sensitive material is processed through processing steps, including a color developing step, a bleaching-fixing step or a bleaching step and a fixing step, and a stabilizing step, wherein the chromaticity of an unexposed portion of the silver halide color photographic sensitive material after the processing satisfies 91≤L<SP>*</SP>≤97 and -8.0≤b<SP>*</SP>≤-3.5, and a stabilizing solution for the stabilizing step contains a sulfinic acid derivative, represented by Formula (I): RSO<SB>2</SB>M in an amount of 2.0-30.0 mmol/l. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for processing a silver halide color light-sensitive material with reduced processing unevenness and improved image storability of yellow images.

  Usually, a method for forming a dye image by developing a silver halide color photographic light-sensitive material (hereinafter also referred to as color photographic paper or light-sensitive material) is to perform color development with a color developer after imagewise exposure. Then, after passing through a desilvering process and a fixing process for removing the silver image that is no longer needed, the image is processed by a water washing process and a stabilization process for stabilizing the formed dye image. In recent years, shopfront processing at photo shops by minilabs has become widespread, and there is a time of over-competition, and there is a need for ultra-rapid processing that allows users to obtain photo prints on the spot without having to go twice.

  On the other hand, recently, low replenishment that reduces the replenishment amount of processing solution during development processing to reduce the cost of development processing agents or reduce the amount of used processing waste liquid that requires cost for recovery and disposal to reduce pollution. The process is being carried out quickly.

  In silver halide color photographic light-sensitive materials, particularly color photographic paper that is an ornamental silver halide color photographic light-sensitive material, high-quality image quality is required along with rapid processing. However, the white background characteristics tend to be deteriorated by speeding up processing, reducing the amount of replenishment, or performing continuous processing as described above, and the improvement thereof is strongly desired.

In general, as a method for improving the white background of color photographic paper, a method for improving whiteness by adding a fluorescent whitening agent to a processing solution is employed. However, in the white background improvement means using such a fluorescent whitening agent, the b ^* value which is a perceptual chromaticity index can be shifted in the negative direction as the white chromaticity of the unexposed portion. When the whiteness is adjusted with the agent, there is a problem that the density of the black portion is lowered, that is, the bluening due to the so-called fluorescent whitening agent occurs. In particular, when the addition amount of the fluorescent brightener is increased, the density reduction of the black portion is remarkably exhibited.

  Furthermore, if the amount of fluorescent brightening agent added is too large, it also causes the problem that hue unevenness is likely to occur in the white background during processing, and in particular, a method that can stably improve the white background characteristics under rapid processing conditions. It is the present situation that development of is strongly desired.

  On the other hand, as a silver halide color photographic light-sensitive material, reduction of the amount of silver used is strongly desired from the viewpoint of resource saving or production efficiency. However, in general, yellow couplers are used as couplers as color formers in the blue-sensitive layer. However, this yellow color image is difficult to produce a visual density, and many color-applied papers are blue-sensitive. Since the layer is often applied to the lowermost layer, it is the current situation that sufficient color developability cannot be obtained due to delay in development, etc. In order to obtain a desired color density, the blue sensitive layer is inevitably obtained. There is a problem that the amount of coated silver increases, and it has been desired to reduce the amount of coated silver.

  Several methods can be used to achieve a reduction in the amount of silver applied to the blue-sensitive layer. Typical examples include the use of a high color-developing yellow coupler with good color development performance. It is done. However, when the amount of silver in the blue-sensitive emulsion layer is reduced and a high color developing yellow coupler is applied, it is continuously processed in a developing machine with a low processing amount per day when processed continuously under low replenishment and rapid processing conditions. When processing was performed, a new problem was found that the yellow image easily fades when the formed yellow image is irradiated with light for a long time in a high-temperature and high-humidity environment.

On the other hand, as a method for processing a silver halide color photographic light-sensitive material, a method for preventing stain by adding sulfinic acid having a specific structure or a salt thereof to a processing solution has been proposed (for example, see Patent Document 1). .) In Patent Document 1, the addition of a sulfinic acid derivative to a specific cyan coupler and a bleach-fixing solution is particularly effective in preventing stains associated with sulfurization of thiosulfate, etc. There is no mention about the method of adding, and there is no mention of the processing unevenness of the white background when the b ^* value is small and the stability of the yellow image, and no suggestion about the improvement method is made.
JP 11-133562 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for processing a silver halide color photosensitive material in which hue unevenness in a white background portion is reduced and image storability of a yellow color image is excellent. There is.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
A silver halide color photographic light-sensitive material for developing an exposed silver halide color photographic light-sensitive material through at least a color developing step, a bleach-fixing step or a processing step comprising a bleaching step and a fixing step, and a stabilization step. In the processing method, the chromaticity (L ^* , b ^* ) of the unexposed portion of the silver halide color photographic light-sensitive material after the development processing is 91 ≦ L ^* ≦ 97, −8.0 ≦ b ^* ≦ -3. 5 and the stabilizing solution constituting the stabilizing step contains a sulfinic acid derivative represented by the following general formula (I) in an amount of 2.0 mmol / L or more and 30.0 mmol / L or less. A method for processing a silver halide color light-sensitive material.

Formula (I)
RSO ₂ M
[Wherein, R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group. M represents a hydrogen atom, an alkali metal atom, an ammonium group or a quaternary amine. ]

  According to the present invention, it is possible to provide a method for processing a silver halide color light-sensitive material in which hue unevenness of a white background portion is reduced and image storability of a yellow image is excellent.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

As a result of intensive studies in view of the above problems, the inventors of the present invention comprise an exposed silver halide color photographic material comprising at least a color development step, a bleach-fixing step or a bleaching step and a fixing step, and a stabilization step. In the method for processing a silver halide color photographic light-sensitive material that is developed through the processing steps, the chromaticity (L ^* , b ^* ) of the unexposed portion of the silver halide color photographic light-sensitive material after the development processing is 91. ≦ L ^* ≦ 97, −8.0 ≦ b ^* ≦ −3.5, and the stabilizing liquid constituting the stabilizing step is a sulfinic acid derivative represented by the following general formula (I): The processing method of the silver halide color light-sensitive material, containing 0.0 mmol / L or more and 30.0 mmol / L or less, reduces the hue unevenness of the white background and is excellent in image storability of yellow images. halogen Found to be able to implement the method of processing the silver color photographic material, it is completed the invention. That is, even if the b * value of the white background portion is small, by performing treatment with a stabilizing solution containing a specific amount of sulfinic acid derivative, continuous processing is performed under severe processing conditions such as rapid processing. However, the occurrence of uneven hue on the white background is suppressed, and fading of the yellow image can be effectively suppressed even when the formed yellow image is irradiated with light for a long time in a high temperature and high humidity environment. It is a thing.

In addition, as a result of further investigations by the inventors,
Processing of a silver halide color photographic light-sensitive material that is processed through at least a color development step, a bleach-fixing step or a bleaching step and a fixing step, and a processing step comprising a stabilization step. In the method, the chromaticity (L ^* , b ^* ) of the unexposed portion of the silver halide color photographic light-sensitive material after the development processing is 91 ≦ L ^* ≦ 97, −8.0 ≦ b ^* ≦ −3.5. And at least one layer of the silver halide color photographic light-sensitive material contains a compound represented by the following general formula (II). In addition, the present inventors have found that it is possible to realize a method for processing a silver halide color light-sensitive material in which hue unevenness in a white background portion is reduced and the yellow image is excellent in image storability. A specific example is shown in a reference example described later.

[Wherein R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom, an aliphatic group or an aryl group, R _b represents an n1-valent aliphatic group, an aryl group or a heterocyclic group, and X ₂ represents Represents a divalent organic group. n1 represents an integer of 1 or more, and n2 represents an integer of 0 or more. Here, when n2 is 2 or more, the plurality of X ₂ may be the same as or different from each other. ]
Details of the present invention will be described below.

  First, the silver halide color photographic light-sensitive material according to the present invention will be described.

  The silver halide color photographic light-sensitive material according to the present invention mainly comprises a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, a green-sensitive silver halide emulsion layer containing a magenta dye-forming coupler, and cyan on a support. It comprises a photographic constituent layer comprising at least one red-sensitive silver halide emulsion layer containing a dye-forming coupler and a non-photosensitive hydrophilic colloid layer. The silver halide emulsion layer containing the yellow dye-forming coupler is used as a yellow coloring layer, the silver halide emulsion layer containing the magenta dye-forming coupler is used as a magenta coloring layer, and the silver halide containing the cyan dye-forming coupler. The emulsion layer functions as a cyan coloring layer. The silver halide emulsions contained in the yellow coloring layer, the magenta coloring layer and the cyan coloring layer, respectively, are sensitive to light in different wavelength regions (for example, light in the blue region, green region and red region). It is preferable to have. The silver halide color photographic light-sensitive material according to the present invention includes an anti-halation layer, an intermediate layer, and a colored layer as a non-photosensitive hydrophilic colloid layer, which will be described later, if desired, in addition to the yellow coloring layer, the magenta coloring layer, and the cyan coloring layer. You may have.

In the silver halide color photographic light-sensitive material according to the present invention, the chromaticity in the white background portion (unexposed area) after the development processing described later is 91 ≦ L ^* ≦ 97, −8.0 ≦ b ^* ≦ −3.5, preferably L ^* is 96 ≦ L ^* ≦ 97, and b ^* is −8.0 ≦ b ^* ≦ −4.0, more preferably −7. 0 ≦ b ^* ≦ −4.5.

The chromaticity (L ^* , b ^* ) referred to in the present invention is a lightness index L ^* and a perceptual chromaticity index a ^* , b ^* in the CIE color space, and details of these CIE 1976 L ^* a ^* b ^* color space. Is described in detail in “Fine Imaging and Color Hardcopy”, page 354 (1999, published by Corona) edited by the Japan Photography Society and the Japan Imaging Society. The tristimulus values when using this color space are values obtained in accordance with the method described in JIS Z8717 that defines the tristimulus value measurement method for the X, Y, and Z coordinates of the fluorescent reflecting object. The chromaticity in the CIE 1976 L ^* a ^* b ^* color space is measured based on the standard white chromaticity according to CIED65 (6504K) which is an international standard for daylight. In the present invention, as a chromaticity measuring apparatus capable of measuring chromaticity in the CIE 1976 L ^* a ^* b ^* color space, for example, a C-2000 color analyzer manufactured by Hitachi, Ltd., a color analyzer (CMS-1200 manufactured by Murakami Color Co., Ltd.) Alternatively, it can be measured using a color chromaticity meter CR-100 manufactured by Konica Minolta Sensing Co., Ltd. and CIE D65 (6504K) as a reference light source.

In the silver halide color photographic light-sensitive material (hereinafter also simply referred to as light-sensitive material) according to the present invention, the blue-sensitive silver halide content of the blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler is calculated in terms of silver amount. is preferably 0.25 g / m ² or less, more preferably 0.05 g / m ² or more, 0.20 g / m ² or less, particularly preferably 0.05 g / m ² or more, 0.16 g / m ² or less It is.

  The average grain size of the blue-sensitive silver halide emulsion of the blue-sensitive silver halide emulsion layer according to the present invention is preferably 0.20 μm or more and 0.55 μm or less, more preferably 0.20 μm or more, It is 0.50 μm or less, particularly preferably 0.20 μm or more and 0.47 μm or less.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the chromaticity (L ^* , b ^* ) of the unexposed portion of the silver halide color photographic light-sensitive material after the development processing is 91 ≦ L ^*. ≦ 97, −8.0 ≦ b ^* ≦ −3.5, and at least one layer of the silver halide color photographic light-sensitive material contains the compound represented by the general formula (II). This is one of the preferred embodiments, and the object of the present invention can also be achieved by adopting the configuration defined above.

  Hereinafter, the detail of the compound represented by general formula (II) is demonstrated.

In the general formula (II), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, an aliphatic group (preferably an alkyl group having 1 to 24 carbon atoms which may have a substituent, Each group such as methyl, ethyl, isopropyl, dodecyl, hexadecyl, methoxyethyl) or an aryl group (preferably an aryl group having 6 to 30 carbon atoms which may have a substituent, such as phenyl _Rb represents an n1-valent aliphatic group (preferably an n1-valent alkyl group having 1 to 24 carbon atoms which may have a substituent, for example, Each group such as methyl, ethyl, isopropyl, dodecyl, hexadecyl, methoxyethyl, methylene, methylidene, 1,2,3-propanetriyl), an aryl group (preferably an optionally substituted carbon number) To 30 n1-valent aryl groups, for example, a phenyl group, a 4-methylphenyl group, a phenylene group, or the like, or a heterocyclic group (preferably at least one nitrogen, oxygen, or a heterocyclic ring having from 2 to 30 carbon atoms containing a sulfur atom, for example, heterocycles pyridine, represents triazine, morpholine, what) thiophene, X ₂ represents a divalent organic group. Here, when n2 is 2 or more, the plurality of X ₂ may be the same as or different from each other. A divalent organic group is an organic group having two single bond bonds (two locations). For example, an arbitrary hydrogen atom is removed from a substituent (monovalent group). It is an organic group (a divalent group) having two bonds. For example, groups such as described below, -O -, - S -, - SO -, - SO 2 -, - NRX- (RX represents a hydrogen atom, an aliphatic group, a heterocyclic group).

  However, the compound represented by the general formula (II) has a molecular weight of 200 or more.

In the general formula (II), R ₁ , R ₂ and R ₃ are preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom or an alkyl group, and most preferably a hydrogen atom. . In the present invention, R _b is preferably an n1-valent aliphatic group or a heterocyclic ring, and more preferably an n1-valent alkyl group.

In general formula (II), the case where n1 is 1-6 is preferable, and the case where it is 2-4 is more preferable. X ₂ is preferably a divalent group shown below, among which (1) to (10), (14) to (17), (20), and (23) are more preferable, and (1 ) To (4), (6) to (8), (20), and (23) are most preferable.

  The compound represented by the general formula (II) has a molecular weight of 200 or more (preferably 200 to 3000), but in the present invention, the molecular weight is more preferably 350 or more (preferably 350 to 2000). The case of ~ 1000 is more preferable.

In general formula (II), when n1 is 1, n1 is 2, and n1 is 3, respectively. When n1 is 3, _Rb is preferably a heterocyclic group.

Further, X ₂ is preferably a group represented by the following general formula (III), particularly preferably n1 is 3.

In the general formula (III), R _c represents an alkylene group, preferably an alkylene group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms which may have a substituent. , Ethylene, propylene, 2-methyl-1,3-propylene, 1,6-hexylene. When n2 is 2 or more, the plurality of —R _c O— may be the same or different.

In the general formula (II), R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are hydrogen atoms, n1 is 2, 3 or 4 and n2 is 1 or 2. X ₂ is preferably (1) to (4), (6) to (8), (20) or (23), and R _b is an n1-valent alkyl group, and R ₁ , R ₂ , R ₃ are all hydrogen atoms, n1 is 3 or 4, X ₂ is (1) to (4), (6) to (8) or (20) or (23), The case where R _b is an n1-valent alkyl group is more preferable.

  Hereinafter, although the preferable specific example of a compound represented by general formula (II) is shown, this invention is not limited to these.

  The compound represented by the general formula (II) according to the present invention may be used alone or as a mixture of a plurality of compounds. In addition, many of these compounds are commercially available. For example, a product marketed under the trade name NK ester AMP-60G from Shin-Nakamura Chemical Co., Ltd. is a product containing exemplary compound (B-1). . Similarly, the product marketed under the trade name KAYARAD HDDA from Nippon Kayaku Co., Ltd. is the exemplified compound (B-24), and the product marketed under the trade name Aronics M315 from Toagosei Co., Ltd. (B-38). ) And is readily available. These compounds are synthesized, for example, by reacting a starting compound such as pentaerythritol with esterification, amidation, an alkylating agent, or a lactone, and a derivative such as acrylic acid, depending on the compound. be able to. Other compounds can also be easily synthesized by ordinary reactions such as esterification and amidation.

  Next, main components of the silver halide color photographic light-sensitive material according to the present invention will be described.

  The silver halide grains in the silver halide emulsion according to the present invention preferably have a silver chloride content of 90 mol% or more, more preferably a silver chloride content of 93 mol% or more, and 95 mol%. More preferably, the above is true. The silver bromide content is preferably 0.1 to 10 mol%, more preferably 0.5 to 8 mol%, and still more preferably 2 to 8 mol%. The silver iodide content is preferably 0.05 to 2 mol%, more preferably 0.05 to 1 mol%.

  In the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration is also preferably used. In this case, the portion containing silver bromide at a high concentration is epitaxially bonded to the silver halide emulsion grains. Or a so-called core-shell emulsion, or a complete layer may not be formed and only regions having different compositions may exist. Further, although the composition may change continuously or discontinuously, it is preferable that the silver halide grains have a silver bromide localized phase in at least a part of the outermost shell, in the vicinity of the vertex. It is more preferable to have a silver bromide localized phase.

  In the present invention, the silver bromide localized phase is a silver halide phase containing silver bromide having a silver bromide content of at least twice the average silver bromide content of the silver halide grains according to the present invention, It preferably contains silver bromide having a silver bromide content of 3 times or more of the average silver bromide content of the silver halide grains, and preferably contains silver bromide having a silver bromide content of 5 times or more.

  The silver bromide localized phase preferably contains a group 8 metal compound described later. In this case, the Group 8 metal compound used is preferably an iridium complex.

  In the present invention, silver halide grains having at least one silver iodide localized phase inside the grains can also be preferably used. In the present invention, the term “grain interior” refers to a silver halide phase excluding the grain surface in silver halide grains. In the present invention, the silver iodide localized phase is a silver halide phase containing silver iodide having a silver iodide content of at least twice the average silver iodide content of the silver halide grains according to the present invention, It preferably contains silver iodide having a silver iodide content of at least 3 times the average silver iodide content of the silver halide grains, and preferably contains silver iodide having a silver iodide content of 5 times or more. In the present invention, the position of the silver iodide localized phase is preferably 60% or more outside the silver halide volume from the grain center, more preferably 70% or more, and more preferably 80% or more outside. Is most preferred.

  One of the preferred forms of the silver iodide localized phase is that the silver iodide localized phase is present in a layered form inside the silver halide grains (hereinafter also referred to as a silver iodide localized layer). It is also preferable to introduce two or more silver halide localized layers. In that case, at least one layer (hereinafter referred to as sublayer) having a main layer introduced under the above conditions and having a concentration lower than the maximum iodide concentration is more than the main layer. Further, it is preferably introduced near the particle surface. The I concentration of the main layer and sublayer can be arbitrarily selected according to the purpose. From the viewpoint of latent image stability, the main layer preferably has a high density as much as possible, and the sublayer preferably has a lower density than the main layer. In the present invention, another preferred form of the silver iodide localized phase is that the silver iodide localized phase is present in the vicinity of the apex or the ridge line of the silver halide grain, and is used in combination with the above-mentioned silver iodide localized layer. It is also preferable to do.

  When the silver halide emulsion in the present invention contains silver bromide and / or silver iodide, the silver bromide content of silver halide grains and / or the inter-grain variation coefficient of silver iodide content are respectively It is preferably less than 30%, more preferably less than 20%. The lower limit of the coefficient of variation between grains of the silver bromide content is 0.01%.

  The silver bromide content and silver iodide content of the silver halide grains can be determined by the EPMA method (Electron Probe Micro Analyzer method). Specifically, a sample in which silver halide grains are well dispersed so as not to contact each other is prepared, and irradiated with an electron beam while being cooled to −100 ° C. or lower with liquid nitrogen, and emitted from individual silver halide grains. By determining the characteristic X-ray intensities of silver, bromine and iodine, the silver bromide content and silver iodide content of the individual silver halide grains can be determined.

  By the above method, the silver bromide content and silver iodide content of the silver halide grains determined for each silver halide grain were determined for 300 or more silver halide grains, and the averages were average silver bromide, respectively. The content ratio and the silver iodide content, and the grain-to-grain variation coefficient of the silver bromide content and the silver iodide content of the silver halide grains according to the present invention are determined by the following formula.

Coefficient of variation between grains of silver bromide content = (standard deviation of silver bromide content of silver halide grains) / (average silver bromide content) × 100 (%)
Coefficient of variation between grains of silver iodide content = (standard deviation of silver iodide content of silver halide grains) / (average silver iodide content) × 100 (%)
In the present invention, it is also preferable to use silver halide grains having dislocation lines inside the grains.

  In the present invention, various bromides or iodides can be used to contain silver bromide or silver iodide in the silver halide grains. For example, silver halide fine particles containing silver bromide or silver iodide disclosed in JP-A-2-68538, etc., a method using an aqueous solution of bromide salt or iodide salt such as potassium bromide aqueous solution or potassium iodide Alternatively, a method using a halide ion releasing agent can be arbitrarily used. In the present invention, the silver iodide content, silver bromide content, silver iodide localized phase, silver bromide localized layer, or dislocation line introduction in the silver halide grains, the concentration and amount of these additives, etc. Can be adjusted arbitrarily.

  In order to obtain a silver halide emulsion according to the present invention, it is advantageous to contain heavy metal ions. Heavy metal ions that can be used for such purposes include Group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt, and twelfth metals such as cadmium, zinc, and mercury. Group transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium can be given.

  In the present invention, the silver halide grains preferably contain one or more group 8 metal complexes, and include one or more group 8 metal complex complexes having one or more water ligands and / or organic ligands. It is more preferable to contain.

  The group 8 metal complex used in the present invention is preferably a metal complex of iron, iridium, rhodium, osmium, ruthenium, cobalt and platinum. As the metal complex, a six-coordinate complex, a five-coordinate complex, a four-coordinate complex, a two-coordinate complex, and the like can be used, and a six-coordinate complex and a four-coordinate complex are preferable. The group 8 metal complex having one or more water ligands and / or organic ligands is more preferably an iridium metal complex.

  In the present invention, the ligand constituting the Group 8 metal complex is a carbonyl ligand, a fullinate ligand, a thiocyanate ligand, a nitrosyl ligand, a thionitrosyl ligand, a cyano ligand, or water coordination. Arbitrary, halogen ligands, ammonia, hydroxide, nitrous acid, sulfurous acid, peroxide ligands and organic ligands can be used, but nitrosyl ligands, thionitrosyls. It is preferable to contain one or more ligands selected from a ligand, a cyano ligand, a water ligand, a halogen ligand, and an organic ligand.

  In the present invention, an organic ligand refers to a compound that contains one or more H—C, C—C, or C—N—H bonds and can be coordinated to a metal ion. The organic ligand used in the present invention is selected from pyridine, pyrazine, pyrimidine, pyran, pyridazine, imidazole, thiazole, isothiazole, triazole, pyrazole, furan, furazane, oxazole, isoxazole, thiophene, phenanthroline, bipyridine, and ethylenediamine. It is preferable that the compound is a compound, an ion, or a compound obtained by introducing a substituent into these compounds.

  In the silver halide emulsion according to the present invention, a group 8 metal complex represented by the following general formula (A) can also be preferably used.

Formula (A)
R _n [MX _m Y _6-m ]
In the formula, M represents a metal selected from Group 8 elements of the periodic table, and is iron, cobalt, ruthenium, iridium, rhodium, osmium, or platinum, and more preferably iron, ruthenium, rhodium, iridium, or osmium. R represents an alkali metal, preferably cesium, sodium or potassium. m represents an integer of 0 to 6, and n represents an integer of 0 to 4. X and Y represent ligands, such as a carbonyl ligand, a fullinate ligand, a thiocyanate ligand, a nitrosyl ligand, a thionitrosyl ligand, a cyano ligand, a halogen ligand, ammonia, water Represents oxide, nitrous acid, sulfurous acid, and peroxide ligands.

  These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. When metal ions form a complex, any counter cation such as potassium ions, calcium ions, sodium ions, ammonium ions, etc. can be used. Moreover, when a metal complex is a cation, what is known in this industry, such as a nitrate ion, a halogen ion, a perchlorate ion, can be used as a counter anion.

  In order to contain heavy metal ions in the silver halide emulsion according to the present invention, the heavy metal compound is added before the formation of silver halide grains, during the formation of silver halide grains, during physical ripening after the formation of silver halide grains. What is necessary is just to add in the arbitrary places of each process. In order to obtain a silver halide emulsion satisfying the above-mentioned conditions, the heavy metal compound can be dissolved together with the halide salt and continuously added throughout the grain forming process or a part thereof.

The amount of the heavy metal ion added to the silver halide emulsion is preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻² mol per mol of silver halide, and 1 × 10 ⁻⁸ mol to 5 × 10 ⁻⁵ mol. Mole is more preferred.

  Any shape can be used for the silver halide grains according to the present invention, but a preferred example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, and JP-B-55-42737, The Journal of Photographic Science (J. Photogr. Sci.) Volumes of 21, 39 (1973) etc. are used to make particles having shapes such as octahedron, tetrahedron, twenty-fourhedron, dodecahedron, etc. Can also be used. Further, grains having a twin plane other than normal crystals or tabular grains may be used.

  The silver halide grains according to the present invention are preferably grains having a single shape, but two or more monodispersed silver halide emulsions can be added to the same layer.

  The particle diameter of the other silver halide grains excluding the blue-sensitive silver halide emulsion according to the present invention is not particularly limited, but preferably 0.1 to 0.1 when considering other photographic performances such as rapid processability and sensitivity. It is 5.0 μm, more preferably in the range of 0.2 to 3.0 μm. In particular, when cubic particles are used, it is preferably in the range of 0.1 to 1.2 μm, more preferably 0.15 to 1.0 μm.

  The grain size distribution of the silver halide grains according to the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, more preferably 0.10 or less. Here, the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R
(Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)
The particle diameter here means the diameter in the case of spherical silver halide grains, and the diameter when the projected image is converted into a circular image of the same area in the case of grains other than a cube or a sphere. To express.

  As a silver halide emulsion preparation apparatus and method, various methods known in the art can be used.

  The silver halide emulsion according to the present invention may be obtained by any of acidic method, neutral method and ammonia method. The particles may be grown at one time, or may be grown after the seed particles are made. The method for making seed particles and the method for growing them may be the same or different.

  Further, the form of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, and the like, but those obtained by the simultaneous mixing method are preferred. Furthermore, the pAg controlled double jet method described in JP-A No. 54-48521 can be used as one type of the simultaneous mixing method.

  Further, an apparatus for supplying a water-soluble silver salt solution and a water-soluble halide salt aqueous solution from an addition device arranged in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524, German Published Patent No. 2921164 An apparatus for continuously adding a water-soluble silver salt solution and a water-soluble halide salt aqueous solution described in JP-A No. 56-501776, etc. An apparatus that forms grains while maintaining the distance between silver halide grains constant by concentration by a method may be used.

  Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound, or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

  The silver halide photographic emulsion according to the present invention is preferably desalted after grain formation. Desalting can be performed, for example, by the method of RD17643, Item II. More specifically, in order to remove unnecessary soluble salts from the precipitated product or the emulsion after physical ripening, a noodle water washing method in which gelatin is gelled may be used, and inorganic salts and anionic surfactants may be used. An anionic polymer (eg, polystyrene sulfonic acid) can be used, but a precipitation method using gelatin derivatives and chemically modified gelatin (eg, acylated gelatin, carbamoylated gelatin) or ultrafiltration using membrane separation. Desalting is preferred.

  As the dispersion medium used in the production of the silver halide emulsion according to the present invention, a compound having a protective colloid property for silver halide grains can be arbitrarily used. Examples of the dispersion medium that can be preferably used in the present invention include gelatin and hydrophilic colloid. Examples of gelatin include alkali-treated gelatin and acid-treated gelatin having a molecular weight of about 100,000, or oxidized gelatin and enzyme-treated gelatin. Can be preferably used. The average molecular weight of gelatin at the time of nucleation of silver halide grains is preferably 10,000 to 70,000, and more preferably 10,000 to 50,000. It is also preferable to use gelatin having a low methionine content during nucleation, and the methionine content per unit mass (gram) of the dispersion medium is preferably 50 μmol or less, more preferably 20 μmol or less. Examples of hydrophilic colloids include 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, sodium alginate, starch derivatives Sugar derivatives such as: polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, various kinds such as copolymers such as polyvinyl pyrazole A synthetic hydrophilic polymer substance or the like can be used.

  The silver halide emulsion according to the present invention can be used in combination of a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.

  As a chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used, and a sulfur sensitizer and / or a selenium sensitizer are usable. Agents are preferred.

  Sulfur sensitizers include 1,3-diphenylthiourea, triethylthiourea, thiourea derivatives such as 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, thiosulfuric acid Salt, sulfur alone and the like are preferable. In addition, as sulfur simple substance, the alpha-sulfur which belongs to an orthorhombic system is preferable. In addition, U.S. Pat. Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313, No. 3,656,955, etc., West German Published Application (OLS) 1,422,869, JP-A-56-24937, 55-45016, etc. are used. be able to.

  As the selenium sensitizer, an unstable selenium compound capable of reacting with silver nitrate in an aqueous solution to form a silver selenide precipitate is preferably used. For example, U.S. Pat. Nos. 1,574,944, 1,602,592, 1,623,499, JP-A-60-150046, JP-A-4-25832, and 4-109240. 4-147250 and the like. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (such as allyl isoselenocyanate), selenoureas (such as N, N-dimethylselenourea, N, N, N'-triethylseleno). Urea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'- 4-nitrophenylcarbonylselenourea etc.), selenoketones (eg selenoacetone, selenoacetophenone etc.), selenoamide (eg selenoacetamido, N, N-dimethylselenobenzamide etc.), selenocarboxylic acids and selenoesters (eg 2-selenopropionic acid, methyl-3-selenobutyrate, etc.) Phosphates (eg, tri-p-triselenophosphate, etc.), selenides (eg, dimethyl selenide, triphenylphosphine selenide, pentafluorophenyl-diphenylphosphine selenide, trifurylphosphine selenide, Trypyridylphosphine selenide). Particularly preferred selenium sensitizers are selenourea, selenoamides, and selenides.

  In the present invention, noble metal salts such as gold, platinum, palladium, iridium and the like described in RD magazine 307, 307105 are preferably used, and in particular, a gold sensitizer is preferably used in combination. Useful gold sensitizers include U.S. Pat. Nos. 2,597,856, 5,049,485, and Japanese Patent Publication No. 44-15748 in addition to chloroauric acid, gold thiosulfate, gold thiocyanate and the like. And organic gold compounds disclosed in JP-A-1-147537 and 4-70650, gold sulfide, and gold sulfide silver. Further, when performing a sensitization method using a gold complex salt, it is preferable to use a gold ligand such as thiosulfate, thiocyanate, and thioether as an auxiliary agent, and in particular, it is preferable to use thiocyanate. .

  In the above-mentioned various chemical sensitizers, postscript inhibitors, oxidizing agents and the like according to the present invention, JP 2001-318443, JP 2003-29472, JP 2004-37554, 2004-4144, 2004-4446, 2004-4442, 2004-4456, 2004-4458, 2004-4656, 2004-4672, 2003-307803, 2003-287841, 2003 287842, 2003-233146, 2003-172990, 2003-172991, 2003-113193, 2003-113194, 2003-114489, 2002-372765, 2002-296721 No. 2002-278011, No. 2002 No. 268169, No. 2002-244241, No. 2002-259882, No. 2002-258427, No. 2002-268168, No. 2002-268170, No. 2000-193942, No. 2001-75214, No. 2001-75215 2001-75216, 2001-75217, 2001-75218, 2001-100352, 2004-70363, 2004-67695, 2002-131858, 2001-166612, etc. The compounds described in the gazette, European Patent Nos. 1094360, 13888752, U.S. Pat. Nos. 6,686,143 and 6,322,961, and the techniques for using them can also be preferably used.

The addition amount of the chalcogen sensitizer and gold sensitizer is not uniform depending on the type of silver halide emulsion, the type of compound used, and the ripening conditions, but usually 1 × 10 ⁻⁹ per mole of silver halide. It is preferably ˜1 × 10 ⁻⁵ mol. More preferably, it is 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁴ mol. Depending on the nature of the sensitizer used, the above-mentioned various sensitizers may be added by dissolving them in water or an organic solvent such as methanol alone or in a mixed solvent, or by premixing with a gelatin solution. The method of addition may be the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer.

  In the present invention, reduction sensitization may be used, and reducing compounds described in RD magazine 307, 307105, JP-A-7-78685, and the like may also be used.

  In the silver halide color photographic light-sensitive material according to the present invention, it is preferable that at least one of the constituent layers contains a compound represented by the following general formula [1] from the viewpoint of further achieving the object effect of the present invention.

In the above general formula [1], R ₁ represents a tertiary alkyl group, and R ₂ represents a primary or secondary alkyl group. However, R ₂ is not substituted by a phenyl group. R ₃ , R ₄ and R ₅ represent a hydrogen atom, an alkyl group, an alkoxycarbonyl group, a phenoxycarbonyl group, an alkoxy group, a phenoxy group or a phenylthio group.

In the general formula [1] according to the present invention, R ₁ represents a tertiary alkyl group (for example, t-butyl group, t-pentyl group, t-octyl group, etc.), preferably a t-butyl group. R ₂ represents a primary or secondary alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, etc.), preferably a methyl group. However, R ₂ may be substituted with a substituent, but is not substituted with a phenyl group. R ₃ , R ₄ and R ₅ are each a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, a butyl group, a dodecyl group, etc.), an alkoxycarbonyl group (for example, an ethoxycarbonyl group), a phenoxycarbonyl group (for example, 2, 4-di-t-butylphenoxycarbonyl group, etc.), alkoxy groups (eg, 2-ethylhexyloxy group, etc.), phenoxy groups (eg, 4- (2-ethylhexyl) phenoxy group, 4-dodecyl-phenoxy group, etc.), A phenylthio group (for example, 3-tbutyl-4-hydroxy-5-methylphenylthio group and the like) is represented.

In addition, the group represented by R ₁ to R ₅ may be substituted with a substituent. In addition, the compound represented by the general formula [1] is preferably a compound that does not contain a primary, secondary, or tertiary amino group in the structural formula, or a compound that does not contain an acylamino group. More preferred are compounds that do not contain primary, secondary or tertiary amino groups. The group represented by R ₄ is preferably an alkyl group.

The group represented by R ₄ is more preferably a group containing the following linking group.

[Wherein, R ₆ , R ₆ ′, R ₇ , R ₇ ′, R ₈ , R ₈ ′, R ₉ and R ₉ ′ each represent a hydrogen atom, an alkyl group or a phenyl group. ]
Of the compounds represented by the general formula [1], preferred compounds are those represented by the following general formula [1A] or [1B].

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ have the same meanings as R ₁ to R _{5 in the} general formula [1], respectively. R ₁₁ represents an alkylene group (for example, an ethylene group or an isobutylene group). ]
Of the compounds of the general formulas [1A] and [1B], more preferred compounds are those represented by the general formula [1B].

  Next, although the specific example of a compound shown by General formula [1] is shown, this invention is not limited to these.

  The silver halide emulsion according to the present invention is known for the purpose of preventing fog generated during the preparation process of the silver halide color photographic light-sensitive material, reducing performance fluctuation during storage, and preventing fog generated during development. Antifoggants, oxidizing agents, inhibitors, stabilizers, and the like can be used. Examples of preferred compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A-2-14636, page 7, lower column, and more preferred specific compounds. As the compounds (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and 1- (3-methoxyphenyl) -5-mercapto Compounds such as tetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole, general formula (S) compounds described in JP-A-8-6201, thiosulfonic acid compounds, disulfide compounds, polysulfide compounds and the like are preferable. -145202, 2004-226434, 2004-240182 and the like can be preferably used.

Depending on the purpose, these compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, a chemical sensitization step, and a coating solution preparation step. A preferable addition amount of these compounds is 1 × 10 ⁻⁸ to 1 × 10 ⁻¹ mol / mol Ag ×, more preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻² mol per mol of silver halide. For the addition of these compounds, methods commonly used in the art when additives are added to photographic emulsions, coating solutions, preparation solutions and the like can be applied. For example, in the case of a water-soluble compound, an aqueous solution having an appropriate concentration is used. In the case of a compound that is insoluble or sparingly soluble in water, any organic solvent that can be mixed with water, for example, alcohols, glycols, ketones It can be dissolved in a solvent that does not adversely affect photographic properties such as esters and amides, and added as a solution.

  In the silver halide color photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used. In particular, as dyes having absorption in the visible region, the dyes AI-1 to 11 described in JP-A-3-252840, page 30 and The dyes described in JP-A-6-37706 are preferably used, and the infrared absorbing dyes are represented by the general formulas (I), (II), and (III) described in JP-A-1-280750, page 2, lower left column. The compounds have preferred spectral properties and are preferred without affecting the photographic properties of the silver halide emulsion and without contamination by residual colors. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the same publication, page 3, lower left column to page 5, lower left column.

  For the purpose of improving sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of the unprocessed sample of the photosensitive material is 0.7 to 3.0. More preferably 0.

  It is preferable to add a fluorescent brightening agent to the silver halide color photographic light-sensitive material according to the present invention because white background can be improved. Preferred examples of the compound include compounds represented by the general formula (II) described in JP-A-2-232652.

  The silver halide color photographic light-sensitive material according to the present invention has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler, and a cyan coupler. The silver halide emulsion contains one or a combination of two or more sensitizing dyes.

  As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any known compound can be used. As the blue-sensitive sensitizing dye, it is described in JP-A-3-251840, page 28. BS-1 to BS-8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. In addition, when performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared photosensitive sensitizing dye. As the infrared photosensitive sensitizing dye, JP-A-4-285950 is disclosed. The pigments IRS-1 to IRS11 described in JP-A No. 6-8 are preferably used. Further, these infrared, red, green and blue photosensitive sensitizing dyes are supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pages 8 to 9 and JP-A-5-66515. It is preferable to use a combination of compounds S-1 to S-17 described in JP-A No. 15-17.

  These sensitizing dyes may be added at any time from silver halide grain formation to coating solution preparation.

  As a method for adding a sensitizing dye, it may be added as a solution by dissolving it in water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or water, or as a solid dispersion. Also good.

  As a coupler used in the silver halide color photographic light-sensitive material according to the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm can be formed by a coupling reaction with an oxidized form of a color developing agent. Any compound can be used, but particularly representative couplers include yellow dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 350 to 500 nm, and magenta dye formation having a spectral absorption maximum wavelength in the wavelength range of 500 to 600 nm. Examples of couplers include those known as cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

  Examples of cyan dye-forming couplers that can be preferably used in the silver halide color photographic light-sensitive material according to the present invention include general formulas (CI) and (C-II) described in JP-A-4-114154, page 5, lower left column. ) Can be mentioned. Specific compounds include those described as CC-1 to CC-9 in page 5, lower right column to page 6, lower left column.

  As a magenta dye-forming coupler which can be preferably used in the silver halide color photographic light-sensitive material according to the present invention, general formulas (M-I) and (M-II) described in JP-A-4-114154, page 4, upper right column. ) Can be mentioned. Specific compounds include those described as MC-1 to MC-11 in page 4, lower left column to page 5, upper right column. Among the magenta dye-forming couplers, a coupler represented by the general formula (M-I) described in the upper right column on page 4 of the same publication is preferred. Among them, the RM of the general formula (M-I) is used. A coupler in which is a tertiary alkyl group is particularly preferred because of excellent light resistance. MC-8 to MC-11 described in the upper column of page 5 of the same publication are preferable because they are excellent in color reproduction from blue to purple and red, and are excellent in detail descriptive power.

  Examples of preferred couplers represented by the above general formula (M-I) are exemplified compounds 1 to 64 described on pages 5 to 9 of JP-A No. 63-253934 and JP-A No. 2-100048. Exemplified compounds M-1 to M-29 described on pages 5 to 6, Exemplified compounds (1) to (36) described on pages 5 to 12 of JP-A-7-175186, JP-A-7-219170 Exemplified compounds M-1 to M-33 described on pages 14 to 22 of the publication, Exemplified compounds M-1 to M-16 described on pages 5 to 9 of JP-A-8-304972, and JP-A-10- Exemplified compounds M-1 to M-26 described on pages 5 to 10 of 207024, Exemplified compounds M-1 to M-36 described on pages 5 to 22 of JP-A-10-207025, US Patent Exemplified compounds described on pages 3 to 6 of No. 5,576,150 -1 to M-24, Exemplified compounds M-1 to M-48 described on pages 3 to 9 of US Pat. No. 5,609,996, 3 of US Pat. No. 5,667,952 Exemplified compounds M-1 to M-23 described on pages 5 to 5, Exemplified compounds M-1 to M-26 described on pages 3 to 6 of US Pat. No. 5,698,386, etc. Can do.

Examples of yellow dye-forming couplers that can be preferably used include couplers represented by general formula (Y-I) described in JP-A-4-114154, page 3, upper right column. Specific compounds include those described as YC-1 to YC-9 in the lower left column on page 3 of the publication. Among them, a coupler in which RY _{1 in the} general formula [Y-1] is an alkoxy group, or a coupler represented by the general formula [I] described in JP-A-6-67388 is preferable because it can reproduce a yellow color having a preferable color tone. Among these, as particularly preferred compound examples, YC-8, YC-9 described in JP-A-4-114154, page 4, upper left column, and No. described in JP-A-6-67388, pages 13-14 The compound shown by 1)-(47) can be mentioned. The most preferred compounds are those represented by the general formula [Y-1] described in JP-A-4-81847, pages 1 and 11-17.

  When using an oil-in-water emulsion dispersion method to add a coupler or other organic compound used in the silver halide color photographic light-sensitive material according to the present invention, it is usually a water-insoluble high-boiling organic material having a boiling point of 150 ° C. or higher. If necessary, the solvent is dissolved in combination with a low boiling point or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low boiling point organic solvent may be added after the dispersion or simultaneously with the dispersion.

  Examples of the high-boiling organic solvent that can be used to dissolve and disperse the coupler include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate, and dibutyl phthalate, and phosphoric acid such as tricresyl phosphate and trioctyl phosphate. Esters are preferably used. Further, the dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high boiling point organic solvents can be used in combination.

  Further, instead of using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound is dissolved in a low-boiling and / or water-soluble organic solvent as necessary. In addition, a method of emulsifying and dispersing by various dispersing means using a surfactant in a hydrophilic binder such as an aqueous gelatin solution can also be used. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

  Compounds containing a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof as one of the surfactants used for dispersing the photographic additive and adjusting the surface tension during coating. Is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant in which a fluorine atom is substituted on the alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is better that the time until dispersion is added to the coating solution after dispersion and the time from addition to coating after coating is shorter. It is preferably within 10 hours, more preferably within 3 hours and within 20 minutes.

  Each of the above couplers is preferably used in combination with an anti-fading agent in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by the general formulas [I] and [II] described on page 3 of JP-A-2-66541, and a general formula [IIIB] described in JP-A-3-1741503. A phenol compound represented by formula (A), an amine compound represented by formula [A] described in JP-A No. 64-90445, a general formula [XII], [XIII], [XIV described in JP-A No. 62-182741 ] And [XV] are particularly preferable for magenta dyes. Further, compounds represented by the general formula [I] described in JP-A-1-196049 and compounds represented by the general formula [II] described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

  For the purpose of shifting the absorption wavelength of the coloring dye, compounds such as compound (d-11) described in JP-A-4-114154, page 9, lower left column, compound (A'-1) described in page 10, lower left column, etc. Can be used. In addition, fluorescent dye releasing compounds described in US Pat. No. 4,774,187 can also be used.

  In the silver halide color photographic light-sensitive material according to the present invention, a compound that reacts with an oxidized developing agent is added to the layer between the photosensitive layer to prevent color turbidity or added to the silver halide emulsion layer. Thus, it is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Particularly preferred compounds are compounds represented by the general formula [II] described in JP-A-4-133056, compounds II-1 to II-14 described on pages 13 to 14 and compound-1 described on page 17 Is mentioned.

  In the silver halide color photographic light-sensitive material according to the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of a dye image. Preferred ultraviolet absorbers include benzotriazoles, and particularly preferred compounds are those represented by general formula [III-3] described in JP-A-1-250944, and general formulas described in JP-A-64-66646. Compounds represented by [III], UV-1L to UV-27L described in JP-A-63-187240, compounds represented by general formula [I] described in JP-A-4-16333, JP-A-5-165144 And compounds represented by the general formulas (I) and (II) described in Japanese Patent Publication.

  In the silver halide color photographic light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, gelatin and other polymer graft polymers, other than gelatin. Hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer materials such as mono- or copolymers can also be used. The calcium content in gelatin is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 30 ppm or less. Further, the content of heavy metals such as zinc, copper, manganese, and iron in gelatin is preferably 10 ppm or less, more preferably 5 ppm or less, and still more preferably 3 ppm or less.

  As the hardener of these binders, it is preferable to use a vinyl sulfone type hardener, a chlorotriazine type hardener, or a carboxyl group active hardener alone or in combination. It is preferable to use compounds described in JP-A Nos. 61-249054 and 61-245153. In order to prevent the growth of soot and bacteria that adversely affect photographic performance and image storage stability, it is preferable to add preservatives and antifungal agents as described in JP-A-3-157646 to the colloid layer. In order to improve the physical properties of the surface of the photosensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 and JP-A-2-73250 to the protective layer.

In the silver halide color photographic material according to the present invention, the total Coating amount of gelatin structure layer is 3 g / m ² or more, preferably 6 g / m ² or less, 3 g / m ² or more, 5 g / m More preferably, it is ² or less. Further, even in the case of ultra-rapid processing, in order to satisfy development progress, fixing bleachability, and residual color, the total thickness of the constituent layers is preferably 3 μm to 7.5 μm, and more preferably 3 μm to 6.5 μm. It is preferable that The dry film thickness can be measured by measuring the change in film thickness before and after peeling the dry film, or by observing the cross section with an optical microscope or an electron microscope. In the present invention, the swelling film thickness is preferably 8 μm to 19 μm, and more preferably 9 μm to 18 μm, in order to achieve both development progress and increase in the drying speed. The swollen film thickness can be measured by the dot method in a state where the dried photosensitive material is immersed in an aqueous solution at 35 ° C. and swelled to reach a sufficient equilibrium. Coated silver amount in the present invention is ^{0.3g / m 2 ~0.6g / m 2} .

  Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of soot and bacteria that adversely affect photographic performance and image storage stability. In order to improve the physical properties of the surface of the photosensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer. The film pH of the photosensitive material is preferably from 4.0 to 7.0, more preferably from 4.0 to 6.5.

  The silver halide color photographic light-sensitive material according to the present invention may have at least one yellow image forming layer, magenta image forming layer, and cyan image forming layer, but may form a plurality of color images as necessary. Units may be formed of layers.

  As the support used in the silver halide color photographic light-sensitive material according to the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride. Sheets, polypropylene that may contain a white pigment, polyethylene terephthalate support, baryta paper, and the like can be used. Especially, the support body which has a water-resistant resin coating layer on both surfaces of a base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

  As the white pigment used for the support, inorganic and / or organic white pigments can be used, and inorganic white pigments are preferably used. For example, alkaline earth metal sulfate such as barium sulfate, alkaline earth metal carbonate such as calcium carbonate, silica such as fine silicate, synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples thereof include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

  The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, and more preferably 15% by mass for improving sharpness.

  The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, and more preferably 0.15 or less, as the coefficient of variation described in the above publication.

  Further, the value of the center plane average roughness (SRa) of the support is preferably 0.15 μm or less, and more preferably 0.12 μm or less, because the effect of good gloss is obtained. Also, in order to improve the whiteness by adjusting the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the coated hydrophilic colloid layer, a trace amount of ultramarine, oil-soluble dyes, etc. It is preferable to add a blue tinting agent or a red tinting agent.

  The silver halide color photographic light-sensitive material according to the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and then directly or undercoat layer (adhesion of the support surface, antistatic property). One or more subbing layers for improving the properties, dimensional stability, rub resistance, hardness, antihalation properties, frictional properties and / or other properties.

  When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve the coating property. As the coating method, extrusion coating and curtain coating capable of simultaneously coating two or more layers are particularly useful. As the coating device, a slide coater, a curtain coater, an extrusion coater, or the like can be used.

  In order to form a photographic image using the silver halide color photographic light-sensitive material according to the present invention, an image recorded on the negative is optically imaged on the silver halide photographic light-sensitive material to be printed. Alternatively, after the image is converted into digital information, the image is formed on a CRT (cathode ray tube), and the image is formed on the silver halide photographic material to be printed and printed. Alternatively, printing may be performed by changing the intensity of laser light based on digital information and scanning.

  The silver halide color photographic light-sensitive material according to the present invention is preferably applied to a silver halide color photographic light-sensitive material that does not contain a developing agent, and in particular, a silver halide color photographic light-sensitive material that directly forms an image for viewing. A material is preferred. Examples thereof include color paper, color reversal paper, photosensitive material for forming a positive image, photosensitive material for display, and photosensitive material for color proof, and among them, a silver halide color photographic photosensitive material having a reflective support. It is preferable to apply to.

  Next, the processing method for the silver halide color photographic light-sensitive material of the present invention will be described.

  The silver halide color photographic light-sensitive material processing method of the present invention (hereinafter also simply referred to as a processing method) comprises subjecting an exposed silver halide color photographic light-sensitive material to bleaching following a color processing step (color developer). It is dried after passing through a process (bleaching solution), a fixing step (fixing solution), a bleach-fixing step (bleaching fixing solution), and a stabilizing step (stabilizing solution). Further, development processing can be continuously performed while replenishing a replenishing color developer, a replenishing bleaching solution, a replenishing fixing solution, a replenishing bleach-fixing solution, a replenishing stabilizing solution, or the like.

  In the treatment method of the present invention, the stabilizing solution constituting the stabilization step contains 2.0 mmol / L or more and 30.0 mmol / L or less of the sulfinic acid derivative represented by the general formula (I). It is characterized, Preferably it is 3.0 mmol / L or more and 25.0 mmol / L or less, Especially preferably, it is 5.0 mmol / L or more and 20.0 mmol / L or less. If the addition amount of the sulfinic acid derivative represented by the general formula (I) is 2.0 mmol / L or more, the storage stability (fading resistance) of the formed yellow image, which is the objective effect of the present invention, is further improved. Moreover, if it is 30.0 mmol / L or less, it does not generate | occur | produce in the stabilization liquid but can exist more stably.

  Hereinafter, the sulfinic acid derivative represented by the general formula (I) according to the present invention will be described.

  In the general formula (I), R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group, and when R is an alkyl group, it preferably has 1 to 10 carbon atoms, and more Preferably it is 1-3 alkyl groups. Moreover, in the case of a cycloalkyl group, C6-C10 is preferable and the case of C6-C is the most preferable. In the case of an alkenyl group and an alkynyl group, it preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. In the case of an aryl group, 6 to 10 carbon atoms are preferable, and the case of 6 carbon atoms is most preferable. These groups may be substituted by various substituents, and preferred substituents include a hydroxyl group, an alkyl group, an aryl group, an amino group, a sulfonic acid group, a carboxylic acid group, a nitro group, a phosphoric acid group, and a halogen atom. , Alkoxy groups, mercapto groups, cyano groups, alkylthio groups, sulfonyl groups, carbamoyl groups, carbonamido groups, sulfonamido groups, acyloxy groups, sulfonyloxy groups, ureido groups, and thioureido groups. Moreover, when these substituents are acid groups, the case of the above salt with M is included.

  Among the above, preferred R is preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group, and preferred substituents include an amino group, a carboxylic acid group, and a hydroxyl group. M in the general formula (I) represents a hydrogen atom, an alkali metal atom, an ammonium group or a quaternary amine group, preferably a hydrogen atom, a sodium atom, a potassium atom, an ammonium group or a trimethylammonium group.

  Among the sulfinic acid derivatives represented by the general formula (I), the arylsulfinic acid derivative in which R is an aryl group is particularly effective for the purpose of the present invention.

  Specific examples of the sulfinic acid derivative represented by the general formula (I) according to the present invention are illustrated below, but the sulfinic acid derivative represented by the general formula (I) is not limited thereto. Further, in the exemplified compounds below, the sulfinic acid group and the carboxylic acid group are mainly shown in the form of a neutral salt, but may be in the form of the salt shown by M above.

  The sulfinic acid derivative represented by the general formula (I) according to the present invention is generally synthesized by reduction of a sulfonyl chloride compound. Examples of the reducing agent include zinc powder, sulfite ion, alkali metal sulfide, and the like. Used. Other methods are also known. Including the above, a general synthesis method of the sulfinic acid derivative represented by the general formula (I) includes, for example, Chemical Review (Chem. Rev.), 4508, 69 (1951), Organic Synthesis (Organic Synthesis). ), Collective Vol. I. 492 (1941), Journal of American Chemical Society (J. Am. Chem. Soc.), 72, 1215 (1950), ibid, 50, 792, 274, (1928), etc. Yes.

  In addition to the sulfinic acid derivative represented by the general formula (I) according to the present invention, the stabilizing solution used in the stabilization step includes a chelating agent (ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1 -Diphosphonic acid, etc.), buffer (potassium carbonate, borate, acetate, phosphate, etc.), antifungal agent (Dearside 702 (made by Dearborn, USA), p-chloro-m-cresol, benzoisothiazoline- 3-one, etc.), optical brighteners (triazinyl stilbene compounds, etc.), antioxidants (ascorbates, etc.), water-soluble metal salts (zinc salts, magnesium salts, etc.), etc. Components can be used as appropriate.

Furthermore, the stabilizing solution may contain arylsulfinic acid such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid from the viewpoint of liquid storage stability, and may contain sulfite, bisulfite or metabisulfite. Is also preferably included. Any organic or inorganic substance may be used as long as it releases sulfite ions, but inorganic salts are preferred. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and the like. These salts are preferably added in an amount of at least 1 × 10 ⁻³ mol / L or more, more preferably 5 × 10 ⁻³ mol / L to 5 × 10 ⁻² mol / L in the stabilizing solution. It is added to become L.

  4-10 are preferable and, as for the preferable pH of a stabilization process, More preferably, it is 5-8.

  The temperature of the stabilization step can be variously set depending on the use and characteristics of the silver halide color photographic light-sensitive material to be processed, but is generally preferably 15 to 45 ° C, more preferably 20 to 40 ° C. Although the time can be set arbitrarily, a shorter time is desirable from the viewpoint of reducing the processing time. The time required for the stabilization process is preferably 8 to 26 seconds.

  A smaller replenishment amount is preferable from the viewpoint of running cost, reduction of discharge amount, handling property, and the like.

A specific preferable replenishing amount is preferably 0.5 to 50 times, more preferably 3 to 40 times the amount of silver halide color photographic light-sensitive material, which is brought from the previous bath per unit area. Alternatively, the amount is preferably 1 liter or less per 1 m ^{2 of} silver halide color photographic light-sensitive material, more preferably 500 ml or less. The replenishment may be performed continuously or intermittently.

  In the treatment method according to the present invention, the structure of the stabilization process using the stabilizing liquid may be composed of one tank or may be composed of two or more layers, preferably two or more tanks. It is preferable to use a multistage countercurrent system constituted by:

  Multi-stage counter-current system is a method of conveying silver halide photographic light-sensitive materials in a stabilizing tank divided into a plurality of stages, while the stabilizing solution overflows into each multi-stage divided stabilizing tank from the downstream to the upstream in the conveying direction of the photosensitive material. It is a system that flows along the road and performs a stabilization process.

  Next, the color developer, bleach solution, bleach-fix solution, and fixer used in the present invention will be described.

  Preferred examples of the color developing agent used in the color developing solution according to the present invention are known aromatic primary amine color developing agents, particularly p-phenylenediamine derivatives. Representative examples are shown below, but are not limited thereto. It is not something.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-methylaniline 4) 4 -Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline 6) 4-amino-3-methyl-N -Ethyl-N- (3-hydroxypropyl) aniline 7) 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline 8) 4-Amino-3-methyl-N-ethyl-N -(Β-Methanesulfonamidoethyl) aniline 9) 4-Amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-Amino-3-methyl-N-ethyl-N- (β- Me Xylethyl) aniline 11) 4-Amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-Amino-3-methyl-N- (3-carbamoylpropyl) -Nn-propyl -Aniline 13) 4-amino-N- (4-carbamoylbutyl) -Nn-propyl-3-methylaniline 14) N- (4-amino-3-methylphenyl) -3-hydroxypyrrolidine 15) N- (4-Amino-3-methylphenyl) -3- (hydroquinmethyl) pyrrolidine 16) N- (4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide Among the p-phenylenediamine derivatives, particularly preferred Illustrative compounds 5), 6), 7), 8) and 12), among which exemplary compounds 5) and 8) are preferred. These p-phenylenediamine derivatives are in the form of salts such as sulfates, hydrochlorides, sulfites, naphthalene disulfonates, p-toluenesulfonates, or free base types (also referred to as free forms). The concentration of the aromatic primary amine developing agent in the working solution is preferably 2 mmol to 200 mmol, more preferably 6 mmol to 100 mmol, and particularly preferably 10 mmol to 40 mmol per liter of the developing solution.

  The color developer used in the present invention preferably contains a preservative to reduce the disappearance of the color developing agent due to oxidation. Representative preservatives include hydroxylamine derivatives. Examples of the hydroxylamine derivatives that can be used in the present invention include hydroxylamine salts such as hydroxylamine sulfate and hydroxylamine hydrochloride, as well as JP-A-1-97953, 1-186939, 1-186940, Although the hydroxylamine derivative described in 1-187557 etc. can be used, the hydroxylamine derivative represented with the following general formula [A] is especially preferable.

  In the above general formula [A], L represents an alkylene group which may be substituted, and A represents a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, an amino group which may be alkyl-substituted, or an alkyl-substituted group. Represents an ammonio group which may be substituted, a carbamoyl group which may be substituted with alkyl, a sulfamoyl group which may be substituted with alkyl, an alkylsulfonyl group, a hydrogen atom, an alkoxyl group, or —O— (B—O) n—R ′; , R ′ each represents a hydrogen atom or an optionally substituted alkyl group. B represents an alkylene group which may be substituted, and n represents an integer of 1 to 4.

  In the general formula [A], L is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Specifically, groups such as methylene, ethylene, trimethylene and propylene are preferred examples. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, and an ammonio group that may be alkyl-substituted, and preferred examples include a carboxyl group, a sulfo group, a phosphine group, and a hydroxyl group. A represents a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, or an amino group, an ammonio group, a carbamoyl group, or a sulfamoyl group, each of which may be alkyl-substituted. Preferred examples include a carbamoyl group which may be substituted with a group or an alkyl group. As examples of -LA, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group can be mentioned as preferred examples. The group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, phosphonoethyl group can be mentioned as particularly preferred examples. R is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, particularly preferably having 1 to 5 carbon atoms. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an amino group, an ammonio group, a carbamoyl group, a sulfamoyl group, an alkoxyl group, -O- (B -O) n-R 'and the like. B and R ′ are synonymous with those described in the description of A. There may be two or more substituents. Preferred examples of R include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. The group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, phosphonoethyl group can be mentioned as particularly preferred examples. L and R may be linked to form a ring.

  Although the typical compound example is shown below among the compounds represented by general formula [A], this invention is not limited to these compounds.

  It is also preferable to use sulfite as a preservative, and the concentration is preferably 0 to 0.1 mol / L in the color developer. Examples of sulfites that can be used in the present invention include sodium sulfite, potassium sulfite, and ammonium sulfite.

  In the color developer, in addition to the preservative according to the present invention described above, use of the preservative shown below is not limited. Hydroxamic acids, hydrazides, phenols, α-hydroxy ketones, α-amino ketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds And condensed amines. These are disclosed in JP-A 63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63- 58346, 63-43138, 63-146041, 63-44657, 63-44656, U.S. Pat.Nos. 3,615,503, 2,494,903, JP-A 52- No. 143,020, Japanese Patent Publication No. 4,830,496 and the like.

  In addition, various metals described in JP-A-57-44148 and JP-A-57-53749, salicylic acids described in JP-A-59-180588, triethanolamine, and triisopananolamine The alkanolamines described in US Pat. No. 54-3532, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544 and the like may be contained as necessary.

  The color developer used in the present invention is preferably 9.0 or more and 13.5 or less, more preferably 9.5 or more and 12.0 or less, and an alkaline agent and a buffer so that the pH value can be maintained. Agents and optionally acids can be included.

  From the viewpoint of maintaining the pH when the color developing solution is prepared, it is preferable to use the buffer shown below. Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroquinaminomethane salt, lysine salt, and the like can be used. Carbonate, phosphate, tetraborate, and hydroxybenzoate are particularly excellent in buffering ability in a high pH range of pH 10.0 or higher, and even when added to a color developer, they adversely affect photographic performance (capriformation). Etc.) and a preferable buffer from the viewpoint of being inexpensive.

  Exemplary compounds of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate , Sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) And potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

  These buffers are preferably 0.01 to 2 mol, more preferably 0.1 to 0.5 mol, per liter of color developer.

  As the other components, for example, calcium and magnesium precipitation inhibitors and various chelating agents that are also stability improvers can be added to the color developer used in the present invention. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transsirohexasidiaminetetraacetic acid, 1,2-diaminopropan tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid, 1,2 -Dihydroxybenzene-4,6-disulfonic acid and the like It is. These chelating agents may be used in combination of two or more as required. Further, the amount of these chelating agents may be an amount sufficient to sequester metal ions during color developer processing. For example, 0. 1 per liter. It is added so as to be about 1 to 10 g.

  If necessary, an arbitrary development accelerator can be added to the color developer used in the present invention. Examples of the development accelerator include JP-B-37-16088, JP-A-37-5987, JP-A-38-7826, JP-A-44-12380, JP-A-45-9019, and U.S. Pat. No. 3,813,247. Or neo ether compounds represented in the specification, p-phenylenediamine compounds represented in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B 44-30074 Quaternary ammonium salts, U.S. Pat. Nos. 2,494,903, 3,128,182, and 4,230,796, which are described in JP-A-56-156826 and JP-A-52-43429. No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926, and 3,582,346, etc. Amine compounds described in the report or specification, Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, US Pat. No. 3,128,183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and US Pat. Polyalkylene oxide, other 1-phenyl-3-virazolitones or imidazoles represented in each publication or specification such as 3,532,501 can be added as necessary. Their concentration is preferably 0.001 to 0.2 mol, more preferably 0.01 to 0.05 mol, per liter of the color developer.

  In addition to halogen ions, an optional antifoggant can be added to the color developer as required. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Representative examples include nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

  In addition, a fluorescent whitening agent can be used in the color developer used in the present invention, if necessary. As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stilbene sulfonic acid compound, a known or commercially available diaminostilbene-based auto-enhancing agent can be used. As the known bis (triazinylamino) stilbene sulfonic acid compound, for example, compounds described in JP-A-6-329936, JP-A-7-140625, JP-A-10-14049 and the like are preferable. Commercially available compounds are described, for example, in “Dyeing Note”, 9th edition (Colored Dyeing), pages 165 to 168, and among the compounds described therein, Blankophor BSU liq. And Hakkol BRK.

  As other bis (triazinylamino) stilbene sulfonic acid compounds, compounds I-1 to I-48 and JP-A-2001-2001 described in paragraphs [0038] to [0049] of JP-A No. 2001-281823 are disclosed. The compounds II-1 to II-16 described in paragraph Nos. [0050] to [0052] of JP-A-281823 can also be mentioned. The addition amount of the above-described optical brightener is preferably 0.1 to 0.1 mol per liter of color developer.

When bromine ions are contained in the color developing solution, it is preferably 1.0 × 10 ⁻³ mol / liter or less. The color developing solution preferably contains chlorine ions of 3.5 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / liter, but chlorine ions are usually added to the developer as a by-product of development. Since it is released, it may not be necessary to add it to the replenisher.

In the present invention, the color development processing temperature that can be applied in the processing method is preferably 30 to 55 ° C, more preferably 35 to 55 ° C, and more preferably 38 to 45 ° C. The color development processing time is preferably from 5 to 90 seconds, more preferably from 15 to 60 seconds. The replenishment amount is preferably small, but 15 to 600 ml per 1 m ^{2 of} the light-sensitive material is suitable, preferably 15 to 120 ml, particularly preferably 30 to 60 ml. In the present invention, the color development time refers to the time from when the photosensitive material enters the color developer to the next processing step (for example, bleach-fixing solution). When processed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leave the color developer, and the solution is prepared for the next processing step. The total of both the time for transporting outside (so-called crossover time) is called color development time. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less.

  In the present invention, any bleaching agent may be used as the bleaching agent used in the bleaching solution or the bleach-fixing solution. Particularly, an organic complex salt of iron (III) (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid). Aminopolycarboxylic acids such as cyclohexanediaminetetraacetic acid and ethylenediaminedisuccinic acid, complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates Hydrogen peroxide is preferred.

  Of these, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, ethylenediaminedisuccinic acid, and iron (III) complex salt of methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, and phosphonocarboxylic acid may be used to form a ferric ion complex salt in a solution. Moreover, you may use a chelating agent in excess rather than forming a ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount is preferably 0.01 to 1.0 mol / liter, more preferably 0.05 to 0.50 mol / liter.

  In the bleaching solution or the bleach-fixing solution, various compounds can be used as a bleaching accelerator. For example, a compound having a mercapto group or disulfide bond described in Research Disclosure No. 17129 (July 1978), a thiourea compound, or a halide such as iodine or bromine ion is preferable in terms of excellent bleaching power. .

  In addition, the bleaching solution or the bleach-fixing solution may contain a rehalogenating agent such as bromide (for example, potassium bromide), chloride (for example, potassium chloride) or iodide (for example, ammonium iodide). One or more inorganic acids with pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, citric acid, sodium citrate, tartaric acid, succinic acid, maleic acid, glycolic acid Organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

  Fixing agents used in the fixing solution or the bleach-fixing solution are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid Water-soluble silver halide solubilizers such as thioether compounds such as 3,6-dithia-1,8-octanediol and thioureas can be used singly or in combination of two or more. In the present invention, it is preferable to use thiosulfuric acid, particularly ammonium thiosulfate. The amount of the fixing agent per liter is preferably 0.1 to 5.0 mol, more preferably 0.3 to 2.0 mol. The pH range of the bleach-fixing solution or the fixing solution is preferably from 3 to 10, more preferably from 5 to 9.

  In addition, the bleaching solution, the fixing solution, and the bleach-fixing solution may contain various other kinds of fluorescent whitening agents, antifoaming agents or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

  Bleaching solutions, fixing solutions, bleach-fixing solutions are sulphites as preservatives, for example, sodium sulfite, potassium sulfite, ammonium sulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, metabisulfite. Addition of ammonium sulfate or the like is common, but in addition, ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like may be added.

  Furthermore, you may add a buffering agent, a fluorescent whitening agent, a chelating agent, an antifoamer, an antifungal agent, etc. as needed. The ammonium cation concentration in the bleaching solution, the fixing solution, and the bleach-fixing solution is preferably 50 mol% or less with respect to the total cations from the viewpoint of workability, but from the viewpoint of processability, the ammonium cation concentration is 50 mol% or more. It is preferable that there is.

The time required for the bleach-fixing step that can be applied to the method for processing a silver halide color photographic light-sensitive material of the present invention is preferably 90 seconds or less, more preferably 45 seconds or less. The time required for the bleach-fixing step here refers to the time from when the photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the subsequent rinsing or stabilizing solution, and includes the crossover time therebetween. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Also. The temperature of the bleach-fixing solution is preferably 20 to 70 ° C, and desirably 25 to 50 ° C. Further, the replenishment rate of the bleach-fixing solution is preferably 200 ml / m ² or less, and more preferably ^{20ml / m 2 ~100ml / m 2} .

The replenishment rate of the bleaching treatment solution is preferably 200 ml / m ² or less, and more preferably ^{50ml / m 2 ~200ml / m 2} . The total processing time of the bleaching step is preferably 15 seconds to 90 seconds. The time required for the bleaching step here refers to the time from when the photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the rinse or stabilizing solution, and includes the crossover time between them. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Moreover, it is preferable that processing temperature is 25 degreeC-50 degreeC. The replenishment rate of the fixing treatment solution is preferably 600 ml / m ² or less, and more preferably ^{20ml / m 2 ~500ml / m 2} . The total processing time of the fixing process is preferably 15 seconds to 90 seconds. The time required for the fixing process here refers to the time from when the photosensitive material is immersed in the first tank until it exits the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the rinse or stabilizing solution, and includes the crossover time between them. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Moreover, it is preferable that processing temperature is 25 degreeC-50 degreeC.

The development processing apparatus used for processing the silver halide color photographic light-sensitive material of the present invention fixes the light-sensitive material to the belt even if it is a roller transport type that conveys the light-sensitive material sandwiched between rollers arranged in a processing tank. It may be an endless belt system that conveys
From the viewpoint of exhibiting the objective effects of the present invention, it is preferable to use a roller transport type in which the silver halide color photographic light-sensitive material cut into a sheet is conveyed by being sandwiched between rollers.

  In addition, as the processing tank, the processing tank is formed in a slit shape, and the processing liquid is supplied to the processing tank and the photosensitive material is transported, the spraying method of spraying the processing liquid, and the processing liquid is impregnated. A web system using contact with a carrier, a system using a viscous treatment liquid, or the like can also be used. In the case of processing in large quantities, it is normal that the running processing is performed using an automatic processor. In this case, the replenishing amount of the replenisher is preferably as small as possible, and the most preferable processing form in view of environmental suitability is the tablet as a replenishing method. The method described in the published technique 94-16935 is most preferable.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Examples << Preparation of silver halide emulsion >>
[Preparation of silver halide emulsion (B-1)]
While stirring vigorously using a mixing and stirring apparatus described in JP-A-62-160128, a double ion exchange treated ossein gelatin (calcium content 10 ppm) 2% gelatin aqueous solution kept at 40 ° C. Using the jet method, the following (A1 liquid) and (B1 liquid) were simultaneously added over 17 minutes while controlling pAg = 7.3 and pH = 3.0. Subsequently, the following (A2 solution) and (B2 solution) were simultaneously added over 90 minutes while controlling pAg = 8.0 and pH = 5.5. Furthermore, the following (A3 liquid) and (B3 liquid) were simultaneously added over 15 minutes, controlling pAg = 8.0 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled and adjusted using sulfuric acid or an aqueous sodium hydroxide solution.

(A1 solution)
Sodium chloride 3.42g
Potassium bromide 0.021g
Water was added to make up to 200 ml.

(A2 liquid)
Sodium chloride 72.0g
K ₂ [IrCl ₆ ] 4.8 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrBr ₆ ] 3.2 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrCl ₅ (H ₂ O)] 2.9 × 10 ⁻⁷ mol / mol AgX
K ₂ [IrCl ₅ (thiazole)] 1.6 × 10 ⁻⁸ mol / mol AgX
K ₄ Fe (CN) ₆ 8.0 × 10 ⁻⁶ mol / mol AgX
Potassium bromide 0.44g
Water was added to make 420 ml.

(A3 liquid)
Sodium chloride 30.7g
Potassium bromide 0.63g
Water was added to make 180 ml.

(B1 solution)
Silver nitrate 10g
Water was added to make up to 200 ml.

(B2 liquid)
210g silver nitrate
Water was added to make 420 ml.

(B3 liquid)
90g silver nitrate
Water was added to make 180 ml.

  After completion of the addition, a 15% aqueous solution containing 30 g of chemically modified gelatin (modified ratio 95%) in which the amino group is phenylcarbamoylated was added using the method described in JP-A-5-72658, and then desalted. By mixing with an aqueous solution, a silver halide emulsion (B-1) having an average particle size of 0.56 μm was prepared.

[Preparation of silver halide emulsion (G-1)]
In the preparation of the silver halide emulsion (B-1), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl ₅ (H ₂ O)], K ₂ [IrCl] in (A2 liquid) ₅ (thiazole)] and the amount of K ₄ Fe (CN) ₆ were changed to 2.0 times each, and (A1 solution), (A2 solution), (A3 solution), (B1 solution), (B2 solution) The silver halide emulsion (G-1) having an average particle size of 0.55 μm was prepared in the same manner except that the addition time of (B3 solution) was appropriately changed.

[Preparation of silver halide emulsion (GG-1)]
In the preparation of the silver halide emulsion (B-1), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl ₅ (H ₂ O)], K ₂ [IrCl] in (A2 liquid) ₅ (thiazole)] and the amount of K ₄ Fe (CN) ₆ were each changed to 3.8 times, and (A1 solution), (A2 solution), (A3 solution), (B1 solution), (B2 solution) The silver halide emulsion (GG-1) having an average grain size of 0.43 μm was prepared in the same manner except that the addition time of (B3 solution) was appropriately changed.

[Preparation of silver halide emulsion (R-1)]
In the preparation of the silver halide emulsion (B-1), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl ₅ (H ₂ O)], K ₂ [IrCl] in (A2 liquid) ₅ (thiazole)] and K ₄ Fe (CN) ₆ are each changed to 4.5 times, and (A1 solution), (A2 solution), (A3 solution), (B1 solution), (B2 solution) The silver halide emulsion (R-1) having an average grain size of 0.43 μm was prepared in the same manner except that the addition time of (B3 solution) was appropriately changed.

[Preparation of silver halide emulsion (RR-1)]
In the preparation of the silver halide emulsion (B-1), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl ₅ (H ₂ O)], K ₂ [IrCl] in (A2 liquid) ₅ (thiazole)] and K ₄ Fe (CN) ₆ were each changed to 8.0 times, and (A1 solution), (A2 solution), (A3 solution), (B1 solution), (B2 solution) The silver halide emulsion (RR-1) having an average grain size of 0.40 μm was prepared in the same manner except that the addition time of (B3 solution) was appropriately changed.

  In each silver halide emulsion prepared as described above, cubic silver halide grains accounted for 99% or more of the number of silver halide grains.

<Preparation of blue-sensitive silver halide emulsion>
[Preparation of blue-sensitive silver halide emulsion (B-1a)]
To the silver halide emulsion (B-1) prepared above, the following sensitizing dyes BS-1 and BS-2 were added at 60 ° C., pH 5.8, and pAg 7.5, followed by sodium thiosulfate and trifurylphosphine. Selenide and chloroauric acid were sequentially added to perform spectral and chemical sensitization. After the chemical sensitizer is added and optimally ripened, the compounds (S-1), (S-2), and (S-3) are sequentially added to stop the ripening, and the blue-sensitive silver halide emulsion (B -1a) was obtained.

Sodium thiosulfate 3.9 × 10 ⁻⁶ mol / mol AgX
Trifurylphosphine selenide 2.6 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.9 × 10 ⁻⁵ mol / mol AgX
Compound (S-1) 2.0 × 10 ⁻⁴ mol / mol AgX
Compound (S-2) 2.0 × 10 ⁻⁴ mol / mol AgX
Compound (S-3) 2.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-1 5.2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-2 1.3 × 10 ⁻⁴ mol / mol AgX
<< Preparation of green sensitive silver halide emulsion >>
[Preparation of green-sensitive silver halide emulsion (G-1a)]
The following sensitizing dye (GS-1) is added to the silver halide emulsion (G-1) at 60 ° C., pH 5.8, and pAg 7.5, and then sodium thiosulfate, trifurylphosphine selenide and chloride. Gold acid was sequentially added to perform spectral sensitization and chemical sensitization. After the chemical sensitizer was added and optimally ripened, the compound (S-1) was added to stop the ripening to obtain a green sensitive silver halide emulsion (G-1a).

Sensitizing dye: GS-1 5.3 × 10 ⁻⁴ mol / mol AgX
Sodium thiosulfate 3.3 × 10 ⁻⁶ mol / mol AgX
Trifurylphosphine selenide 2.2 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.5 × 10 ⁻⁵ mol / mol AgX
Compound (S-1) 1.5 × 10 ⁻⁴ mol / mol AgX
[Preparation of green-sensitive silver halide emulsion (GG-1a)]
In the preparation of the green-sensitive silver halide emulsion (G-1a), the silver halide emulsion (GG-1) was replaced with the silver halide emulsion (GG-1) prepared above, and sodium thiosulfate, Silver halide accompanying addition of trifurylphosphine selenide, chloroauric acid, and sensitizing dye (GS-1) as the average grain size of silver halide grains is changed from 0.55 μm to 0.43 μm A green-sensitive silver halide emulsion (GG-1a) was prepared in the same manner except that the addition amount per unit surface area was changed in consideration of the increase in grain surface area.

<< Preparation of red-sensitive silver halide emulsion >>
[Preparation of red-sensitive silver halide emulsion (R-1a)]
The following sensitizing dyes (RS-1) and (RS-2) were added to the silver halide emulsion (R-1) at 60 ° C., pH 5.0, and pAg 7.1, followed by sodium thiosulfate, Furylphosphine selenide and chloroauric acid were sequentially added to give spectral and chemical sensitization. After the chemical sensitizer was added and optimally ripened, compound (S-1) was added to stop ripening, and a red-sensitive silver halide emulsion (R-1a) was prepared.

Sodium thiosulfate 7.2 × 10 ⁻⁶ mol / mol AgX
Trifurylphosphine selenide 4.8 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.5 × 10 ⁻⁵ mol / mol AgX
Compound (S-1) 1.2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-1 1.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-2 1.0 × 10 ⁻⁴ mol / mol AgX
[Preparation of red-sensitive silver halide emulsion (RR-1a)]
In the preparation of the red-sensitive silver halide emulsion (R-1a), the silver halide emulsion (RR-1) prepared above was used instead of the silver halide emulsion (R-1), and sodium thiosulfate, The addition amount of furylphosphine selenide, chloroauric acid, sensitizing dye (RS-1) and sensitizing dye (RS-2) was changed from 0.43 μm to 0.40 μm in average grain size of silver halide grains. In consideration of the increase in the surface area of the silver halide grains accompanying the formation of the red-sensitive silver halide emulsion (RR-1a), except that each addition amount was changed so that the addition amount per unit surface area was the same. ) Was prepared.

In the preparation of each red-sensitive silver halide emulsion, 2.0 × 10 ⁻³ mol / mol AgX of SS-1 was added at the end of the preparation.

<< Preparation of silver halide color photographic material >>
[Preparation of Sample 101]
High-density molten polyethylene containing anatase-type titanium oxide dispersed in a content of 15% by mass is laminated on the photosensitive layer coated surface of paper pulp having a basis weight of 180 g / m ² , and the back surface has a high density. A silver halide color photographic light-sensitive material is formed by subjecting a reflective support laminated with polyethylene to corona discharge treatment, and then providing a gelatin subbing layer and further coating each photographic constituent layer having the constitution shown in Tables 1 and 2. Sample 101 was prepared. In addition, the silver halide emulsion described in the table is represented by a value converted to silver.

In addition, a surfactant (SU-2) is used for preparing a coupler dispersion of each layer, and surfactants (SU-1) and (SU-3) are used as coating aids for adjusting the surface tension of each constituent layer. Was added. Moreover, the antifungal agent (F-1) was added to each layer so that the whole quantity might be set to 0.04 g / m < ² >. In addition, hardening agents (H-1), (H-2), dyes (AI-1), (AI-2), (AI-3) and additive-1 were added as appropriate.

  Details of each additive used for preparation of the sample 101 are as follows.

Sol-1: tricresyl phosphate Matting agent 1: SiO ₂ (average particle size: 3.0 μm)

[Production of Sample 102]
Sample 102 was prepared in the same manner as in the preparation of Sample 101 except that the average grain size of the blue-sensitive silver halide emulsion of the first layer (blue-sensitive layer) was changed from 0.56 μm to 0.45 μm.

[Production of Sample 103]
Sample 103 was prepared in the same manner as in the preparation of Sample 102 except that the compound represented by the general formula [1] (Exemplary Compound 1-2) was removed from the first layer (blue sensitive layer).

<Development processing>
A color paper automatic developing machine manufactured by Konica Minolta Photo Imaging Co., Ltd. was remodeled so that the processing conditions were as follows, each of the prepared samples was imagewise exposed, and continuous processing (running) with the combinations shown in Table 3 Treatment) 1 to 10 were performed. The processing was carried out by running the automatic processor for 12 hours a day until it reached 2R. In the present invention, 2R means that a color developer replenisher that is twice the volume of the color developer tank capacity (10.2 L) is replenished.

(Processing conditions)
<Processing process><Processingtemperature><Processingtime><Tankcapacity><Replenishmentamount>
Color development 38.0 ° C. 30 seconds 10.2 L 50 ml / m ²
Bleach fixing 38.0 ° C. 30 seconds 10.0 L 37 ml / m ²
Stabilization-1 38.0 ° C 24 seconds 8.0L-
Stabilization-2 38.0 ° C 24 seconds 8.3L-
Stabilization-3 38.0 ° C 24 seconds 8.6L-
Stabilization-4 38.0 ° C 24 seconds 9.0L 150ml / m ²
Drying 60 to 80 ° C. 30 seconds The stabilization process was a multi-stage countercurrent system of stabilization-4 → stabilization-3 → stabilization-2 → stabilization-1.

(Preparation of each treatment solution)
<Color developer: per liter>
Tank liquid Replenisher Diethylene glycol 10.0 g 10.0 g
Polyethylene glycol (average molecular weight 4000) 6.0 g 6.0 g
p-Toluenesulfonic acid 10.0 g 10.0 g
Potassium chloride 4.0 g −
Diethylenetriaminepentaacetic acid 6.0 g 6.0 g
Bis (triazinylamino) stilbene fluorescent whitening agent 1.0 g 1.0 g
N, N-bis (sulfoethyl) hydroxylamine 5.0 g 11.0 g
Lithium hydroxide-3.5g
Potassium carbonate 14.0g 14.0g
Sodium carbonate 10.0g 10.0g
4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline 2/3 sulfate 6.0 g 12.0 g
1-octane sodium sulfonate 1.0 g 1.0 g
pH 10.00 12.10
Water was added to 1 L, and the pH was adjusted with potassium hydroxide solution, sodium hydroxide solution or sulfuric acid.

<Bleach fixer: per liter>
Tank liquid Replenisher Ferric ammonium tetraacetate 0.20 mol 0.37 mol
Ammonium thiosulfate 0.54 mol 1.0 mol
Ammonium sulfite 0.15 mol 0.25 mol
Succinic acid 10.0g 18.0g
N-lauroyl sarcosine sodium 1.5g 1.5g
Nitric acid (67%) 10.0 g 16.0 g
pH 6.0 4.8
Water was added to 1 L, and the pH was adjusted with aqueous ammonia or sulfuric acid.

<Stabilizing liquid per 1: 1 L>
Tank liquid = replenisher 1-hydroxyethylidene-1,1-diphosphonic acid tetrasodium 2.0 g
Ethylenediaminetetraacetic acid disodium 2.0g
o-Phenylphenol 0.1g
Bis (triazinylamino) stilbene fluorescent whitening agent 1.0 g
Sodium sulfite 4.0mmol
1-octane sodium sulfonate 0.2g
pH 7.5
Water was added to 1 L, and the pH was adjusted using an aqueous ammonia solution or sulfuric acid.

<Stabilizing liquid 2-8: per 1 L>
In the preparation of the stabilizing solution 1, the addition amount of the bis (triazinylamino) stilbene fluorescent whitening agent is appropriately adjusted so that b ^* of the white background after the development processing becomes the value described in Table 3, Further, stabilizing solutions 2 to 8 were prepared in the same manner except that Exemplified Compound I-38 was added in the amount shown in Table 3 as a sulfinic acid derivative. The white background after the development treatment was measured using a color analyzer (CMS-1200 manufactured by Murakami Color Co., Ltd.).

<Evaluation of formed image>
[Evaluation of hue unevenness on white background]
For each of the continuous treatments 1 to 10, each processing solution after development to 2R was used to develop 100 L-size samples in an unexposed state, and then between the 100 samples. The maximum fluctuation value (ΔDb) of the blue reflection density was measured, and this was used as a measure of hue unevenness on a white background.

[Evaluation of light resistance of yellow images under high temperature and high humidity]
Each sample was exposed to a yellow flower image (blue reflection density of about 1.0) and developed in the same manner, and then each yellow flower image (blue reflection density of about 1.0) was prepared at 70 ° C. In a 60% RH environment, irradiation was continued for 14 days using a fade-O-meter with an illuminance of 15 klux.

  Next, the reduced density width (ΔDY) of the yellow flower image part before and after the irradiation was measured, and this was used as a measure of the light resistance of the yellow image.

  The results obtained as described above are shown in Table 3.

As is clear from the results shown in Table 3, a sample in which the chromaticity of the unexposed portion after the development processing is in the range of 91 ≦ L ^* ≦ 97 and −8.0 ≦ b ^* ≦ −3.5, An image formed by treating with a stabilizing solution containing the sulfinic acid derivative represented by the general formula (I) in a range of 2.0 mmol / L to 30.0 mmol / L is uneven in hue on a white background. It was confirmed that even when the formed yellow image was irradiated with light for a long time, it had excellent light resistance. Further, it was confirmed that the black images formed by the continuous treatments 4 to 9 were able to reproduce a preferable black color without causing bluing.

Reference Example <Preparation of silver halide color photographic material>
In the preparation of the sample 101 described in Example 1, the compound represented by the general formula [II] (Exemplary Compound II) as the average grain size and additional additive of the blue-sensitive silver halide emulsion of the first layer (blue-sensitive layer) Reference samples A to C were prepared in the same manner except that the presence or absence of addition of -36) was changed as shown in Table 4.

<Development processing>
The added amount of the bis (triazinylamino) stilbene fluorescent brightening agent is adjusted as appropriate so that the prepared reference samples A to C and b ^* of the white background after the development processing have the values shown in Table 4. Further, continuous processing 11 to 15 was performed in the same manner as in the development processing described in Example 1 except that the stabilizing solution added with the amount of Exemplified Compound I-38 described in Table 4 as a sulfinic acid derivative was used. Samples 11 to 15 were obtained.

  Next, for each of the image samples, evaluation of light resistance of the yellow image under white hue unevenness and high temperature and high humidity was performed in the same manner as described in Example 1, and the obtained results are shown in Table 4.

As is apparent from the results shown in Table 4, the chromaticity of the unexposed portion after the development processing, which is a preferred embodiment of the present invention, is 91 ≦ L ^* ≦ 97, −8.0 ≦ b ^* ≦ −3.5. In the case of a sample containing the compound represented by the general formula (II), the image formed by continuous processing, particularly, the hue unevenness of the white background is reduced and the light resistance of the yellow image is also synergistic. It can be seen that there has been a general improvement. In particular, it can be seen that the effect is further exhibited by using a treatment step including a treatment solution containing a sulfinic acid derivative represented by the general formula (I) in the stabilization solution.

Claims (1)

A silver halide color photographic light-sensitive material for developing an exposed silver halide color photographic light-sensitive material through at least a color developing step, a bleach-fixing step or a processing step comprising a bleaching step and a fixing step, and a stabilization step. In the processing method, the chromaticity (L ^* , b ^* ) of the unexposed portion of the silver halide color photographic light-sensitive material after the development processing is 91 ≦ L ^* ≦ 97, −8.0 ≦ b ^* ≦ -3. 5 and the stabilizing solution constituting the stabilizing step contains a sulfinic acid derivative represented by the following general formula (I) in an amount of 2.0 mmol / L or more and 30.0 mmol / L or less. A method for processing a silver halide color light-sensitive material.
Formula (I)
RSO ₂ M
[Wherein, R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group. M represents a hydrogen atom, an alkali metal atom, an ammonium group or a quaternary amine. ]