JP2006227256A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a processing method for a silver halide color photographic sensitive material excellent in development stability, white background stability, and uneven processing resistance in continuous processing. <P>SOLUTION: In the processing method for a silver halide color photographic sensitive material, an exposed silver halide color photographic sensitive material is continuously processed through processing steps including at least a color developing step, a blix step or a bleaching step and a fixing step, and a stabilizing step while replenishing each replenisher according to the process amount of the silver halide color photographic sensitive material. A replenishing amount of the replenisher is set according to the discriminated kind of the silver halide color photographic sensitive material, and a stabilizing solution for the stabilizing step contains a sulfinic acid derivative represented by the formula (I): RSO<SB>2</SB>M. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for processing a silver halide color photographic light-sensitive material having improved development stability, white background stability and processing unevenness resistance in continuous processing.

  Usually, a method for developing a dye image by developing a silver halide color photographic light-sensitive material (hereinafter also referred to as a light-sensitive material) is to perform image-wise exposure, then color development with a color developer, After the desilvering process and the fixing process for removing the silver image that is no longer needed, the dye image formed is processed by a stabilization process for stabilizing the dye image.

  In the color photographic market, a silver halide color photographic light-sensitive material that has already been photographed, for example, a color film is developed in a developing place, and the resulting color image is printed on color photographic paper (color paper) to obtain a color print. A so-called color negative / positive system is usually used. As a recent trend seen in the color photographic market, the development bases are decentralized. Specifically, color film is collected from storefronts such as photo shops, and development processing and color print creation are carried out at large labs. From a centralized large-scale development system that delivers finished color prints to customers via a photo shop, the customer's color film received at the store is developed using a minilab machine, and color prints are created immediately on the spot. In addition to the fact that it has undergone a major change to the over-the-counter development processing system that is handed over, in addition to the expansion of the use of digital photographic images, that is, with the advent of digital minilabs that handle photographic images as digital, the captured images of the color film that has been taken are converted into electronic images Is a print service through electronic images, optical recording, magnetic recording, magneto-optical recording, semiconductor elements Momentum of development of the various image media, such as recording is becoming noticeable.

  On the other hand, as the types of color paper, various types of color paper are offered to the market by each color paper manufacturer depending on the required image characteristics, but each color paper is used depending on the intended characteristics. The amount of silver halide, developability, and gradation characteristics are different. If you use a minilab machine etc. in a mixed state with color papers with different characteristics depending on the application, if you replenish a certain amount according to the processing area only with processing area information, development will continue as the continuous processing progresses It has been found that fluctuations in sex, white background fluctuations, and image unevenness are likely to occur. In particular, when processing silver halide color photographic light-sensitive materials for professional use, such as weddings, adult ceremonies, and Shichigosan, where stable and high-quality quality is required, the above-mentioned fluctuations in characteristics are fatal. Problem.

As a method for improving the stability under the continuous processing conditions as described above, for example, a development processing apparatus is disclosed in which both the standard development processing and the rapid development processing are variable (see, for example, Patent Document 1). However, only by changing the development processing time as disclosed in Patent Document 1, it is difficult to cope with the case where the development characteristics of the processing liquid fluctuate, resulting in fluctuations in the processing liquid composition, and stable development characteristics are sufficient. Could not be maintained. In addition, when trying to cope with extremely shortened processing time, it causes a decrease in developability and an increase in noise, and satisfactory finish performance cannot be obtained even with digital image processing. It is. On the other hand, a color image forming method is disclosed in which the type of color negative film for photographing is determined, and the processing time and the replenishment amount of the processing liquid are controlled according to the type information (see, for example, Patent Document 2). In this method, both the processing time and the replenishment amount of the processing liquid are controlled depending on the type of color negative film to be processed. However, there is no mention of the color paper having the above-mentioned problems, and continuous processing is also possible. There is no suggestion about the white background variability and processing unevenness of the color paper and the description about the solution.
Japanese Patent Laid-Open No. 10-309831 JP 2001-209159 A

  The present invention has been made in view of the above problems, and its object is to provide a method for processing a silver halide color photographic material excellent in development stability, white background stability and processing unevenness resistance in continuous processing. is there.

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

(Claim 1)
Processing amount of the silver halide color photographic light-sensitive material at least in the processing step 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 processing method of a silver halide color photographic light-sensitive material that is continuously processed while replenishing each replenisher according to the above, the replenishment amount of the replenisher determines the type of the silver halide color photographic light-sensitive material, A silver halide color characterized in that the replenishing amount is independently set according to each of the above and the stabilizing solution constituting the stabilizing step contains a sulfinic acid derivative represented by the following general formula (I) Method for processing photographic 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. ]
(Claim 2)
The silver halide color photographic light-sensitive material according to claim 1, wherein the content of the sulfinic acid derivative represented by the general formula (I) is 2.0 mmol / L or more and 30.0 mmol / L or less. Processing method.

(Claim 3)
The silver halide color photographic light-sensitive material is a color paper, and the stabilization step is composed of two or more stabilization tanks, and the processing time per one tank of the stabilization tank is 8.0 seconds or more, 3. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the processing time is 26.0 seconds or less.

  According to the present invention, it is possible to provide a method for processing a silver halide color photographic material excellent in development stability, white background stability and processing unevenness resistance in continuous processing.

  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 processing method of the silver halide color photographic light-sensitive material that is continuously processed while replenishing each replenisher according to the processing amount of the silver halide color photographic light-sensitive material, the replenishment amount of the replenisher is: The type of the silver halide color photographic light-sensitive material is discriminated, the replenishment amount is independently set according to the type, and the stabilizing solution constituting the stabilizing step is represented by the general formula (I). By developing a method for processing a silver halide color photographic light-sensitive material characterized by containing a sulfinic acid derivative, development stability, white background stability and processing unevenness resistance in continuous processing It found to be able to realize a processing method excellent silver halide color photographic light-sensitive material, a completed the invention.

  Details of the present invention will be described below.

  First, each processing step in the processing method (hereinafter also simply referred to as processing method) of the silver halide color photographic light-sensitive material of the present invention and the replenishment method of the replenisher will be described.

  In the processing method of the present invention, at least a color developing step, a bleach-fixing step or a bleaching step and a fixing step, and a stabilizing step, and a replenisher according to the processing amount of the silver halide color photographic light-sensitive material. In the processing step of continuously processing while replenishing, the type of silver halide color photographic light-sensitive material to be processed can be discriminated, and the replenisher can be replenished by setting the replenishment amount independently for each type. One of the features.

  In such a continuous processing system using a replenisher, the color developing agent is consumed by the developing process, the pH changes, or the activity of the developing solution by bromide ions and various inhibitors eluted from the silver halide color photographic light-sensitive material. In order to always maintain constant processing conditions, in order to compensate for the decrease in bleaching, bleaching ability due to consumption of bleaching agent, fixing agent, reduction in fixing ability, or concentration of processing solution due to evaporation of moisture etc. Processing is performed while replenishing each replenisher according to the processing amount of the silver halide color photographic light-sensitive material.

  However, in the method of performing replenishment according to the conventional processing amount, that is, the processing area of the silver halide color photographic light-sensitive material, when simultaneously processing silver halide color photographic light-sensitive materials having various characteristics, It has been found that it is difficult to maintain a stable treatment solution composition under the same replenishment conditions.

  For example, when the following requirements constituting the silver halide color photographic light-sensitive material that are continuously processed at the same time are different, the influence appears.

1) When the total amount of silver halide contained in the silver halide color photographic material is different,
2) When the halogen composition of the contained silver halide emulsion is different,
3) If the developability (consumption of color developing agent) of the silver halide emulsion is different,
4) When halogens eluted from silver halide color photographic light-sensitive materials differ in the amount of inhibitor In the present invention, in order to maintain a more stable processing solution composition and processing characteristics in consideration of the above situation, halogens to be processed respectively. One feature is that continuous processing is performed by setting the optimum replenisher replenishment amount according to the processing characteristics (processing agent consumption, dissolved mass, etc.) of the silver halide color light-sensitive material.

  An automatic developing machine for color paper that can be applied to the present invention will be described below.

  FIG. 1 is an overall configuration diagram illustrating an example of an automatic developing machine for color paper in which an automatic developing machine and a printing machine for color paper are integrated.

  In FIG. 1, a magazine M in which color paper, which is an unexposed silver halide color photographic light-sensitive material, is stored in a roll shape is set in the lower left portion of the photographic printing machine B of the automatic developing machine AP for color paper. The color paper p drawn out from the magazine is cut into a predetermined size via the feed roller R1 and the cutter unit Ct to form a sheet-like color paper p. The sheet-like color paper p is conveyed by the belt conveying means Be, and the image of the original image O is exposed by the light source and the lens L in the exposure unit E. The exposed sheet-like color paper p is further transported by a plurality of pairs of feed rollers R2, R3, and R4, and is introduced into the automatic machine AP. In the self-acting machine AP, the sheet-like color paper p is in the color developing tank 1A, the bleach-fixing tank 1B, the stabilizing tanks 1C, 1D, 1E, and 1F, which are processing liquid tanks (substantially stabilizing the structure of four tanks). The liquid tank 1) is sequentially conveyed by a roller conveying means (reference symbol pear), and is subjected to color development processing, bleach-fixing processing, and stabilization processing, respectively. The sheet-like color paper p that has been subjected to the above processes is dried in the drying unit 6 and discharged outside the apparatus.

  In the processing liquid tanks of the color developing tank 1A, the bleach-fixing tank 1B, and the stabilizing tank 1F, dissolution tanks 2A, 2B, 2F, circulation tanks 2C, 2D, 2E and solid processing agents for preparing the replenishers are prepared. 3A, 3B and 3F are provided. A replenishing water tank 4 supplies replenishing water to the color developing tank 1A and the stabilizing tank 1F.

  In the present invention, an optimum processing solution replenishment amount is set by a prior processing test according to the characteristics of each silver halide color light-sensitive material, and the setting information is registered in the storage unit of the automatic processor. Next, an identification display (for example, a bar code or an IC chip) corresponding to the silver halide color photographic material to be stored is attached to the magazine M that stores each silver halide color photographic material, and a predetermined magazine storage unit When set, the control information of the automatic processor is read according to the identification information and the replenisher addition pumps provided in the dissolution tanks 2A, 2B, 2E, and 2F are controlled by the control unit. A replenisher optimal for the silver halide color photographic material to be used is replenished according to the processing area. Similarly, when processing different types of silver halide color photographic light-sensitive materials, the magazine M that contains the silver halide color photographic light-sensitive materials is also compatible with the silver halide color photographic light-sensitive materials to be stored. In the same manner, optimal replenishment is performed.

  In the transport of color paper automatic developing machines, the development process is performed after the color paper is cut to the final size (sheet type transport system) and the roll-shaped silver halide color photographic light-sensitive material. There is a method of cutting to the final size (cine type conveyance method). The cine type conveyance method is preferably a sheet type conveyance method because a photosensitive material of about 2 mm is wasted between images.

In the present invention, from the viewpoint of realizing more stable continuous processing, it is preferable that the area (opening area) where the liquid contacts the air in the processing tank and the replenisher tank is as small as possible. For example, when the opening ratio is a value obtained by dividing the opening area (cm ² ) by the liquid tank (cm ³ ) in the tank, the opening ratio is preferably 0.08 (cm ⁻¹ ) or less, more preferably 0.01 ( cm ⁻¹ ) or less.

  In order to reduce the area in contact with air, it is preferable to provide solid or liquid air non-contact means floating on the liquid surface in the treatment tank and the replenishment tank. Specifically, it is preferable to cover a plastic float or the like on a liquid surface or a liquid that does not mix with the processing liquid and does not cause a chemical reaction. As examples of the liquid, liquid paraffin, liquid saturated hydrocarbon, and the like can be used.

  In the present invention, in order to prevent the processing solution in the previous tank from being mixed into the next tank when the photosensitive material is transported, a structure of a crossover rack provided with a mixing prevention plate is preferable. Each processing solution according to the present invention is preferably subjected to so-called evaporation correction in which water corresponding to the evaporated amount of the processing solution is supplied, and particularly preferably applied to a color developer or a bleach-fixing solution.

  The processing tank of the automatic developing machine described above may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a squeegee, a nitrogen stirrer, an air stirrer, and the like as necessary.

  In the processing method of the silver halide color photographic light-sensitive material of the present invention, the exposed silver halide color photographic light-sensitive material is subjected to a bleaching step (bleaching solution), a fixing step (following the color developing step (color developing solution)). Fixing solution) or bleach-fixing step (bleaching fixing solution), stabilizing step (stabilizing solution), and processing, depending on the type of silver halide color photographic material, replenishing color developer, replenishing bleaching solution The replenishment fixing solution, or the replenishment bleach-fixing solution, the replenishment stabilizing solution, and the like are continuously developed while being replenished under respective replenishment conditions set.

  In the treatment method of the present invention, it is one of the characteristics that the stabilizing solution constituting the stabilizing step contains the sulfinic acid derivative represented by the general formula (I). It is preferable to contain 0.0 mmol / L or more and 30.0 mmol / L or less, more preferably 3.0 mmol / L or more and 25.0 mmol / L or less, and particularly preferably 5.0 mmol / L or more and 20.0 mmol. / L or less. By adding 2.0 mmol / L or more of the sulfinic acid derivative represented by the general formula (I) to the stabilizing solution, white background stability in continuous processing in which replenishment is performed according to the type of silver halide color photographic light-sensitive material. In addition, it is possible to dramatically improve the processing unevenness resistance. Moreover, if it is 30.0 mmol / L or less, there will be no generation | occurrence | production of precipitation in a stabilization liquid, and it 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.

  In this invention, it is preferable that a stabilization process is comprised from the stabilization tank of 2 or more tanks, and the processing time which each stabilization tank requires is 8.0 second or more and 26.0 seconds or less.

  The time required for the stabilization processing step in the present invention means that in each stabilization bath, the silver halide color photographic light-sensitive material is immersed in the stabilization bath in each stabilization bath. , Meaning the time to get out of the stabilizing solution in the stabilization tank.

The replenishment amount is set according to specific conditions according to the type of the silver halide color photographic material to be processed in the present invention, but a specific preferable replenishment amount is from the silver halide color photographic light-sensitive material, the pre-bath per unit area. 0.5 to 50 times the carry-in amount is more preferable, and more preferably 3 to 40 times. 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 the organic antifoggant 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 set according to the type of silver halide color light-sensitive material to be processed in the present invention, but is generally 15 to 600 ml per 1 m ^{2 of} light-sensitive material, preferably 15 to 120 ml, particularly Preferably it is 30-60 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 from 0.1 to 5.0 mol, more preferably from 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.

The replenishing amount of the bleach-fixing solution is set to specific conditions according to the type of the silver halide color photographic material to be processed in the present invention, but is generally preferably 200 ml / m ² or less, more preferably 20 ml / m. ^{2 to} 100 ml / m ² .

The replenishing amount of the bleaching solution is set to specific conditions depending on the type of silver halide color light-sensitive material to be processed in the present invention, but is generally preferably 200 ml / m ² or less, more preferably 50 ml / m ² to 200 ml / 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 replenishing amount of the fixing processing solution is set to specific conditions depending on the type of the silver halide color light-sensitive material to be processed in the present invention, but is preferably about 600 ml / m ² or less, more preferably 20 ml / m ² to 500 ml / 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 the processing of the silver halide color photographic light-sensitive material of the present invention may be a roller transport type that conveys the light-sensitive material sandwiched between rollers arranged in the processing tank as described above. It may be an endless belt system that fixes and conveys the photosensitive material, but from the standpoint of fully achieving the object and effects of the present invention, the silver halide color photographic photosensitive material cut into a sheet is conveyed between rollers. It is preferable to be a roller transport type.

  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. When processing in large quantities, it is normal to use an automatic processor for running processing. However, the smaller the replenisher replenishing amount, the better. The treatment agent is added in the form, and the method described in the published technique 94-16935 is most preferable.

    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.

  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 grain size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 5.0 μm, more preferably 0.8, considering other photographic performance such as rapid processability and sensitivity. It is in the range of 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 of 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.

  The silver halide emulsion according to the present invention is known for the purpose of preventing fogging that occurs during the preparation process of a silver halide photographic light-sensitive material, reducing fluctuations in performance during storage, and preventing fogging that occurs 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 Preferred are 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. The compounds described in Nos. 29472, 2003-10482, 2002-31557 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 of 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 photographic 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 of the present invention because the 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 of 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 of the present invention, any coupler capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent. Although a compound can also be used, particularly representative couplers include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, and a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm. And those known as cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

  As a cyan dye-forming coupler that can be preferably used in the silver halide color photographic light-sensitive material of the present invention, general formulas (CI) and (C-II) described in JP-A-4-114154, page 5, lower left column. The coupler represented by these 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 that can be preferably used in the silver halide color photographic light-sensitive material of the present invention, general formulas (M-I) and (M-II) described in JP-A-4-114154, page 4, right upper column. The coupler represented by these 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 of the present invention, it is usually a water-insoluble high boiling organic solvent having a boiling point of 150 ° C. or higher. In addition, if necessary, it 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, the compound represented by the general formula [I] described in JP-A-1-196049 and the compound 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 of 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 it is added to the silver halide emulsion layer. 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 of the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of the 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 of 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, and proteins other than gelatin. Hydrophilic colloids such as 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 these binder hardeners, vinylsulfone type hardeners, chlorotriazine type hardeners, and carboxyl group active hardeners are preferably used alone or in combination. It is preferable to use compounds described in JP-A Nos. 61-249054 and 61-245153. Further, in order to prevent the growth of soot and bacteria that adversely affect photographic performance and image storage stability, 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 improve the physical properties of the surface of the photosensitive material or 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 light-sensitive material of 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 ² More preferably, it is as follows. 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 of the present invention may have at least one yellow image forming layer, magenta image forming layer, and cyan image forming layer, but a plurality of color image forming layers as necessary. A unit may be formed by.

  As the support used for the silver halide color photographic light-sensitive material of the present invention, any material may be used, paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet Polypropylene which may contain a white pigment, polyethylene terephthalate support, baryta paper or 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 of the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and directly or undercoat layer (adhesiveness of the support surface, antistatic properties). , One or more subbing layers for improving dimensional stability, rub resistance, hardness, antihalation properties, friction 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 material of the present invention, an image recorded on the negative is optically imaged on the silver halide photographic material to be printed. The image may be printed, or once converted into digital information, the image is formed on a CRT (cathode ray tube), and the image is formed on a 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.

  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.

<< 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 rate of 95%) in which the amino group is phenylcarbamoylated is 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 0.59 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]
In the preparation of the sample 101, the addition amount of the photosensitive silver halide emulsion used in the first layer (blue-sensitive layer), the third layer (green-sensitive layer) and the fifth layer (red-sensitive layer) was 1. Sample 102 was produced in the same manner except that the ratio was changed to 10 times.

[Production of Sample 103]
In the preparation of the sample 101, the addition amount of the photosensitive silver halide emulsion used in the first layer (blue-sensitive layer), the third layer (green-sensitive layer) and the fifth layer (red-sensitive layer) was 1. Sample 103 was produced in the same manner except that the magnification was changed to 25 times.

<< Preparation of each treatment liquid >>
<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 0.2g
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: per 1 L>
Stabilizing liquid 2 was prepared in the same manner as in the preparation of stabilizing liquid 1, except that 5.0 mmol of Exemplified Compound I-38 was added as a sulfinic acid derivative.

<Stabilizing liquid 3-8: per 1 L>
In the preparation of the stabilizing solution 2, the amount of sulfinic acid derivative (Exemplary Compound I-38) added was changed to 1.0 mmol, 2.5 mmol, 8.0 mmol, 16.0 mmol, 25.0 mmol, and 35.0 mmol, respectively. Stabilized liquids 3 to 8 were prepared in the same manner as described above.

《Continuous processing》
[Continuous processing 1]
The color paper automatic processor shown in FIG. 1 was modified so that the processing conditions were as follows, and the prepared sample 101 was subjected to imagewise exposure to perform continuous processing (running processing). In the treatment, the stabilizing solution 1 was used as the stabilizing solution, and the sample 101 was treated for 9 m ² per day and continuously processed until 2R was reached. 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.

[Continuous processing 2]
In continuous processing 1 (stabilizing solution 1), the samples to be continuously processed are changed to samples 101, 102, and 103 having different total silver coating amounts, and the processing amount per day is 3 m ² for sample 101 and 3 m for sample 102. ² , Continuous treatment 2 was performed in the same manner except that the sample 103 was changed to 3 m ² . However, the replenishment condition of the replenisher was the same as that of the continuous process 1 and was performed under a constant replenishment condition (this is referred to as replenishment method: quantitative replenishment).

[Continuous processing 3]
In the continuous treatment 2 (stabilized solution 1), the continuous treatment 3 was performed in the same manner except that the stabilized solution 1 was replaced with the stabilized solution 2 containing 5.0 mmol / L of the sulfinic acid derivative. However, the replenishment conditions of the replenisher were the same as those in the continuous process 1 and were performed under constant replenishment conditions.

[Continuous processing 4]
In the continuous process 2 (stabilized liquid 1), each time the sample 101, the sample 102, and the sample 103 are processed, the continuous process 4 is performed in the same manner except that the continuous process is performed while changing to the following replenisher amount. went. The amount of replenisher was changed by mounting an IC chip with replenishment amount data on the cassette containing each sample, and reading the information on the IC chip each time the cassette was changed, and controlling the replenishment amount as follows (this Replenishment method: called variable replenishment).

Color developer replenishment amount Bleach fixer replenishment amount Stabilizer replenishment amount (Stabilization-4)
Sample ^{101 50ml / m 2 37ml / m} 2 150ml / m 2
Sample 102 53 ml / m ² 39 ml / m ² 155 ml / m ²
Sample 103 60 ml / m ² 44 ml / m ² 175 ml / m ²
[Continuous treatment 5-11]
In the above-mentioned continuous treatment 4 (stabilizing solution 1), instead of the stabilizing solution 1, each of the continuous treatments 5 to 5 was carried out in the same manner except that they were changed to stabilizing solutions 2 to 8 containing 5.0 mmol / L of the sulfinic acid derivative. 11 was done. The replenishment conditions for the replenisher were the same as in the continuous process 4, with the amount of replenisher set for each sample type.

[Continuous processing 12-14]
In the above-described continuous treatment 5 (stabilization liquid 2), the treatment time per layer of each stabilization tank in the stabilization step was changed from 24 seconds to 5 seconds, 12 seconds, and 32 seconds, respectively. Continuous treatment 12-14 was performed.

<Evaluation of continuous processing characteristics>
[Evaluation of continuous treatment stability]
In each continuous processing, the sample 101 subjected to the wedge exposure is processed at the start of the continuous processing and at the end of the continuous processing of 2R, and the density of the obtained wedge-shaped color image is set to X-Rite 938 (reflection type spectrophotometric / densitometer). X-Rite Co.) was used to measure the status A reflection density, and a characteristic curve consisting of horizontal axis: exposure amount (Log E) and vertical axis: color density (D) was prepared. Next, the point of yellow density 1.0 in the characteristic curve is connected to the density 2.0 by a straight line, the slope γ of this straight line is obtained, and when γ of the sample processed at the start of continuous processing is 1.00, 2R The relative γ of the sample treated at the end of the continuous treatment was determined and used as a measure of the stability of the continuous treatment. The closer the numerical value is to 1.00, the more the initial development characteristics are maintained even after continuous processing and the stability is excellent.

[Evaluation of stability on white background]
In each continuous processing, at the start of the continuous processing and at the end of the continuous processing of 2R, the unexposed sample 101 is processed, and the chromaticity of the white background portion is determined using a color analyzer (CMS-1200 manufactured by Murakami Color Co., Ltd.), b ^* The difference Δb ^* between the b ₁ ^* of the sample at the start of the continuous treatment and the b ₂ ^* of the sample at the end of the 2R continuous treatment was determined, and this was used as a measure of the stability of the white background. The smaller Δb *, the smaller the white background fluctuation in the continuous processing, and the better the white background stability.

[Evaluation of image unevenness resistance]
At the end of the 2R continuous processing, the exposure amount was adjusted so that each of the blue, green, and red densities was 0.8, and the sample 101 subjected to the entire solid exposure was processed. After visually observing the presence or absence of image unevenness on the monitor and ranking according to the following evaluation criteria, the average value was obtained. The higher the average value, the better the image unevenness resistance.

5: An image having no density unevenness at all in the image and an extremely high density uniformity 4: An image having almost no density unevenness in the image and having a high density uniformity 3: One of the images Although extremely weak density unevenness is observed in the area, it is a quality that is practically acceptable. 2: A weak density unevenness is recognized in the image and is a quality that is problematic in practice. 1: Strong density unevenness on the entire surface of the image. Table 3 shows the evaluation results obtained as described above.

  As is clear from the results shown in Table 3, the type of the sample is determined, the replenishment amount is set independently according to the type, and the sulfinic acid derivative represented by the general formula (I) is contained. It can be seen that by performing the continuous processing using the stabilizing liquid, the continuous processing stability and the white background stability are excellent and the image unevenness resistance is improved as compared with the comparative example. Further, among the treatment methods of the present invention, the addition amount of the sulfinic acid derivative represented by the general formula (I) in the stabilizing solution is in the range of 2.0 mmol / L or more and 30.0 mmol / L or less, or It can be seen that the above characteristics are further improved by setting the treatment time per stabilization tank to 8.0 seconds or more and 26.0 seconds or less. At the level of 35 mmol / L of the sulfinic acid derivative represented by the general formula (I) in the stabilizing liquid, minute precipitation of the sulfinic acid derivative was observed in the stabilizing liquid, and one stabilization tank When the per-time processing time is extended to 32 seconds, there is no characteristic difference from 24 seconds, and only the total processing time is extended, which is not a desirable condition from the viewpoint of rapid processing.

1 is an overall configuration diagram illustrating an example of an automatic developing machine for color paper in which an automatic developing machine and a printing machine for color paper are integrated. FIG.

Explanation of symbols

Automatic developing machine for AP color paper B Photo printing machine C Replenisher part E Exposure part p Sheet-like photographic paper 1A Color developing tank 1B Bleach fixing tank 1C, 1D, 1E, 1F Stabilizing tank (rinse tank)
2A, 2B, 2F Dissolution tank 2C, 2D Circulation tank 3A, 3B, 3F Solid processing agent supply device 4 Replenishment water tank 6 Drying section

Claims (3)

Processing amount of the silver halide color photographic light-sensitive material at least in the processing step 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 processing method of a silver halide color photographic light-sensitive material that is continuously processed while replenishing each replenisher according to the above, the replenishment amount of the replenisher determines the type of the silver halide color photographic light-sensitive material, A silver halide color characterized in that the replenishing amount is independently set according to each of the above and the stabilizing solution constituting the stabilizing step contains a sulfinic acid derivative represented by the following general formula (I) Method for processing photographic 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. ] The silver halide color photographic light-sensitive material according to claim 1, wherein the content of the sulfinic acid derivative represented by the general formula (I) is 2.0 mmol / L or more and 30.0 mmol / L or less. Processing method. The silver halide color photographic light-sensitive material is a color paper, and the stabilization step is composed of two or more stabilization tanks, and the processing time per one tank of the stabilization tank is 8.0 seconds or more, 3. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the processing time is 26.0 seconds or less.

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