JP4149952B2 - Image forming method using silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to an image forming method according to the silver halide photographic color light-sensitive material, particularly relates to an image forming method according to the silver halide photographic color light-sensitive material suitable for color printing, and more particularly can create a large amount of prints in a short time The present invention also relates to an image forming method using a silver halide photographic color light-sensitive material capable of high-quality printing with few print defects.

  In the photo processing service industry, color negatives, reversal light-sensitive materials, and in recent years, color print systems for obtaining color prints from digital cameras and the like have become widespread not only in laboratories specializing in print development processing, but also in photo shops. . The exposure method of this color print system is a digital camera that can obtain color prints from a digital camera from the so-called direct (analog) exposure method, in which the projection light of a film such as a color negative is incident on color paper and the photosensitive material is surface exposed. The mainstream is shifting to a printing apparatus using exposure. Even for images recorded on a film, a digital exposure method has been widely used in which information is photoelectrically read and the information is converted into digital signals and image processing is performed, and then scanning exposure is performed with recording light modulated in accordance with the image data to record an image. It is being done.

  On the other hand, as a color printing method, technologies such as an ink jet method, a sublimation type method, and color xerography have advanced, and are being recognized as a color printing method, such as improving the quality of photographs. Among these, the characteristics of the digital exposure method by laser scanning exposure using color photographic paper are high image quality, high productivity, and high image robustness. It is desired to provide a simpler and cheaper. In particular, if you can quickly perform the process from exposure of color photographic paper to the end of processing, you will be able to return high-quality prints within a few minutes after receiving the digital camera recording media at the store, and the advantages of color printing Sexuality increases more and more.

  Conventionally, studies have been made from various viewpoints so that the process from the exposure of color photographic paper to the end of processing can be performed quickly. For example, as a silver halide emulsion used for color photographic paper, a silver halide emulsion having a high silver chloride content is used because of a demand for rapid processability. A high silver chloride emulsion has a fast development progress, does not generate a development inhibitor such as Br ions or I ions during development processing, and does not accumulate in the developer, and is stable against fluctuations in processing factors. Patent Document 1 discloses a sensitizing dye with little residual color for the purpose of shortening the washing step. Such speeding up is very important because it improves the print productivity per unit time.

  In these color printing systems, the photosensitive material is loaded in a photosensitive material-containing light-shielding magazine while being wound in a roll shape, and is pulled out from the magazine and conveyed during exposure and development. Conventionally, a photosensitive material is exposed to light and developed without being cut in the form of a roll, and is cut into a desired length after the developing process to obtain a print for each sheet. Although paper was produced, it was necessary to form frame information for clearly indicating the boundary for each print, and this portion was wasted, resulting in a decrease in productivity.

  Therefore, recently, the photosensitive material is cut into a size equivalent to one print sheet in advance, and then the light beam modulated according to the image data is deflected in the main scanning direction and printed in the sub-scanning direction orthogonal to the main scanning direction. A color printing system that employs a sheet conveying method that conveys paper and further performs development processing in a sheet state has been put into practical use. However, this transport method has a problem in that vibration occurs due to various factors during transport, and this vibration is transmitted to the exposed portion of the photographic paper, thereby causing uneven exposure. For example, when the leading or trailing edge of the photographic paper passes through the step between the flutter guide that supports the photographic paper and the conveyance guide before the exposure unit in the exposure unit, or the photographic paper moves over the conveyance roller protruding from the flutter guide As a result, vibration is transmitted to the exposed portion of the photographic paper, load fluctuation occurs, and uneven exposure occurs.

  Therefore, in Patent Document 2, a metal roller with little deformation is used for the pair of conveyance rollers, and a special metal hard roller with a rubber layer provided on the surface is used to improve the conveyance performance, and the nip position is protruded. Thus, a good image forming method without exposure unevenness by controlling the vibration of the photosensitive material is disclosed. In this case, the photosensitive material is guided to the exposure position by the transport roller pair and the transport guide, and is nipped by the transport roller pair at two points sandwiching the exposure position in the vicinity of the exposure position, thereby fixing the photographic paper and ensuring flatness. And record images.

  However, when a hard roller with improved exposure unevenness is used in the above-mentioned sheet conveyance method, streak unevenness occurs near the passage of the hard roller when the sub-scanning speed during exposure is increased for the purpose of speeding up. It has been found that it may occur. As a result of extensive studies by the inventor, it was estimated that pressure sensitization was caused by direct damage to the emulsion due to pressure, and various photosensitive materials were tested. It was found that this is not a phenomenon that occurs. Furthermore, it becomes clear that this streak irregularity occurs remarkably when a photosensitive material stored in a high-temperature and low-humidity environment is exposed to light, and changes over time due to the storage history of the photosensitive material and the photosensitive material during roller conveyance. It was found that this phenomenon was caused by damage.

  The storage of the photosensitive material shipped from the factory is preferably refrigerated, but the actual situation is often left in a place that is not refrigerated, and depending on the region, it is often exposed to a high temperature and high humidity environment. As color printing systems are diversifying, including rapid models, sheet-type high-speed conveyance type color printing systems with improved productivity are required to have the same quality as ever.

  Patent Document 1 discloses that an emulsion excellent in pressure resistance can be obtained by spectral sensitization with a specific monomethine dye. There is no discussion of performance changes.

  Patent Document 3 discloses that a specific disulfide compound can improve the stability of changes in photographic performance with respect to temperature fluctuations during exposure. However, these known techniques disclose photographic performance in aging variations of photosensitive materials. There is no discussion about change.

Japanese Patent Laid-Open No. 2002-23295 JP-A-2003-212384 Japanese Patent Laid-Open No. 2001-166411

An object of the present invention is to provide, by the fast and the image forming method high image forming productivity is due to a silver halide color photographic light-sensitive material as possible, the silver halide color photographic light-sensitive material particularly suitable for color printing with a high image quality An image forming method is provided. In particular, it is an object of the present invention to provide an image forming method using a silver halide color photographic light-sensitive material capable of producing a large number of prints in a short time and capable of producing a high quality print with few print defects. Furthermore, it is to provide an image forming method using a silver halide color photographic light-sensitive material with little sensitivity fluctuation during continuous processing.

The inventors of the present invention further improve image quality, speed up output, and increase productivity in silver halide color photographic light-sensitive materials, particularly color photographic paper for laser scanning exposure and an image forming method using the same. To this end, we have intensively studied high-density and high-speed exposure and shortened color development time. However, in such an image forming method, a problem has been revealed that when conventional color photographic paper is used, stripe unevenness may occur in the print. As a result of further analysis, it has been found that this streak unevenness occurs on the image exposure transport roller before exposure, particularly when the photosensitive material is a photosensitive material stored under high temperature and high humidity conditions. Turned out to be high. In order to solve this problem, the present inventors have made various studies, and spectral sensitization using a specific sensitizing dye in a silver halide emulsion used for color photographic paper, or inorganic sulfur or a specific compound. It has been found that the generation of streaks can be eliminated by the inclusion, and the present invention has been achieved.
That is, the means for solving the above problems are the following means.

(1) At least one yellow dye-forming coupler-containing blue-sensitive silver halide emulsion layer, magenta dye-forming green-sensitive silver halide emulsion layer, and cyan dye-forming red-sensitive silver halide emulsion layer, respectively, on the support. An image forming method for forming an image by starting color development after carrying out scanning exposure on a silver halide color photographic light-sensitive material possessed by a pair of conveying rollers for image exposure, The silver halide color photographic light-sensitive material has a sub-scanning conveyance speed of 90 mm / sec or more, the scanning exposure is performed during horizontal conveyance, and the image exposure conveyance roller is provided with a urethane coat containing resin beads on a metal shaft. The silver halide emulsion contained in the blue-sensitive silver halide emulsion layer of the silver halide color photographic material is silver chloride. In Yuritsu 90 mol% or more and a color image forming method, characterized by being spectrally sensitized by at least one dye represented by the following general formula (I).

In general formula (I), X ¹ and X ² each independently represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a nitrogen atom or a carbon atom. Y ¹ represents a furan ring, a pyrrole ring, a thiophene ring, or a benzene ring that may be condensed with another 5- to 6-membered carbon ring or heterocyclic ring or may have a substituent. Y ² represents an atomic group necessary for forming a benzene ring or a 5- to 6-membered unsaturated heterocyclic ring, and has a substituent even if it is condensed with another 5- to 6-membered carbocyclic or heterocyclic ring. You may do it. Note that the bond between two carbon atoms to which Y ¹ and Y ² are condensed may be a single bond or a double bond. One of R ¹ and R ² represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. L ¹ represents a methine group. M ¹ represents a counter ion, and m ¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule.
(2) The color image forming method as described in (1), wherein the dye represented by the general formula (I) is a dye represented by the following general formula (II) or (III).

In the general formula (II), Y ¹¹ represents an oxygen atom, a sulfur atom or N—R ¹³ , and R ¹³ represents a hydrogen atom or an alkyl group. V ¹⁵ and V ¹⁶ each independently represents a hydrogen atom or a monovalent substituent. X ¹¹ and X ¹² each independently represents an oxygen atom or a sulfur atom. One of R ¹¹ and R ¹² represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. V ¹¹ , V ¹² , V ¹³ and V ¹⁴ each independently represents a hydrogen atom or a monovalent substituent. M ¹¹ represents a counter ion, and m ¹¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule.

In the general formula (III), Y ²¹ represents an oxygen atom, a sulfur atom or N—R ²³ , and R ²³ represents a hydrogen atom or an alkyl group. V ²⁵ and V ²⁶ each independently represents a hydrogen atom or a monovalent substituent. X ²¹ and X ²² each independently represent an oxygen atom or a sulfur atom. One of R ²¹ and R ²² represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. V ²¹ , V ²² , V ²³ and V ²⁴ represent a hydrogen atom or a monovalent substituent. M ²¹ represents a counter ion, and m ²¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule.
(3) The color image forming method as described in (1), wherein the dye represented by the general formula (I) is a dye represented by the following general formula (IV).

In the general formula (IV), X ³¹ and X ³² represent an oxygen atom or a sulfur atom. One of R ³¹ and R ³² represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. V ³¹ , V ³² , V ³³ , V ³⁴ , V ³⁵ , V ³⁶ , V ³⁷ and V ³⁸ each independently represent a hydrogen atom or a monovalent substituent, and two adjacent substituents are linked to each other. A condensed ring may be formed. M ³¹ represents a counter ion, m ³¹ is to display the number of 0 or more necessary for neutralizing a charge in the molecule.
(4) At least one yellow dye-forming coupler-containing blue-sensitive silver halide emulsion layer, magenta dye-forming green-sensitive silver halide emulsion layer, and cyan dye-forming red-sensitive silver halide emulsion layer, respectively, on the support. An image forming method for forming an image by starting color development after carrying out scanning exposure on a silver halide color photographic light-sensitive material possessed by a pair of conveying rollers for image exposure, The scanning exposure of the photosensitive material is 90 mm / sec or more, the scanning exposure is performed at the time of horizontal conveyance, and the image exposure conveyance roller is formed by applying a urethane coat containing resin beads on a metal shaft. And a silver halide emulsion contained in the blue-sensitive silver halide emulsion layer of the silver halide color photographic light-sensitive material having a silver chloride content of 90 mol% or more. Color image forming method characterized in that it contains at least one represented by inorganic sulfur or downward following general formula (Z).
General formula (Z)
R ⁴¹ -S-S-R ⁴²
In the general formula (Z), R ⁴¹ and R ⁴² each independently represents an aliphatic group or an aromatic group. Here, R ⁴¹ and R ⁴² may be bonded to each other to form a ring.

The silver halide photographic color light-sensitive material used in the present invention is capable of rapid and highly productive imaging with high image quality, particularly suitable for color printing.
The image forming method using the silver halide photographic color light-sensitive material of the present invention can produce a large amount of prints in a short time and can produce high quality prints with few print defects.

The present invention is described in detail below.
[Image formation method]
First, an image forming method according to the present invention will be described.
The image forming method of the present invention uses a hard roller formed by applying a urethane coat containing a resin bead on a metal shaft to a transport roller for image exposure, a sub-scan transport speed of 90 mm / sec or more, and a horizontal transport. Sometimes color development is started after the scanning exposure is performed. Here, the sub-scan is transport for transporting the photosensitive material in a direction perpendicular to the main scan to be scanned and exposing the photosensitive material in a two-dimensional manner. The image exposure transport roller refers to a driving roller that transports the photosensitive material in the sub-scanning direction, and is paired with a nip roller that applies a clamping force (collectively referred to as a sub-scanning roller pair) to transport the photosensitive material. A hard roller refers to a roller having a metal roller surface with a special coating.
An example of an image forming apparatus that exposes a photosensitive material will be specifically described below.

In the present invention, an image forming apparatus for exposing a photosensitive material is, for example, as shown in FIG.
First, the sub-scanning roller pair will be described.
The sub-scanning roller pair includes an image exposure conveying roller (driving roller) and a nip roller, and indicates 46 and 48 in FIG. The sub-scanning roller (driving roller for applying a driving force to the sheet member) is a hard roller with a special coating, and the nip roller for applying a clamping force is composed of a rubber roller having a predetermined axial rigidity and rubber hardness. Is done.
The drive roller is a hard roller formed by applying a urethane coating process containing resin beads on the surface of the metal shaft. By processing the metal shaft, it is possible not only to prevent deformation of the roller surface and enable high-precision sub-scanning conveyance, but also to keep the roller surface smooth to prevent scratches on the sheet and wear of the nip roller. Can be suppressed. In order to increase the durability of the surface of the drive roller itself, the urethane coat preferably contains resin beads. The resin beads contained in the urethane coat preferably have a bead diameter of 5 to 90 μm, more preferably 5 to 30 μm, and the content ratio is preferably 10 to 40%. In the present invention, the thickness of the urethane coat layer of the driving roller is preferably 20 to 100 μm, more preferably 25 to 50 μm. The minimum coat thickness is determined by the selected bead diameter.
The nip roller is a rubber roller provided with a rubber layer on a metal shaft. In the present invention, the nip roller hardness is preferably A35 to A75 (JIS K 6253), more preferably 45 to 60. When the rubber hardness is reduced, the contact load between the driving roller and the nip roller is increased, resulting in poor conveyance accuracy. When the rubber hardness is increased, the impact of the landing / separation operation of the nip roller is increased, and the conveyance speed is changed. The material is not particularly limited as long as it is a material that can be adjusted to the hardness of the present invention. Examples of the rubber material include EPDM, silicon, NBR, urethane, and the like. The rigidity of the nip roller shaft is preferably set to a strength that suppresses the deformation amount during nip to a predetermined value or less. The amount of deformation is a combination of rubber deformation and roller shaft deflection, preferably 1.5 times or less, more preferably 1.0 times or less the sheet thickness.

  An image forming apparatus 10 illustrated in FIG. 1 includes a scanner 12, an image processing apparatus 13, a printer 14, a processor 15, and a sorter 19. The printer 14 is a recording apparatus that exposes and records a photosensitive material using light beam scanning exposure, and is a cut sheet that is drawn and cut by a predetermined length from a long photosensitive material A wound in a roll shape. A photosensitive material (hereinafter also referred to as a sheet member) is conveyed to the exposure position, while the light beam L modulated in accordance with the image data supplied from the image processing device 13 is deflected in the main scanning direction and the main scanning is performed. The photosensitive material is scanned and conveyed in the sub-scanning direction orthogonal to the direction, and the photosensitive material is scanned and exposed by the light beam L to form an image.

  The printer 14 in the image forming apparatus 10 is connected to the image processing apparatus 13, and the image processing apparatus 13 is connected to the scanner 12. On the other hand, the processor 15 is connected adjacent to the printer 14 so as to receive the exposed photosensitive material carried out from the printer 14. The image forming apparatus 10 includes a control unit (control unit) 34 that controls the overall operation of the image forming apparatus 10. The printer 14 is provided with a plurality of conveyance roller pairs for conveying the sheet member. The sheet body is conveyed by the conveyance roller pair at a preset conveyance speed (hereinafter also referred to as a first conveyance speed).

The scanner 12 photoelectrically reads the projection light of the image photographed on the film with an image sensor such as a CCD sensor, captures the image data (image data signal) of the film, and sends it to the image processing device 13.
The image processing device 13 performs predetermined image processing on the image data and sends it to the printer 14 as image data (exposure conditions) for image recording. The image processing apparatus 13 may be configured to send image data obtained by photographing with a digital still camera or the like to the printer 14.
The processor 15 performs predetermined development processing, drying processing, and the like on the sheet body (photosensitive material) on which the exposed latent image is recorded, and sets the sheet body as a printed image reproduced. Further, the processor 15 is provided with a plurality of conveyance roller pairs for conveying the sheet member. Also in the processor 15, the sheet is conveyed at a preset conveyance speed (hereinafter also referred to as a second conveyance speed) by the conveyance roller pair, and the exposed sheet body is subjected to development processing.
The sorter 19 collects and collects sheets subjected to development processing, drying processing, and the like, for example, for each film.

  The exposure unit 26 is located upstream and downstream in the transport direction so as to sandwich an exposure unit 36 connected to the image processing apparatus 13 and an exposure position r for scanning and exposing the sheet member with the light beam L emitted from the exposure unit 36. Position detection that is provided between a pair of sub-scanning rollers 46 and 48 that conveys the sheet body at a predetermined speed to perform sub-scanning, and is positioned between the exposure position r and the sub-scanning roller pair 46. And a sensor 50.

  The exposure unit 36 is a known light beam scanning device that uses, for example, a light beam such as a laser beam as recording light, and each of red (R) exposure, green (G) exposure, and blue (B) exposure of the sheet member. A light source that emits a light beam L corresponding to the light source, and an AOM (acousto-optic modulator) that modulates the light beam L emitted from the light source according to image data after image processing supplied from the image processing device 13 Modulation means, an optical deflector such as a polygon mirror for deflecting the modulated light beam L in a direction (main scanning direction) orthogonal to the transport direction, and the light beam L deflected in the main scanning direction on the exposure position r It has a mirror for adjusting the optical path of an fθ (scanning) lens that forms an image at a predetermined position with a predetermined beam diameter.

Also, transport directions of PDP (plasma display) array, ELD (electroluminescent display) array, LED (light emitting diode) array, LCD (liquid crystal display) array, DMD (digital micromirror device, registered trademark) array, laser array, etc. Digital exposure means using various light emitting arrays or spatial modulation element arrays extending in the main scanning direction perpendicular to the main scanning direction may be used.
The main scanning width of the light beam L performed at the exposure position r of the exposure unit 36 is set so as to correspond to the width of the sheet member. The above operation of the exposure unit 36 is controlled by a control signal from the control unit 34.

The light beam L, which is recording light, is deflected in the main scanning direction (in FIG. 1, the direction perpendicular to the paper surface), while the sheet member is conveyed by the sub-scanning roller pairs 46 and 48, and thus is modulated according to the image data. The sheet body is two-dimensionally scanned and exposed by the light beam L, and an image is recorded. The effect of the present invention can be obtained when the speed conveyed by the sub-scanning roller pair is 90 mm / sec or more.
Instead of the sub-scanning roller pairs 46 and 48, a scanning conveyance mechanism that uses an exposure drum that conveys the sheet body while holding the sheet at the exposure position r, and two nip rollers that contact the exposure drum across the exposure position r. May be used. The configuration is not particularly limited as long as an image is recorded on the sheet body being conveyed by performing scanning recording at least in the main scanning direction orthogonal to the conveyance direction of the sheet body.

  The sub-scan receiving unit 28 includes a plurality of roller pairs that support a leading end portion of a sheet that is conveyed during recording in the exposure unit 26 and protrudes from the exposure unit 26, and includes, for example, three roller pairs. . Each roller pair includes a driving roller and a nip roller capable of releasing the nip that moves freely with respect to the driving roller. The sheet body is conveyed by the roller pair at the same speed as the conveyance speed of the sub-scanning roller pair.

  At the timing when the leading edge and the trailing edge of the paper pass through the driving roller portion during exposure recording, the nip roller is controlled so as not to be separated from the driving roller and nip the sheet member. That is, after the front end of the sheet member passes through the exposure point downstream roller pair in a separated state, the nip roller of the exposure point downstream roller pair comes into contact with the driving roller to nip and convey the sheet member. Also, immediately before the rear end of the sheet member passes through the roller pair upstream of the exposure point, the nip of the roller pair upstream of the exposure point is released, and the sheet member is nipped and conveyed only by the roller pair downstream of the exposure point. To do. This is because, during exposure recording of the sheet body, minute vibrations occur due to the leading or trailing end of the sheet body passing through the roller section while the nip roller pair remains in the nip state, and the position at which the sheet body is exposed. This is to prevent the occurrence of misalignment and exposure unevenness. Of course, the operation of the sub-scan receiving unit 28 is controlled by a control signal supplied from the control unit 34.

  In the present invention, the sub-scanning conveyance speed needs to be 90 mm / sec or more (preferably 90 mm / sec or more and 300 mm / sec or less), and is preferably 95 mm / sec or more and 200 mm / sec or less. The raster interval is preferably 500 μsec or less, and preferably 200 μsec or more and 450 μsec or less. The raster interval is the time interval of the light beam that is intermittently exposed in the sub-scan transport direction. That is, it means a time interval from when a certain pixel is exposed until the next pixel adjacent in the sub-scanning conveyance direction is exposed.

Next, the compounds used in the present invention will be described in detail.
First, the group used in the present invention will be described.
In the present invention, when a specific moiety is referred to as a “group”, the moiety may be unsubstituted or substituted with one or more (up to the maximum possible) substituents. Means good. For example, “alkyl group” means a substituted or unsubstituted alkyl group. Moreover, the substituent which can be used for the compound in the present invention includes any substituent regardless of the presence or absence of substitution.

  When such a substituent is W, the substituent represented by W is not particularly limited and includes, for example, a halogen atom, an alkyl group {including a cyclic alkyl group), and an alkenyl group. (Including cyclic alkenyl groups) and alkynyl groups. }, Aryl group, heterocyclic group (also called heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyl Oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group Alkyl, arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryl group Xycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phospho group (also called phosphono group), silyl Groups, hydrazino groups, ureido groups, boronic acid groups, phosphato groups, sulfato groups, and other optional substituents.

  More specifically, W represents a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group {[linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1.2.2] heptan-2-yl, bicyclo [2.2.2] octane-3-yl), and tricyclo structures with more ring structures It is intended to free. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituent described below represents an alkyl group having such a concept, but further includes an alkenyl group and an alkynyl group. ],

  Alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or unsubstituted 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2.2.1] hept-2-en-1-yl, bicyclo [2.2 2] is intended to encompass oct-2-en-4-yl). ], An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group)},

  An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 or 6 A monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably a 5- or 6-membered aromatic having 3 to 30 carbon atoms For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, and cationic heterocyclic rings such as 1-methyl-2-pyridinio and 1-methyl-2-quinolinio Group).

  A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2 -Tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 to 30 carbon atoms) Substituted or unsubstituted heterocyclic oxy group, 1-phenyl Trazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms) A carbonyloxy group such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy),

  A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di- n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t- Butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms such as phenoxycarbonyloxy, p Methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms) Substituted anilino groups such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino),

An ammonio group (preferably an ammonio group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, aryl, an ammonio group substituted with a heterocyclic ring, such as trimethylammonio, triethylammonio, diphenylmethylammonio), an acylamino group ( Preferably, formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroyl Amino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino),

  An aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxy; Carbonylamino), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p- Rollo phenoxycarbonylamino, m-(n-octyloxy) phenoxycarbonylamino),

  Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino ), Alkyl or arylsulfonylamino group (preferably substituted or unsubstituted alkanesulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino) , Phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, Echi Thio, n- hexadecylthio),

  An arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted group having 2 to 30 carbon atoms) A substituted heterocyclic thio group such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethyl Sulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′phenylcarbamoyl) sulfamoyl), sulfo Groups, alkyl or arylsulfinyl groups (preferably Substituted or unsubstituted alkylsulfinyl group having prime 1-30, 6-30 substituted or unsubstituted arylsulfinyl group, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p- methyl phenylsulfinyl),

  An alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- Methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, substitution having 4 to 30 carbon atoms) Or a heterocyclic carbonyl group bonded to a carbonyl group with an unsubstituted carbon atom, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2- Furylcarbonyl),

  An aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably having 1 carbon atom) -30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl An aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5 -Ethylthio-1,3,4-thiadiazol-2-ylazo),

  Imido group (preferably N-succinimide, N-phthalimide), phosphino group (preferably substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino) A phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), a phosphinyloxy group (preferably having 2 carbon atoms) -30 substituted or unsubstituted phosphinyloxy groups, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy, phosphinylamino groups (preferably substituted or unsubstituted having 2 to 30 carbon atoms) A phosphinylamino group such as dimethoxyphosphini Amino, dimethylamino phosphinyl amino),

  Phosphor groups, silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms, such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), hydrazino groups (preferably substituted with 0 to 30 carbon atoms) Alternatively, it represents an unsubstituted hydrazino group, such as trimethylhydrazino, or a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, such as N, N-dimethylureido).

  In addition, two Ws can be combined to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These can be further combined to form a polycyclic fused ring. For example, a benzene ring or naphthalene. Ring, anthracene ring, quinoline ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, Pyridazine ring, indolizine ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, carbazole ring, phenanthridine ring, acridine ring, Phenanthroline ring, Ntoren ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring and a phenazine ring.) Can also take a fused structure.

Among the above-mentioned substituents W, those having a hydrogen atom may be substituted with the above groups after removing this. Examples of such substituents, -CONHSO ₂ - group (sulfonylcarbamoyl group, a carbonyl sulfamoyl group), - CONHCO- group (carbonylation carbamoyl group), - SO ₂ NHSO ₂ - group (sulfonylsulfamoyl group ).
More specifically, alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group), alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl), arylsulfonylamino A carbonyl group (for example, p-methylphenylsulfonylaminocarbonyl) is mentioned.

Next, the sensitizing dye used in the present invention will be described in detail.
The silver halide emulsion of the present invention is spectrally sensitized with a sensitizing dye represented by the following general formula (I).

In general formula (I), X ¹ and X ² each independently represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a nitrogen atom or a carbon atom. Y ¹ represents a furan ring, a pyrrole ring, a thiophene ring, or a benzene ring that may be condensed with another 5- to 6-membered carbon ring or heterocyclic ring or may have a substituent. Y ² represents an atomic group necessary for forming a benzene ring or a 5- to 6-membered unsaturated heterocyclic ring, and has a substituent even if it is condensed with another 5- to 6-membered carbocyclic or heterocyclic ring. You may do it. Note that the bond between two carbon atoms to which Y ¹ and Y ² are condensed may be a single bond or a double bond. One of R ¹ and R ² represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. L ¹ represents a methine group. M ¹ represents a counter ion, and m ¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule.

The sensitizing dye represented by the general formula (I) of the present invention will be described in detail below.
X ¹ and X ² each independently represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a nitrogen atom or a carbon atom. The nitrogen atom is preferably -N (Rx)-, the carbon atom is preferably -C (Ry) (Rz)-, and Rx, Ry and Rz are each independently a hydrogen atom or a monovalent substituent. (For example, the above-mentioned W), and these are preferably the same alkyl group, aryl group, or heterocyclic group as described for the above-mentioned W, and more preferably an alkyl group. X ¹ and X ² are preferably an oxygen atom, a sulfur atom and a nitrogen atom, more preferably an oxygen atom and a sulfur atom.

Y ¹ represents a furan ring, a pyrrole ring, a thiophene ring, or a benzene ring that may be condensed with another 5- to 6-membered carbon ring or heterocyclic ring or may have a substituent. The bond between two carbon atoms to which Y ¹ is condensed may be a single bond or a double bond, but is preferably a double bond. Y ¹ can also form a condensed ring (for example, a benzofuran ring, an indole ring, a benzothiophene ring, a naphthalene ring) with another 5- to 6-membered carbon ring or heterocyclic ring. Y ¹ is preferably a thiophene ring. Any substituent may be used for Y ¹ , and examples thereof include the aforementioned W. Preferably, an alkyl group (for example, methyl), an aryl group (for example, phenyl), an aromatic heterocyclic group (for example, 1-pyrrolyl), an alkoxy group (for example, methoxy), an alkylthio group (for example, methylthio), a cyano group, an acyl group (for example, Acetyl), an alkoxycarbonyl group (for example, methoxycarbonyl), a halogen atom (for example, fluorine, chlorine, bromine, iodine), more preferably a methyl group, a methoxy group, a cyano group, or a halogen atom, more preferably a halogen atom. And particularly preferably a fluorine, chlorine or bromine atom, and most preferably a chlorine atom. In particular, when Y ¹ is a thiophene ring, it is preferably unsubstituted or has a halogen substituent, and the substituent is preferably a chlorine or bromine atom, and most preferably a chlorine atom.

Y ² represents an atomic group necessary for forming a benzene ring or a 5- to 6-membered unsaturated heterocyclic ring, and has a substituent even if it is condensed with another 5- to 6-membered carbocyclic or heterocyclic ring. You may do it. The bond between two carbon atoms to which Y ² is condensed may be a single bond or a double bond, but is preferably a double bond. The 5-membered unsaturated heterocycle formed by Y ² includes pyrrole ring, pyrazole ring, imidazole ring, triazole ring, furan ring, oxazole ring, isoxazole ring, thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, selenophene Ring, selenazole ring, isoselenazole ring, tellurophen ring, tellurazole ring, isotelrazole ring, etc., and 6-membered unsaturated heterocyclic ring includes pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyran ring, thiopyran ring, etc. A third condensed ring, which may be further condensed with another 5-6 membered carbocyclic or heterocyclic ring to form, for example, an indole, benzofuran, benzothiophene, or thienothiophene ring. Is preferably absent.

Y ² is preferably a benzene ring, a pyrrole ring, a furan ring, or a thiophene ring, particularly preferably a benzene ring, a furan ring, or a pyrrole ring, and most preferably a benzene ring. Any substituent may be used for Y ² , and examples thereof include the aforementioned W. Preferably, an alkyl group (for example, methyl), an aryl group (for example, phenyl), an aromatic heterocyclic group (for example, 1-pyrrolyl), an alkoxy group (for example, methoxy), an alkylthio group (for example, methylthio), a cyano group, an acyl group (for example, Acetyl), an alkoxycarbonyl group (for example, methoxycarbonyl), a halogen atom (for example, fluorine, chlorine, bromine, iodine), more preferably a methyl group, a methoxy group, a cyano group, or a halogen atom, more preferably a halogen atom. And particularly preferably a fluorine, chlorine or bromine atom, and most preferably a chlorine atom.

One of R ¹ and R ² represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group.

Here, the acid group will be described. An acid group is a group having a dissociable proton.
Specifically, for example, sulfo group, carboxyl group, sulfato group, —CONHSO ₂ — group (sulfonylcarbamoyl group, carbonylsulfamoyl group), —CONHCO— group (carbonylcarbamoyl group), —SO ₂ NHSO ₂ — group ( Sulfonylsulfamoyl group), sulfonamide group, sulfamoyl group, phosphato group, phosphono group, boronic acid group, phenolic hydroxyl group and the like. Depending on the pKa of these groups and the surrounding pH, there are further groups capable of dissociating protons, including the groups specifically exemplified above, and can be dissociated by 90% or more between pH 5-11, for example. Proton dissociable acidic groups are preferred.
In the sensitizing dye represented by the general formula (I), what is preferable as the “alkyl group substituted with an acid group” represented by R ¹ or R ² can be expressed as follows. .

Preferred alkyl group = -Qa-T ¹

Qa represents a linking group (preferably a divalent linking group) necessary for forming an alkyl group. T ¹ represents —SO ₃ ^— , —CO ₂ H, —CONHSO ₂ Ra, —SO ₂ NHCORb, —CONHCORc, or —SO ₂ NHSO ₂ Rd. Here, Ra, Rb, Rc and Rd each independently represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclyloxy group or an amino group.

  Qa may be any linking group as long as it satisfies the above requirements, but preferably consists of an atom or atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Preferably, an alkylene group (for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, methyltrimethylene), an alkenylene group (for example, ethenylene, propenylene), an alkynylene group (for example, ethynylene, propynylene), an amide group, an ester group, a sulfoamide Group, sulfonic acid ester group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (Wa)-(Wa represents a hydrogen atom or a monovalent substituent. Monovalent substitution. As the group, the above-mentioned W can be mentioned.)), Or a combination of one or more carbon atoms of 0 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms. Represents a group.

The above linking group may further have a substituent represented by the aforementioned W, and may contain a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring).
However, it is more preferable that these linking groups do not contain a hetero atom. Moreover, the case where it is not substituted with the substituent represented by the above-mentioned W is more preferable.

  More preferably, Qa is an alkylene group having 1 to 5 carbon atoms (for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, methyltrimethylene), an alkenylene group having 2 to 5 carbon atoms (for example, ethenylene, propenylene), It is a divalent linking group having 1 to 5 carbon atoms constituted by combining one or more alkynylene groups having 2 to 5 carbon atoms (for example, ethynylene and propynylene). Particularly preferred is an alkylene group having 1 to 5 carbon atoms (preferably methylene, ethylene, trimethylene, tetramethylene).

When T ¹ is a sulfo group, Qa is more preferably ethylene, trimethylene, tetramethylene, or methyltrimethylene, and particularly preferably trimethylene. When Xa is a carboxyl group, Qa is more preferably methylene, ethylene or trimethylene, and particularly preferably methylene.
T ¹ is _{-CONHSO 2 Ra, -SO 2 NHCORb,} -CONHCORc, in the case of -SO ₂ NHSO ₂ Rd, and more preferably as Qa methylene, ethylene, trimethylene, particularly preferably methylene.

Ra, Rb, Rc, and Rd each independently represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclyloxy group, or an amino group. Preferred examples include the following.
For example, an unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (for example, methyl, ethyl, propyl, butyl), 1 to 18 carbon atoms, preferably carbon A substituted alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and preferably 2 to 18 carbon atoms, More preferably, an unsaturated hydrocarbon group having 3 to 10 carbon atoms, particularly preferably 3 to 5 carbon atoms (for example, vinyl group, ethynyl group, 1-cyclohexenyl group, benzylidine group, benzylidene group) is also included in the substituted alkyl group. )

A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (for example, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl, 3, 5- Dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl), an optionally substituted heterocyclic group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms (for example, Pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydrofurfuryl), an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-hydroxyethoxy, 2-phenylethoxy), 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to carbon atoms. 0 aryloxy group (for example, phenoxy, p-methylphenoxy, p-chlorophenoxy, naphthoxy), C1-C20, preferably C3-C12, more preferably C3-C10 heterocyclyloxy group (complex) An oxy group substituted with a cyclic group (for example, 2-thienyloxy, 2-morpholinooxy), an amino group having 0 to 20 carbon atoms, preferably 0 to 12 carbon atoms, and more preferably 0 to 8 carbon atoms. An amino group (for example, amino, methylamino, dimethylamino, ethylamino, diethylamino, hydroxyethylamino, benzylamino, anilino, diphenylamino, morpholino formed a ring, pyrrolidino). Furthermore, the above-described W may be substituted for these.
More preferred are a methyl group, an ethyl group, and a hydroxyethyl group, and particularly preferred is a methyl group.

In addition, in the acid group, for example, a carboxyl group, a dissociative nitrogen atom, and the like may be expressed in a non-dissociated form (COOH, NH) or in a dissociated form (COO-, N-). But you can. Actually, it may be in a dissociated state or a non-dissociated state depending on the environment such as pH where the dye is placed.
When a cation is present as a counter ion, for example, it may be expressed as (COO ⁻ Na ⁺ ) or (N ⁻ Na ⁺ ). In the non-dissociated state, they are expressed as (COOH) and (NH). However, if the counter ion cation compound is considered as a proton, it can also be expressed as (COO ⁻ H ⁺ ) and (N ⁻ H ⁺ ).

In the sensitizing dye represented by the general formula (I), ^one of R ¹ and R ² is an alkyl group substituted with an acid group other than a sulfo group, and the other is an alkyl group substituted with a sulfo group. The alkyl group having a sulfo group is preferably a 3-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group, or a 2-sulfoethyl group, and more preferably a 3-sulfopropyl group. An alkyl group substituted with an acid group other than a sulfo group is preferably an alkyl group substituted with a carboxyl group, a —CONHSO ₂ — group, a —SO ₂ NHCO— group, a —CONHCO— group, or a —SO ₂ NHSO ₂ — group. Particularly preferred are a carboxymethyl group and a methanesulfonylcarbamoylmethyl group.

As a combination of R ¹ and R ² , one is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group, and the other is a 3-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group, or a 2-sulfoethyl group. In some cases, more preferably, one is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group, and the other is a 3-sulfopropyl group.

L ¹ represents a methine group, which may be unsubstituted or substituted by a substituent (for example, W described above). Preferred examples of the substituent include an aryl group, an unsaturated hydrocarbon group, a carboxy group, and a sulfo group. Sulfato group, cyano group, halogen atom (eg fluorine, chlorine, bromine, iodine), hydroxy group, mercapto group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, Examples include an acyloxy group, a carbamoyl group, a sulfamoyl group, a heterocyclic group, an alkanesulfonylcarbamoyl group, an acylcarbamoyl group, an acylsulfamoyl group, and an alkanesulfonylsulfamoyl group.
L ¹ is preferably an unsubstituted methine group.

M ¹ represents a counter ion and is included in the formula to indicate the presence of a cation or anion when necessary to neutralize the ionic charge of the dye. Whether a dye is a cation, an anion, or has a net ionic charge depends on its substituents and the environment in solution (such as pH). Typical cations include inorganic cations such as hydrogen ions (H ⁺ ), alkali metal ions (eg, sodium ions, potassium ions, lithium ions), alkaline earth metal ions (eg, calcium ions), ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, 1,8-diazabicyclo [5.4.0] -7-undecenium ion). The anion may be either an inorganic anion or an organic anion, a halide anion (eg, fluoride ion, chloride ion, bromide ion, iodide ion), a substituted aryl sulfonate ion (eg, p-toluene). Sulfonate ion, p-chlorobenzenesulfonate ion), aryl disulfonate ion (for example, 1,3-benzenesulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate Examples thereof include ions (for example, methyl sulfate ion), sulfate ions, thiocyanate ions, perchlorate ions, tetrafluoroborate ions, picrate ions, acetate ions, and trifluoromethanesulfonate ions. Furthermore, you may use the ionic polymer or the other pigment | dye which has a charge opposite to a pigment | dye.

Preferred cations are sodium ion, potassium ion, triethylammonium ion, tetraethylammonium ion, pyridinium ion, ethylpyridinium ion, and methylpyridinium ion. Preferred anions are perchlorate ions, iodide ions, bromide ions, substituted aryl sulfonate ions (eg, p-toluene sulfonate ions).
m ¹ represents a number of 0 or more necessary for balancing the electric charge, and 0 when forming an inner salt. The number is preferably 0 or more and 4 or less.

  The sensitizing dye represented by the general formula (I) is more preferably represented by the general formula (II) or (III) or represented by the general formula (IV).

In the general formula (II), Y ¹¹ represents an oxygen atom, a sulfur atom or N—R ¹³ , and R ¹³ represents a hydrogen atom or an alkyl group. V ¹⁵ and V ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. X ¹¹ and X ¹² each independently represent an oxygen atom or a sulfur atom. One of R ¹¹ and R ¹² represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. V ¹¹ , V ¹² , V ¹³ and V ¹⁴ each independently represent a hydrogen atom or a monovalent substituent. M ¹¹ represents a counter ion, and m ¹¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule.

In the general formula (III), Y ²¹ represents an oxygen atom, a sulfur atom or N—R ²³ , and R ²³ represents a hydrogen atom or an alkyl group. V ²⁵ and V ²⁶ each independently represent a hydrogen atom or a monovalent substituent. X ²¹ and X ²² each independently represent an oxygen atom or a sulfur atom. One of R ²¹ and R ²² represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. V ²¹ , V ²² , V ²³ and V ²⁴ each independently represent a hydrogen atom or a monovalent substituent. M ²¹ represents a counter ion, and m ²¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule.

In the general formula (IV), X ³¹ and X ³² each independently represent an oxygen atom or a sulfur atom. One of R ³¹ and R ³² represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. V ³¹ , V ³² , V ³³ , V ³⁴ , V ³⁵ , V ³⁶ , V ³⁷ and V ³⁸ each independently represent a hydrogen atom or a monovalent substituent, and two adjacent substituents are linked to each other and condensed. A ring may be formed. M ³¹ represents a counter ion, and m ³¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule.

Below, these preferable compounds are demonstrated.
In the general formula (II), Y ¹¹ represents an oxygen atom, a sulfur atom or N—R ¹³ , and R ¹³ represents a hydrogen atom, an unsubstituted alkyl group, or a substituted alkyl group (for example, an alkyl group substituted with the aforementioned W). It is. The substituent of the substituted alkyl group is preferably a substituent having a higher hydrophilicity than the iodine atom, more preferably the same as the chlorine atom, or a more hydrophilic substituent, and particularly preferably the same as the fluorine atom. And an alkyl group substituted with a more hydrophilic substituent. R ¹³ is more preferably a hydrogen atom or an unsubstituted alkyl group, and particularly preferably a hydrogen atom or a methyl group. Y ¹¹ is particularly preferably a sulfur atom.
X ¹¹ and X ¹² each independently represent an oxygen atom or a sulfur atom, preferably at least one is a sulfur atom, and preferably both are sulfur atoms.

V ¹¹ , V ¹² , V ¹³ , V ¹⁴ , V ¹⁵ and V ¹⁶ each independently represent a hydrogen atom or a monovalent substituent, and two adjacent substitutions among V ¹¹ , V ¹² , V ¹³ and V ¹⁴ The groups or V ¹⁵ and V ¹⁶ may be linked to each other to form a saturated or unsaturated condensed ring, but it is preferable not to form a condensed ring. Examples of the monovalent substituent include the aforementioned W, but preferably an alkyl group (for example, methyl), an aryl group (for example, phenyl), an aromatic heterocyclic group (for example, 1-pyrrolyl), an alkoxy group (for example, methoxy), An alkylthio group (for example, methylthio), a cyano group, an acyl group (for example, acetyl), an alkoxycarbonyl group (for example, methoxycarbonyl), a halogen atom (for example, fluorine, chlorine, bromine, iodine), more preferably a methyl group, a methoxy group, It is a cyano group or a halogen atom, more preferably a halogen atom, particularly preferably a fluorine, chlorine or bromine atom, and most preferably a chlorine atom. V ¹¹ , V ¹² and V ¹⁴ are preferably hydrogen atoms.
When Y ¹¹ is a sulfur atom, it is preferred that both V ¹⁵ and V ¹⁶ are hydrogen atoms or one is a halogen atom (eg, fluorine, chlorine, bromine, iodine), more preferably V ¹⁶ is a hydrogen atom, V ¹⁵ Is a hydrogen atom or a chlorine atom.

One of R ¹¹ and R ¹² is an alkyl group substituted with other than a sulfo group (preferably a carboxyl group or an alkanesulfonylcarbamoyl group), and the other is an alkyl group substituted with a sulfo group. Specific examples and preferred combinations of alkyl groups substituted with these acid groups are the same as those described for R ¹ above. More preferably, a case one of R ¹¹ and R ¹² are carboxymethyl group or methanesulfonyl carbamoylmethyl group, still more preferably, an R ¹¹ is carboxymethyl group or a methanesulfonyl carbamoylmethyl methyl radical, R ^This is the case when ¹² is a 3-sulfopropyl group.
M ¹¹ represents a counter ion, and m ¹¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule, and examples thereof include the same as M ¹ and m ¹ described above. M ¹¹ is particularly preferably a cation, and preferred cations are sodium, potassium, triethylammonium, pyridinium, and N-ethylpyridinium.

In the general formula (III), Y ²¹ represents an oxygen atom, a sulfur atom or N—R ²³ , and R ²³ represents a hydrogen atom, an unsubstituted alkyl group, or a substituted alkyl group (for example, an alkyl group substituted with the aforementioned W). It is. The substituent of the substituted alkyl group is preferably a substituent having a higher hydrophilicity than the iodine atom, more preferably the same as the chlorine atom, or a more hydrophilic substituent, and particularly preferably the same as the fluorine atom. And an alkyl group substituted with a more hydrophilic substituent. R ²³ is more preferably a hydrogen atom or an unsubstituted alkyl group, and particularly preferably a hydrogen atom or a methyl group. Y ²¹ is particularly preferably a sulfur atom.
X ²¹ and X ²² each independently represent an oxygen atom or a sulfur atom, preferably at least one is a sulfur atom, and preferably both are sulfur atoms.

V ²¹ , V ²² , V ²³ , V ²⁴ , V ²⁵ and V ²⁶ each independently represent a hydrogen atom or a monovalent substituent, and two adjacent substitutions among V ²¹ , V ²² , V ²³ and V ²⁴ The groups or V ²⁵ and V ²⁶ may be linked together to form a saturated or unsaturated condensed ring, but preferably no condensed ring is formed. Examples of the monovalent substituent include the aforementioned W, but preferably an alkyl group (for example, methyl), an aryl group (for example, phenyl), an aromatic heterocyclic group (for example, 1-pyrrolyl), an alkoxy group (for example, methoxy), An alkylthio group (for example, methylthio), a cyano group, an acyl group (for example, acetyl), an alkoxycarbonyl group (for example, methoxycarbonyl), a halogen atom (for example, fluorine, chlorine, bromine, iodine), more preferably a methyl group, a methoxy group, It is a cyano group or a halogen atom, more preferably a halogen atom, particularly preferably a fluorine, chlorine or bromine atom, and most preferably a chlorine atom. V ²¹ , V ²² and V ²⁴ are preferably hydrogen atoms.
When Y ²¹ is a sulfur atom, it is preferable that both V ²⁵ and V ²⁶ are hydrogen atoms or one is a halogen atom (eg fluorine, chlorine, bromine, iodine), more preferably V ²⁶ is a hydrogen atom, V ²⁵ Is a hydrogen atom or a chlorine atom.

One of R ²¹ and R ²² is an alkyl group substituted with other than a sulfo group (preferably a carboxyl group or an alkanesulfonylcarbamoyl group), and the other is an alkyl group substituted with a sulfo group. Specific examples and preferred combinations of alkyl groups substituted with these acid groups are the same as those described for R ¹ above. More preferably, a case one of R ²¹ and R ²² are carboxymethyl group or methanesulfonyl carbamoylmethyl group, still more preferably, a case R ²¹ is a carboxymethyl group or a methanesulfonyl carbamoylmethyl methyl radical, R ^This is the case when ²² is a 3-sulfopropyl group.
M ²¹ represents a counter ion, and m ²¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule, and examples thereof include the same as M ¹ and m ¹ described above. M ²¹ is particularly preferably a cation, and preferred cations are sodium, potassium, triethylammonium, pyridinium, and N-ethylpyridinium.

In the general formula (IV), X ³¹ and X ³² each independently represent an oxygen atom or a sulfur atom, preferably at least one is a sulfur atom, and preferably both are sulfur atoms.
One of R ³¹ and R ³² is an alkyl group substituted with other than a sulfo group (preferably a carboxyl group or an alkanesulfonylcarbamoyl group), and the other is an alkyl group substituted with a sulfo group. Specific examples and preferred combinations of alkyl groups substituted with these acid groups are the same as those described for R ¹ above. More preferably, a case one of R ³¹ and R ³² is a carboxymethyl group or a methanesulfonyl carbamoylmethyl group, still more preferably, a case R ³¹ is a carboxymethyl group or a methanesulfonyl carbamoylmethyl methyl radical, R ^This is the case when ³² is a 3-sulfopropyl group.

V ³¹ , V ³² , V ³³ , V ³⁴ , V ³⁵ , V ³⁶ , V ³⁷ and V ³⁸ each independently represent a hydrogen atom or a monovalent substituent, and two adjacent substituents are linked to each other and condensed. A ring may be formed. You may be two adjacent substituents are linked to each other to form a condensed ring, saturated or unsaturated, as the condensed naphthalene ring formed by connecting and the V ³³ and V ^34. Examples of the monovalent substituent include the aforementioned W, but preferably an alkyl group (for example, methyl), an aryl group (for example, phenyl), an aromatic heterocyclic group (for example, 1-pyrrolyl), an alkoxy group (for example, methoxy), An alkylthio group (for example, methylthio), a cyano group, an acyl group (for example, acetyl), an alkoxycarbonyl group (for example, methoxycarbonyl), a halogen atom (for example, fluorine, chlorine, bromine, iodine), more preferably a methyl group, a methoxy group, It is a cyano group or a halogen atom, more preferably a halogen atom, particularly preferably a fluorine, chlorine or bromine atom, and most preferably a chlorine atom. V ³¹ , V ³² , V ³⁴ , V ³⁵ , V ³⁶ , and V ³⁸ are preferably hydrogen atoms.

M ³¹ represents a counter ion, and m ³¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule, and examples thereof include the same as M ¹ and m ¹ described above. M ³¹ is particularly preferably a cation, and preferred cations are sodium, potassium, triethylammonium, pyridinium, and N-ethylpyridinium.

In the present invention, the sensitizing dye represented by the general formula (I) is used in the blue-sensitive emulsion layer, and is preferably selected from the general formula (II), (III) or (IV). A sensitizing dye represented by II) or (III) is more preferred, and a sensitizing dye represented by formula (II) is particularly preferred.
X ¹¹ , X ¹² and Y ¹¹ (X ²¹ , X ²² and Y ²¹ ) (X ³¹ , X ³² ) are all sulfur atoms, V ¹⁵ (V ²⁵ ) is a hydrogen atom or chlorine atom, and V ¹⁶ (V ²⁶ ) Is preferably a hydrogen atom. ^{V 11, V 12, V 14} (V 21, V 22, V 24) (V 31, V 32, V 34, V 35, V 36, V 38) is a hydrogen atom, V ¹³ (V ²³⁾ ( V ³³ and V ³⁷ ) are alkyl groups (eg methyl), alkoxy groups (eg methoxy), alkylthio groups (eg methylthio), cyano groups, acyl groups (eg acetyl), alkoxycarbonyl groups (eg methoxycarbonyl), halogen atoms ( For example, fluorine, chlorine, bromine, iodine), more preferably a methyl group, a methoxy group, a cyano group, an acetyl group, a methoxycarbonyl group, or a halogen atom, particularly preferably a halogen atom, most preferably A fluorine atom and a chlorine atom.

One of R ¹¹ and R ¹² (R ²¹ and R ²² ) (R ³¹ and R ³² ) is preferably a carboxymethyl group or a methanesulfonylcarbamoylmethyl group, and the other is preferably a 3-sulfopropyl group. This is the case where R ¹¹ (R ²¹ ) (R ³¹ ) is a carboxymethyl group or methanesulfonylcarbamoylmethyl group, and R ¹² (R ²² ) (R ³² ) is a 3-sulfopropyl group.
M ¹¹ (M ²¹ ) (M ³¹ ) is an organic or inorganic monovalent cation, and m ¹¹ (m ²¹ ) (m ³¹ ) is preferably 0 or 1.

  Specific examples of the sensitizing dye represented by any one of the general formulas (I), (II), (III) and (IV) used in the present invention are shown below, but the present invention is limited thereby. is not.

The sensitizing dyes represented by the general formulas (I), (II), (III), and (IV) used in the present invention can be synthesized based on the methods described in the following documents.
a) “Heterocyclic Compounds—Cyanine dyes and related compounds” by FMHamer (John Wiley & Sons, New York, London, 1964),
b) “Heterocyclic Compounds—Special topics in cyclic chemistry” by DMSturmer, Chapter 8, Section 4, 482-515 (John Wiley & Sons, New York, London, 1977),
c) "Rodd's Chemistry of Carbon Compounds", 2nd Edition, Volume 4, Part B, Chapter 15, pages 369-422 (Elsevier Science Publishing Company Inc.-New York, 1977)

  Further, for the synthesis of a heterocyclic ring used as a raw material for a sensitizing dye represented by any one of the general formulas (I), (II), (III), and (IV) used in the present invention, for example, Bulletin de la Societe Chimique de Reference can be made to descriptions of documents such as France, II-150 (1980) and Journal of Heterocyclic Chemistry, 16, 1563 (1979).

  In order to incorporate the methine dye represented by any one of the general formulas (I), (II), (III) and (IV) used in the present invention into the silver halide emulsion of the present invention, they are directly used in the emulsion. Or may be dispersed in water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy- It may be dissolved in a solvent such as 1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide or a mixed solvent and added to the emulsion.

  Further, as described in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is dispersed in an emulsion. As described in JP-B-46-24185, etc., in which a water-insoluble dye is dispersed in a water-soluble solvent without dissolving it, and this dispersion is added to the emulsion. No. 23389, No. 44-27555, No. 57-22091, etc., the dye is dissolved in an acid and the solution is added to the emulsion, or the acid or base is allowed to coexist. As described in US Pat. Nos. 3,822,135, 4,006,026, etc., a method of adding an aqueous solution to the emulsion to make an aqueous solution or a colloidal dispersion in the presence of a surfactant. To add the product to the emulsion As described in JP-A-53-102733 and JP-A-58-105141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion, JP-A-51-74624 As described in the publication, it is also possible to use a method in which a dye is dissolved using a compound that shifts red and the solution is added to an emulsion. In addition, ultrasonic waves can be used for dissolution.

  The time when the sensitizing dye represented by any one of the general formulas (I), (II), (III) and (IV) used in the present invention is added to the silver halide emulsion of the present invention has been useful so far. It may be during any step of preparing the emulsion that is recognized as For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, JP-A-58-184142, 60- As disclosed in each publication or specification such as No. 196749, the silver halide grain formation step and / or the time before desalting, during the desalting step and / or after the desalting to before the start of chemical ripening As disclosed in Japanese Patent Application Laid-Open No. 58-11939, etc., at any time and before the emulsion is coated immediately before chemical ripening, during the process, or until the coating after chemical ripening. It may be added. Further, as disclosed in the specifications of US Pat. No. 4,225,666 and JP-A-58-7629, the same compound can be used alone or in combination with compounds of different structures, for example, to form particles. Compounds may be added separately during the process and during chemical ripening or after completion of chemical ripening, or may be added separately before or during chemical ripening, or after completion of chemical ripening. It may be added by changing the combination type.

  The amount of the sensitizing dye represented by any one of the general formulas (I), (II), (III) and (IV) used in the present invention varies depending on the shape and size of the silver halide grains. The amount is preferably 0.1 to 4 mmol, more preferably 0.2 to 2.5 mmol, per mol of silver halide, and may be used in combination with other sensitizing dyes.

  In the present invention, other sensitizing dyes may be used in addition to the sensitizing dye represented by any one of the general formulas (I), (II), (III), and (IV). A combination of sensitizing dyes is often used for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703 377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patent 1,344,281, No. 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, Japanese Patent Application Laid-Open Nos. 52-110618, 52-109925 and the like.

The compound represented by general formula (Z) is demonstrated below.
General formula (Z)
R ⁴¹ -S-S-R ⁴²
In the general formula (Z), the aliphatic group represented by R ⁴¹ and R ⁴² represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, or an aralkyl group, having 1 to 18 carbon atoms For example, methyl, ethyl, n-propyl, i-propyl, i-butyl, t-pentyl, n-hexyl, n-decyl, allyl, 3-pentenyl, propargyl, cyclohexyl, cyclohexenyl, benzyl, phenethyl and the like. Is mentioned. The aromatic group represented by R ^41, R ⁴² is a monocyclic or condensed aryl group preferably has 6 to 20 carbon atoms, for example, a phenyl group, a naphthyl group. R ⁴¹ and R ⁴² may be bonded to each other to form a ring, and those that form a 5- to 6-membered ring with —SS— are preferred.

Each group represented by R ⁴¹ and R ⁴² may be substituted with a substituent, and examples of these substituents include the following. In addition, a plurality of different substituents may be substituted. Typical substituents include a carboxyl group, an alkoxycarbonyl group (for example, ethoxycarbonyl), an aryloxycarbonyl group (for example, phenoxycarbonyl group), an amino group, a substituted amino group (for example, ethylamino, dimethylamino, methylphenyl). Amino), hydroxyl group, alkoxy group (for example, methoxy), aryloxy group (for example, phenoxy), acyl group (for example, acetyl), acylamino group (for example, acetamide), ureido group (for example, N, N-dimethylureido) ), Nitro group, sulfonyl group (for example, methylsulfonyl, phenylsulfonyl), sulfo group, mercapto group, alkylthio group (for example, methylthio), cyano group, phosphonyl group, sulfamoyl group (for example, unsubstituted sulfamoyl, N, N- The Tilsulfamoyl), carbamoyl group (eg unsubstituted carbamoyl, N, N-diethylcarbamoyl), alkyl group (eg ethyl), aryl group (eg phenyl), heterocyclic group (eg morphonyl, pyrazolyl), halogen Atoms (for example, chlorine, bromine) and the like.
Specific examples of the compound represented by formula (Z) used in the present invention are shown below, but the present invention is not limited thereto.

The addition time of the compound represented by the general formula (Z) used in the present invention is preferably from the time of preparation of silver halide until the end of chemical sensitization, preferably at the time of gold sensitization. The amount of the compound represented by the general formula (Z) may be appropriately adjusted depending on the silver halide to be used, the timing of addition, and the like, but 1 × 10 ⁻⁹ to 1 × 10 ⁻⁵ per mole of silver halide. A mole, preferably 5 × 10 ⁻⁶ to 1 × 10 ⁻⁵ mole may be used. The compound represented by the general formula (Z) can be dissolved in water or an organic solvent miscible with water (for example, ethanol) or added in a finely dispersed form in a gelatin solution or the like.

[Silver halide emulsion]
Next, the silver halide emulsion relating to the present invention will be explained.
The silver halide emulsion used in the present invention contains specific silver halide grains. The particle shape of this particle is not particularly limited, but is substantially a cubic or tetradecahedral crystal particle having {100} faces (they may have rounded vertices and higher order faces). ), Octahedral crystal grains, and the main surface is preferably composed of tabular grains having an aspect ratio of 3 or more and comprising {100} planes or {111} planes. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of the particle. In particular, cubic or tetrahedral crystal particles are more preferable.

The silver chloride content needs to be 90 mol% or more, and the silver chloride content is preferably 95 mol% or more, more preferably 98 mol% or more. When the silver halide emulsion of the present invention has a silver bromide-containing phase, the silver bromide content needs to be 0.1 to 4 mol%, preferably 0.5 to 2 mol%. When the silver halide emulsion of the present invention has a silver iodide-containing phase, the silver iodide content must be 0.02 to 1 mol%, preferably 0.05 to 0.50 mol%, More preferably, it is 07-0.40 mol%.
The specific silver halide grains used in the present invention are preferably silver iodobromochloride grains having both a silver bromide-containing phase and a silver iodide-containing phase, and particularly preferably silver iodobromochloride grains having the above-described halogen composition.

  The specific silver halide grains in the silver halide emulsion used in the present invention have a silver bromide-containing phase and / or a silver iodide-containing phase. Here, the silver bromide or silver iodide-containing phase means a portion where the concentration of silver bromide or silver iodide is higher than the surroundings. The halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change sharply. Such a silver bromide or silver iodide-containing phase may form a layer having a substantially constant width at a certain portion in the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing phase is preferably 3 mol% or more, more preferably 5 to 40 mol%, and most preferably 5 to 25 mol%. The local silver iodide content of the silver iodide-containing phase is preferably 0.3 mol% or more, more preferably 0.5 to 8 mol%, and more preferably 1 to 5 mol%. Most preferred. Further, there may be a plurality of such silver bromide or silver iodide-containing phases in the form of layers in each grain, and the silver bromide or silver iodide content may be different.

  It is important that the silver bromide-containing phase or the silver iodide-containing phase of the silver halide emulsion used in the present invention is layered so as to surround each grain. In one preferred embodiment, the silver bromide-containing phase or the silver iodide-containing phase formed in layers so as to surround the grains has a uniform concentration distribution in the circumferential direction of the grains in each phase. However, in the silver bromide-containing phase or silver iodide-containing phase that are layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the circumferential direction of the grain, and the concentration distribution You may have. For example, when a silver bromide-containing phase or silver iodide-containing phase is formed in a layer so as to surround the grain in the vicinity of the grain surface, the silver bromide or silver iodide concentration at the grain corner or edge is different from the main surface. There is a case. In addition to the silver bromide-containing phase and the silver iodide-containing phase that are layered so as to surround the grain, the silver bromide-containing phase that is completely isolated in a specific part of the surface of the grain and does not surround the grain Alternatively, there may be a silver iodide containing phase.

  When the silver halide emulsion used in the present invention contains a silver bromide-containing phase, the silver bromide-containing phase is preferably formed in a layered manner so as to have a silver bromide concentration maximum inside the grain. Further, when the silver halide emulsion used in the present invention contains a silver iodide-containing phase, the silver iodide-containing phase may be formed in layers so as to have a silver iodide concentration maximum on the surface of the grain. preferable. Such a silver bromide-containing phase or silver iodide-containing phase is composed of a silver amount of 3% to 30% of the grain volume in order to increase the local concentration with a smaller silver bromide or silver iodide content. It is preferable that the silver content is 3% or more and 15% or less.

  The silver halide emulsion used in the present invention preferably contains both a silver bromide-containing phase and a silver iodide-containing phase. In this case, the silver bromide-containing phase and the silver iodide-containing phase may be at the same place or different places in the grain, but it is preferable that the silver bromide-containing phase and the silver iodide-containing phase are in different places from the viewpoint of facilitating control of grain formation. Further, the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide. In general, iodide added during the formation of high silver chloride grains tends to ooze out on the grain surface than bromide, so the silver iodide-containing phase tends to be formed near the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different locations in the grain, the silver bromide-containing phase is preferably formed inside the silver iodide-containing phase. In such a case, another silver bromide-containing phase may be provided further outside the silver iodide-containing phase near the grain surface.

  It is preferable to concentrate the functions of the silver bromide-containing phase and silver iodide-containing phase that control photographic action close to the surface in the grain. Therefore, the silver bromide-containing phase and the silver iodide-containing phase are preferably adjacent to each other. From these points, the silver bromide-containing phase is formed at any of the positions of 50% to 100% of the grain volume as measured from the inside, and the silver iodide-containing phase is any of the positions at 85% to 100% of the grain volume. It is preferable to form it. Further, the silver bromide-containing phase is formed at any position from 70% to 95% of the grain volume, and the silver iodide-containing phase is further formed at any position from 90% to 100% of the grain volume. preferable.

  When the silver halide emulsion used in the present invention has a silver bromide-containing phase, another preferred embodiment of the silver bromide-containing phase is that the silver bromide content is within a depth of 20 nm from the grain surface. It is a silver halide emulsion having a region of 0.5 to 20 mol%. It is preferable to have a silver bromide-containing phase within 10 nm from the grain surface, preferably a silver bromide-containing phase having a silver bromide content of 0.5 to 10 mol%, and 0.5 to 5 mol More preferably, it has a silver bromide-containing phase. In this case, the silver bromide-containing phase does not necessarily have to be formed in layers. However, in order to further enhance the effects of the present invention, it is preferable that a silver bromide-containing phase is formed in a layered manner so as to surround the grains.

  When the silver halide emulsion used in the present invention has a silver iodide-containing phase, another preferred embodiment of the silver iodide-containing phase is that the silver iodide content is within a depth of 20 nm from the grain surface. It is a silver halide emulsion having a region of 0.3 to 10 mol%. The silver iodide-containing phase preferably has a silver iodide-containing phase within 10 nm from the grain surface, and preferably has a silver iodide-containing phase having a silver iodide content of 0.5 to 10 mol%, preferably 0.5 to 5 mol. % Of silver iodide containing phase is more preferred. In this case, the silver iodide-containing phase is not necessarily formed in a layer form. However, in order to further enhance the effects of the present invention, it is preferable that a silver iodide-containing phase is formed in a layered manner so as to surround the grains.

  Introducing bromide or iodide ions to contain silver bromide or silver iodide in the silver halide emulsion used in the present invention can be carried out by adding a bromide salt or iodide salt solution alone or by adding a silver salt solution. In addition to the addition of a high chloride salt solution, a bromide salt or iodide salt solution may be added. In the latter case, bromide salt or iodide salt solution and high chloride salt solution may be added separately or as a mixed solution of bromide salt or iodide salt and high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can be introduced by cleaving bromide ions or iodide ions from organic molecules described in US Pat. No. 5,389,508. As another bromide or iodide ion source, fine silver bromide grains or fine silver iodide grains can also be used.

The addition of the bromide salt or iodide salt solution may be concentrated at one time of grain formation or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in obtaining an emulsion with high sensitivity and low covering. Iodide ions are introduced more into the emulsion grains and the increase in sensitivity is smaller. Therefore, the iodide salt solution is preferably added outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. Further, the addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. The addition of the iodide salt solution is completed slightly inside from the grain surface, so that an emulsion with higher sensitivity and lower covering can be obtained.
On the other hand, the addition of the bromide salt solution is preferably performed outside 50% of the particle volume, more preferably outside 70%.

  Distribution of bromide or iodide ion concentration in the depth direction in the particle is measured by etching / TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method, for example, using TRIFT II type TOF-SIMS manufactured by Phi Evans. it can. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Secondary Ion Mass Spectrometry” Maruzen Co., Ltd. (1999), edited by the Surface Science Society of Japan. When the emulsion grains are analyzed by the etching / TOF-SIMS method, it is possible to analyze that iodide ions ooze out toward the grain surface even when the addition of the iodide salt solution is finished inside the grains. The emulsion of the present invention is analyzed by etching / TOF-SIMS method, and it is preferable that iodide ions have a maximum concentration on the grain surface, and the iodide ion concentration is attenuated toward the inside. It is preferable to have a concentration maximum inside. The local concentration of silver bromide can also be measured by X-ray diffraction if the silver bromide content is somewhat high.

  In this specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to the volume of each particle. The emulsion of the present invention is preferably composed of grains having a monodispersed grain size distribution. The variation system number of the sphere equivalent diameter of all the particles of the present invention needs to be 20% or less, more preferably 15% or less, and still more preferably 10% or less. The variation coefficient of the equivalent sphere diameter is expressed as a percentage of the standard deviation of the equivalent sphere diameter of each particle with respect to the average equivalent sphere diameter. At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer or to carry out multilayer coating.

  The sphere equivalent diameter of the silver halide emulsion in the yellow dye-forming coupler-containing silver halide emulsion layer is preferably 0.7 μm or less, more preferably 0.6 μm or less, and 0.5 μm or less. Most preferred. The sphere equivalent diameter of the silver halide emulsion of the magenta dye-forming coupler-containing silver halide emulsion layer and the cyan dye-forming coupler-containing silver halide emulsion layer is preferably 0.5 μm or less, and preferably 0.4 μm or less. More preferably, it is most preferably 0.3 μm or less. In this specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to the volume of each particle. Particles with a sphere equivalent diameter of 0.6 μm correspond to cubic particles with a side length of about 0.48 μm, particles with a sphere equivalent diameter of 0.5 μm correspond to cubic particles with a side length of about 0.40 μm, and a sphere equivalent diameter of 0.4 μm. These particles correspond to cubic particles having a side length of about 0.32 μm, and particles having a sphere equivalent diameter of 0.3 μm correspond to cubic particles having a side length of about 0.24 μm.

  The silver halide emulsion used in the present invention may contain silver halide grains other than the silver halide grains (that is, specific silver halide grains) contained in the silver halide emulsion defined in the present invention. However, the silver halide emulsion defined in the present invention requires that 50% or more of the total projected area of all the grains be silver halide grains defined in the present invention, and preferably 80% or more. More preferably, it is 90% or more.

  When specific silver halide grains in the silver halide emulsion used in the present invention contain a hexacoordinate complex having Ir as a central metal having at least two different ligands in the same complex This is one of the embodiments of the present invention and is particularly preferable. Examples of the hexacoordination complex having Ir as a central metal include a hexacoordination complex having Ir as a central metal containing a halogen ligand and an organic ligand in the same complex, and inorganic compounds other than halogen ligands and halogens. Of these, hexacoordinate complexes containing Ir as a central metal and containing a ligand in the same complex are preferred. Hexacoordination complex containing halogen ligand and organic ligand in the same complex with Ir as the central metal, and Ir containing halogen ligand and inorganic ligand other than halogen in the same complex as the central metal It is more preferred to have both hexacoordinate complexes.

  The hexacoordination complex having Ir as a central metal preferably used in the present invention is a metal complex represented by the following general formula (α).

General formula (α)
[IrX ^I _n L ^I _(6-n) ] ^m

In the general formula (α), X ^I represents a pseudohalogen ion other than a halogen ion or a cyanate ion, and L ^I represents an arbitrary ligand different from X ^I. n represents 3, 4 or 5, and m represents 4-, 3-, 2-, 1-, 0 or 1+.
Here, 3-5 X ^I may be the same or different from each other. When L ^I there are a plurality, a plurality of L ^I may be the same or different from each other.
In the above, pseudohalogen (halogenoid) ions are ions having properties similar to halogen ions. For example, cyanide ions (CN ⁻ ), thiocyanate ions (SCN ⁻ ), selenocyanate ions (SeCN ^−). ), Tellurocyanate ion (TeCN ⁻ ), azidodithiocarbonate ion (SCSN ₃ ⁻ ), cyanate ion (OCN ⁻ ), thunderate ion (ONC ⁻ ), azide ion (N ₃ ⁻ ) and the like.

X ^I is preferably fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, isocyanate ion, thiocyanate ion, nitrate ion, nitrite ion, or azide ion, among which chloride Particularly preferred are ions and bromide ions. L ^I is not particularly limited to, may be an organic compound be an inorganic compound, that charge may be also uncharged have a, but an inorganic compound or organic compound uncharged preferable.
Although the preferable specific example of a metal complex represented by general formula ((alpha)) below is given, this invention is not limited to these.

[IrCl ₅ (H ₂ O)] ^2-
[IrCl ₄ (H ₂ O) ₂ ] ^-
[IrCl ₅ (H ₂ O)] ^-
[IrCl ₄ (H ₂ O) ₂ ] ⁰
[IrCl ₅ (OH)] ^3-
[IrCl ₄ (OH) ₂ ] ^2-
[IrCl ₅ (OH)] ^2-
[IrCl ₄ (OH) ₂ ] ^2-
[IrCl ₅ (O)] ^4-
[IrCl ₄ (O) ₂ ] ^5-
[IrCl ₅ (O)] ^3-
[IrCl ₄ (O) ₂ ] ^4-
[IrBr ₅ (H ₂ O)] ^2-
[IrBr ₄ (H ₂ O) ₂ ] ^-
[IrBr ₅ (H ₂ O)] ^-
[IrBr ₄ (H ₂ O) ₂ ] ⁰
[IrBr ₅ (OH)] ^3-
[IrBr ₄ (OH) ₂ ] ^2-
[IrBr ₅ (OH)] ^2-
[IrBr ₄ (OH) ₂ ] ^2-
[IrBr ₅ (O)] ^4-
[IrBr ₄ (O) ₂ ] ^5-
[IrBr ₅ (O)] ^3-
[IrBr ₄ (O) ₂ ] ^4-
[IrCl ₅ (OCN)] ^3-
[IrBr ₅ (OCN)] ^3-
[IrCl ₅ (thiazole)] ^2-
[IrCl ₄ (thiazole) ₂ ] ^-
[IrCl ₃ (thiazole) ₃ ] ⁰
[IrBr ₅ (thiazole)] ^2-
[IrBr ₄ (thiazole) ₂ ] ^-
[IrBr ₃ (thiazole) ₃ ] ⁰
[IrCl ₅ (5-methylthiazole)] ^2-
[IrCl ₄ (5-methylthiazole) ₂ ] ^-
[IrBr ₅ (5-methylthiazole)] ^2-
[IrBr ₄ (5-methylthiazole) ₂ ] ^-

The specific silver halide grains in the silver halide emulsion used in the present invention further preferably have a 6-coordination complex having Ir as a central metal and all six ligands are Cl, Br or I. In this case, Cl, Br, or I may be mixed in the hexacoordinate complex. It is particularly preferable that a hexacoordinate complex containing Ir as a central metal having Cl, Br or I as a ligand is contained in a silver bromide-containing phase in order to obtain a high gradation in high-illuminance exposure.
Specific examples of the 6-coordination complex in which all six ligands are composed of Cl, Br or I and having Ir as a central metal are given below, but iridium in the present invention is not limited to these.
[IrCl ₆ ] ^2-
[IrCl ₆ ] ^3-
[IrBr ₆ ] ^2-
[IrBr ₆ ] ^3-
[IrI ₆ ] ^3-

The metal complex mentioned above is an anion, and when a salt is formed with a cation, the metal complex that is easily dissolved in water as the counter cation is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a mixed solvent with an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. Can do. These iridium complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻³ mol per mol of silver during grain formation, and 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁵ mol is preferably added. Most preferred.

  In the present invention, the above-mentioned iridium complex is added directly to the reaction solution at the time of silver halide grain formation, or added to an aqueous halide solution for forming silver halide grains, or to other solutions to form grains. It is preferably incorporated into the silver halide grains by adding to the reaction solution. It is also preferable to physically ripen the fine particles in which the iridium complex is previously incorporated in the grains and to incorporate them into the silver halide grains. Further, these methods can be combined and contained in the silver halide grains.

  When these complexes are incorporated into silver halide grains, they may be uniformly present inside the grains, but are disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to exist only in the particle surface layer, and it is also preferable to add a layer containing no complex only on the particle surface and containing no complex on the particle surface. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical ripening is performed with fine particles in which the complex is incorporated in the particles to modify the particle surface phase. It is also preferable. Further, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain. The halogen composition at the position where the above complex is contained is not particularly limited, but a hexacoordinate complex having Ir as a central metal, in which all six ligands are Cl, Br, or I, has a silver bromide concentration maximum. It is preferable to contain.

  In the present invention, in addition to iridium, other metal ions can be doped inside and / or on the surface of silver halide grains. As a metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, osmium, or rhodium is particularly preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol It is preferable to use a nitrosyl ion, and it is also preferable to use it in coordination with any of the above metal ions of iron, ruthenium, osmium, lead, cadmium, or zinc, and a plurality of kinds of ligands are contained in one complex molecule. It is also preferable to use it. An organic compound can also be used as the ligand, and preferred organic compounds include a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered or 6-membered heterocyclic compound. . More preferable organic compounds are compounds having a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom in the molecule as a coordination atom to the metal, particularly preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds in which these compounds are used as a basic skeleton and substituents are introduced into them are also preferable.

  A combination of metal ions and ligands is preferably a combination of iron ions, ruthenium ions and cyanide ions. In the present invention, it is preferable to use iridium and these compounds in combination. In these compounds, the cyanide ion preferably accounts for a majority of the coordination number to iron or ruthenium as the central metal, and the remaining coordination sites are thiocyanate, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, It is preferably occupied by pyrazine or 4,4′-bipyridine.

Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron complex or a hexacyanoruthenium complex. It is preferable to add 1 × 10 ⁻⁸ mol to 1 × 10 ⁻² mol per mol of silver, and 1 × 10 ⁻⁶ mol to 5 × 10 5 of these complexes having cyanide ions as ligands. It is most preferable to add ^-4 mol. When ruthenium and osmium are used as the central metals, it is also preferable to use nitrosyl ions, thionitrosyl ions, or water molecules and chloride ions together as ligands. More preferably, a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex is formed, and a hexachloro complex is also preferably formed. These complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ to 1 × 10 ⁻⁶ mol, more preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁶ mol per mol of silver during grain formation. That is.

  The silver halide emulsion used in the present invention is usually chemically sensitized. It is preferable to perform gold sensitization as chemical sensitization. Preferred sensitizers and sensitizing methods are described in JP-A 2003-295375, column 14, line 7 to column 28, line 40.

  In the present invention, in order to perform chalcogen gold sensitization such as selenium gold sensitization and sulfur gold sensitization, a sensitizer that releases chalcogen gold anions described in US Pat. No. 6,638,705B1 is used. Is most preferred. Preferred compounds are described as specific examples of the patent and are preferably incorporated as part of the specification of the present invention.

  To the silver halide emulsion used in the present invention, various compounds or precursors thereof are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. can do. As specific examples of these compounds, those described on pages 39 to 72 of JP-A-62-215272 are preferably used. Furthermore, a 5-arylamino-1,2,3,4-thiatriazole compound (the aryl residue has at least one electron-withdrawing group) described in EP 0447647 is also preferably used.

  In the present invention, in order to enhance the storage stability of the silver halide emulsion, both ends are adjacent to the hydroxamic acid derivative described in JP-A-11-109576 and the carbonyl group described in JP-A-11-327094. Cyclic ketones having a double bond substituted with an amino group or a hydroxyl group (particularly those represented by the general formula (S1), paragraph numbers 0036 to 0071 can be incorporated in the present specification), The sulfo-substituted catechol and hydroquinones described in JP-A-11-143011 (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4- Dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid 3,4,5-trihydroxybenzenesulfonic acid and salts thereof), hydroxylamines represented by the general formula (A) in US Pat. No. 5,556,741 (US Pat. No. 5,556,56) No. 741 column 4 line 56 to 11 column 22 line description is preferably applied to the present invention and is incorporated as part of this specification), JP-A-11-102045 The water-soluble reducing agents represented by the general formulas (I) to (III) are also preferably used in the present invention.

[Silver halide color photographic material]
Next, the silver halide color photographic light-sensitive material relating to the present invention will be described.
As described above, the silver halide color photographic light-sensitive material of the present invention comprises a yellow-colored blue-sensitive silver halide emulsion layer, a magenta-colored green-sensitive silver halide emulsion layer, and a cyan-colored red light sensitive material on a support. A silver halide emulsion layer. Yellow-colored blue-sensitive silver halide emulsion layer is a yellow-colored layer containing a yellow dye-forming coupler, magenta-colored green-sensitive silver halide emulsion layer is a magenta-colored layer containing a magenta dye-forming coupler, cyan-colored red light-sensitive The silver halide emulsion layer functions as a cyan color forming layer containing the cyan dye-forming coupler. 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). Have.

Conventionally known photographic materials and additives can be used in the light-sensitive material of the present invention.
For example, as the photographic support, a transmissive support or a reflective support can be used. As the transmissive support, transparent films such as cellulose nitrate film and polyethylene terephthalate, and polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), NDCA, terephthalic acid and EG are used. A polyester provided with an information recording layer such as a magnetic layer is preferably used. In the present invention, a reflective support (also referred to as a reflective support) is preferable, and the reflective support is particularly laminated with a plurality of polyethylene layers or polyester layers, and such a water-resistant resin layer (laminate layer). A reflective support containing a white pigment such as titanium oxide in at least one layer is preferred.

  In the present invention, more preferred reflective supports include those having a polyolefin layer having fine pores on the paper substrate on the side on which the silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case preferably the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side does not have micropores (eg, polypropylene, polyethylene) and is on a paper substrate. More preferred is a polyolefin (for example, polypropylene or polyethylene) having micropores on the near side. The density of the multi-layer or single-layer polyolefin layer located between the paper substrate and the photographic constituent layer is preferably 0.40 to 1.0 g / ml, more preferably 0.50 to 0.70 g / ml. The thickness of the multilayer or single layer of polyolefin positioned between the paper substrate and the photographic composition layer is preferably 10 to 100 μm, and more preferably 15 to 70 μm. Further, the ratio of the thickness of the polyolefin layer to the paper substrate is preferably 0.05 to 0.2, more preferably 0.1 to 0.15.

  In addition, it is also preferable to provide a polyolefin layer on the opposite side (back surface) to the photographic constituent layer of the paper substrate from the viewpoint of increasing the rigidity of the reflective support. In this case, the back surface polyolefin layer has a matte polyethylene surface. Alternatively, polypropylene is preferable, and polypropylene is more preferable. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further preferably the density is 0.7 to 1.1 g / ml. In the reflective support in the present invention, preferred embodiments relating to the polyolefin layer provided on the paper substrate are disclosed in JP-A-10-333277, JP-A-10-333278, JP-A-11-52513, and JP-A-11-65024. Examples are described in EP0880065 and EP0880066.

Furthermore, it is preferable to contain a fluorescent brightening agent in the water-resistant resin layer. Further, a hydrophilic colloid layer containing the fluorescent brightening agent in a dispersed manner may be separately formed. As the optical brightener, benzoxazole-based, coumarin-based and pyrazoline-based compounds can be preferably used, and benzoxazolylnaphthalene-based and benzoxazolyl stilbene-based fluorescent brighteners are more preferable. Although the usage-amount is not specifically limited, Preferably it is 1-100 mg / m < ² >. The mixing ratio in the case of mixing with a water resistant resin is preferably 0.0005 to 3% by mass, more preferably 0.001 to 0.5% by mass with respect to the resin.

  The reflective support may be a transmissive support or a reflective colloid coated with a hydrophilic colloid layer containing a white pigment. Further, the reflective support may be a support having a specular or second-type diffuse reflective metal surface.

  Further, as a support used in the light-sensitive material of the present invention, a white polyester support or a support in which a layer containing a white pigment is provided on a support having a silver halide emulsion layer is used for a display. May be. In order to further improve the sharpness, an antihalation layer is preferably coated on the silver halide emulsion layer coating side or the back surface of the support. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with either reflected light or transmitted light.

  In the light-sensitive material of the present invention, a dye which can be decolored by processing as described in pages 27 to 76 of European Patent EP0,337,490A2 is applied to a hydrophilic colloid layer for the purpose of improving the sharpness of an image. Among them, oxonol dyes are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or divalent to tetravalent alcohols (for example, trimethylolethane) are added to the water-resistant resin layer of the support. ) Etc. It is preferable to contain 12% by mass or more (more preferably 14% by mass or more) of titanium oxide surface-treated.

  In the light-sensitive material of the present invention, the processing described in pages 27 to 76 of EP 0337490 A2 is carried out on the hydrophilic colloid layer for the purpose of preventing irradiation and halation or improving the safety light safety. It is preferable to add a decolorizable dye (in particular, an oxonol dye or a cyanine dye). Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes degrade color separation and safelight safety when the amount used is increased. As a dye that can be used without deteriorating color separation, water-soluble dyes described in JP-A Nos. 5-127324, 5-127325, and 5-216185 are preferable.

  In the present invention, a colored layer that can be decolored by treatment in place of the water-soluble dye or in combination with the water-soluble dye is used. The colored layer that can be decolored by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably placed under the emulsion layer (support side) that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to select and install only some of them. It is also possible to install a colored layer that has been colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength having the highest optical density in the wavelength range used for exposure (visible light range of 400 nm to 700 nm for normal printer exposure, wavelength of the scanning exposure light source used for scanning exposure). The optical density value at is preferably 0.2 or more and 3.0 or less. More preferably 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

  Any method can be applied to form the colored layer. For example, the dyes described in JP-A-2-282244, page 3 from the upper right column to page 8, and the dyes described in JP-A-3-7931, page 3 from upper right column to page 11, lower left column are solid. A method of incorporating a hydrophilic colloid layer in the form of a fine particle dispersion, a method of mordanting an anionic dye into a cationic polymer, a method of adsorbing a dye to fine particles such as silver halide and fixing it in the layer, JP-A-1-239544 For example, a method using colloidal silver as described in Japanese Patent Publication. As a method of dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but substantially water-soluble at least at pH 8 or more is disclosed in Japanese Patent Application Laid-Open No. Hei. No. 2-308244, pages 4 to 13. Further, for example, a method for mordanting an anionic dye into a cationic polymer is described on pages 18 to 26 of JP-A-2-84737. US Pat. Nos. 2,688,601 and 3,459,563 show preparation methods for colloidal silver as a light absorber. Among these methods, a method of containing a fine powder dye and a method of using colloidal silver are preferable.

  The photosensitive material of the present invention is used for color negative film, color positive film, color reversal film, color reversal photographic paper, color photographic paper display photosensitive material, digital color proof, movie color positive, movie color negative, etc. Materials, digital color proofs, color positives for movies, color reversal photographic papers, and color photographic papers are preferred, and particularly preferred as color photographic papers. As described above, the color photographic paper has at least one yellow-colored blue-sensitive silver halide emulsion layer, magenta-colored green-sensitive silver halide emulsion layer, and cyan-colored red-sensitive silver halide emulsion layer. In general, these silver halide emulsion layers are arranged in the order from the support to the yellow-colored blue-sensitive silver halide emulsion layer, the magenta-colored green-sensitive silver halide emulsion layer, and the cyan-colored red-sensitive halogen halide. It is a silver halide emulsion layer.

However, a different layer structure may be used.
The blue-sensitive silver halide emulsion layer may be disposed at any position on the support. However, when the blue-sensitive silver halide emulsion layer contains tabular grains of green halide, It is preferably coated at a position farther from the support than at least one of the silver halide emulsion layer or the red-sensitive silver halide emulsion layer. From the viewpoint of promoting color development, desilvering, and reducing residual color by sensitizing dye, the blue-sensitive silver halide emulsion layer is coated at the position farthest from the support than the other silver halide emulsion layers. It is preferable to be provided.

  Further, from the viewpoint of reducing Blix fading, the red-sensitive silver halide emulsion layer is preferably the center layer of other silver halide emulsion layers, and from the viewpoint of reducing photobleaching, the red-sensitive silver halide emulsion layer is preferred. Is preferably the lowermost layer. Further, each of the coloring layers of yellow, magenta and cyan may be composed of two layers or three layers. For example, couplers containing no silver halide emulsion as described in JP-A-4-75055, JP-A-9-1114035, JP-A-10-246940, US Pat. No. 5,576,159, etc. It is also preferable to provide a layer adjacent to the silver halide emulsion layer to form a color developing layer.

  As silver halide emulsions and other materials (additives, etc.) and photographic composition layers (layer arrangement, etc.) applied in the present invention, and processing methods and processing additives applied to process this photosensitive material, Disclosed in JP-A-62-215272, JP-A-2-33144, European Patent EP0,355,660A2, and particularly described in European Patent EP0,355,660A2. Are preferably used. Furthermore, JP-A-5-34889, JP-A-4-359249, JP-A-4-313733, JP-A-4-270344, JP-A-5-66527, JP-A-4-34548, JP-A-4-145433. No. 2-854, No. 1-158431, No. 2-90145, No. 3-194539, No. 2-93641, EP-A-0520457A2, and the like. A silver halide color photographic light-sensitive material and a processing method thereof are also preferable.

  In particular, in the present invention, the reflection type support and silver halide emulsion described above, further different metal ion species doped in the silver halide grains, storage stabilizer or antifoggant for silver halide emulsion, chemical enhancement, Sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and its emulsifying dispersion method, color image preservability improving agent (stain inhibitor and anti-fading agent), dye (coloring) As for the layer), the gelatin type, the layer structure of the photosensitive material, the coating pH of the photosensitive material, and the like, those described in each part of the patent literature shown in Table 1 below are particularly preferably applicable.

Other examples of cyan, magenta and yellow couplers used in the present invention include those described in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144. Page 3, upper right column, line 14 to page 18, upper left column, last line, page 30, upper right column, line 6 to page 35, lower right column, line 11 and page 0, line 15 to 27 of EP0355,660A2. Couplers described in the 5th line, 5th page, 30th line to 28th page, 45th page, 29th line to 31st line, 47th page, 23rd line to 63rd page, 50th line are also useful.
In the present invention, compounds represented by the general formulas (II) and (III) of WO 98/33760 and the general formula (D) of JP-A-10-221825 may be added.

  As a cyan dye-forming coupler that can be used in the present invention (sometimes simply referred to as “cyan coupler”), a pyrrolotriazole-based coupler is preferably used, and the general formula (I) or (II) described in JP-A-5-313324 is used. ), Couplers represented by general formula (I) of JP-A-6-347960, and exemplified couplers described in these patents are particularly preferred. Phenol-based and naphthol-based cyan couplers are also preferable. For example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297 are preferable. Other cyan couplers include pyrroloazole-type cyan couplers described in EP 0488248 and EP 0491197A1, and 2,5-diacylaminophenol couplers described in US Pat. No. 5,888,716. US Pat. Nos. 4,873,183 and 4,916,051, pyrazoloazole type cyan couplers having an electron-attracting group and a hydrogen-bonding group at the 6-position, Pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A-8-171185, JP-A-8-311360, and JP-A-8-339060 are also preferable.

  Further, in addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, a 3-hydroxypyridine cyan coupler described in European Patent EP 0333185A2 (among others of the coupler (42) listed as a specific example). A 4-equivalent coupler having a chlorine leaving group to give 2 equivalents, couplers (6) and (9) are particularly preferred) and cyclic active methylene-based cyan couplers described in JP-A 64-32260 (among others) Examples of couplers 3, 8, and 34 listed as specific examples are particularly preferred), pyrrolopyrazole cyan couplers described in EP 0456226A1, and pyrroloimidazole cyan couplers described in EP 0484909 are used. You can also.

  Of these cyan couplers, pyrroloazole cyan couplers represented by the general formula (I) described in JP-A No. 11-282138 are particularly preferred. The couplers (1) to (47) are applied to the present application as they are, and are preferably incorporated as part of the specification of the present application.

  Examples of the magenta dye-forming coupler used in the present invention (sometimes simply referred to as “magenta coupler”) include 5-pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers described in the publicly known literatures in the above table. Among them, a secondary or tertiary alkyl group as described in JP-A-61-65245 is the 2, 3, or 6 position of the pyrazolotriazole ring among them in terms of hue, image stability, color developability, etc. A pyrazolotriazole coupler directly connected to a pyrazoloazole coupler containing a sulfonamide group in the molecule as described in JP-A-61-65246, as described in JP-A-61-147254 Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group, European Patent No. 226,849A, Use of pyrazoloazole couplers having a 6-position alkoxy or aryloxy group as described in the 294,785A Pat are preferred.

  In particular, the magenta coupler is preferably a pyrazoloazole coupler represented by the general formula (M-I) described in JP-A-8-122984. Paragraph Nos. 0009 to 0026 of the patent document are directly applied to the present invention. , Incorporated herein as part of this specification. In addition to this, pyrazoloazole couplers having sterically hindered groups at both the 3-position and the 6-position described in EP 854384 and EP 844640 are also preferably used.

  Further, as yellow dye-forming couplers (sometimes simply referred to as “yellow couplers”), in addition to the compounds described in the above table, a 3- to 5-membered cyclic group is added to the acyl group described in European Patent EP 0447969A1. An acylacetamide type yellow coupler having a structure, a malondianilide type yellow coupler having a cyclic structure described in European Patent EP 0 482 552 A1, European Patent Publication Nos. 935870A1, 953871A1, and 957,72A1 Pyrrole-2 or 3-yl or indole-2 or 3-ylcarbonylacetic acid anilide type couplers described in U.S. Pat. Nos. 5,953,873, 953874, 1,953875A1, etc. Described in the specification of 5,118,599 Acylacetamide yellow couplers or JP acetanilide type yellow couplers heterocyclic acyl group is substituted as described in 2003-173007 JP preferably used having a dioxane structure. Among them, an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group, a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring, or an acetanilide in which a heterocyclic ring is substituted on the acyl group The use of type yellow couplers is preferred.

  These couplers can be used alone or in combination. Is preferably used. Among them, an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group, a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring, or an acetanilide in which a heterocyclic ring is substituted on the acyl group The use of type yellow couplers is preferred. These couplers can be used alone or in combination.

  The coupler used in the present invention is impregnated into a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvent described in the above table. Alternatively, it is preferably dissolved together with a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15, and International Publication WO 88/00723, pages 12 to 30. The described homopolymers or copolymers are mentioned. More preferably, use of a methacrylate or acrylamide polymer, particularly an acrylamide polymer is preferred in view of color image stability.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable.
For example, high molecular weight redox compounds described in JP-A-5-333501, phenidone and hydrazine compounds described in WO98 / 33760, U.S. Pat. No. 4,923,787, etc. White couplers described in Japanese Patent No. 249637, Japanese Patent Application Laid-Open No. 10-282615, German Patent No. 19629142A1, and the like can be used. In particular, in the case of increasing the pH of the developer and speeding up development, German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 842975A1, German Patent No. 1980646A1 And redox compounds described in French Patent No. 2760460A1 and the like are also preferably used.

  In the present invention, it is preferable to use a compound having a triazine skeleton with a high molar extinction coefficient as an ultraviolet absorber, and for example, compounds described in the following patents can be used. These are preferably added to the light-sensitive layer or / and non-photosensitive. For example, JP-A-46-3335, JP-A-55-15276, JP-A-5-197074, JP-A-5-232630, JP-A-5-307232, JP-A-6-218131, and 8- No. 53427, No. 8-234364, No. 8-239368, No. 9-31067, No. 10-115898, No. 10-147777, No. 10-182621, German Patent No. The compounds described in the specification of 19739797A, European Patent No. 711804A and JP-A-8-501291 can be used.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or in combination with gelatin. As a preferable gelatin, the heavy metal contained as impurities such as iron, copper, zinc and manganese is preferably 5 ppm or less, more preferably 3 ppm or less. The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

  In the present invention, an antibacterial / antifungal agent as described in JP-A-63-271247 is added in order to prevent various wrinkles and bacteria that propagate in the hydrophilic colloid layer and degrade the image. Is preferred. Further, the film pH of the photosensitive material is preferably 4.0 to 7.0, more preferably 4.0 to 6.5.

In the present invention, a surfactant can be added to the photosensitive material from the viewpoints of improving the coating stability of the photosensitive material, preventing the generation of static electricity, and adjusting the charge amount. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. In particular, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but are preferably used in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , preferably 1 × 10 ⁻⁴ to 1 × 10 ^{−. 1} g / m ² , more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ² .

  The photosensitive material of the present invention, as shown in the specific example of the image forming apparatus that performs exposure processing on the photosensitive material, develops the exposure process in which light is irradiated according to image information and the light-irradiated photosensitive material. An image can be formed by the development process.

  The photosensitive material of the present invention is a monochromatic high light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) using a combination of a solid state laser using a semiconductor laser and a nonlinear optical crystal. A digital scanning exposure method using density light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) that combines a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and at least one of the exposure light sources is preferably a semiconductor laser.

  The photosensitive material of the present invention is preferably imagewise exposed with coherent light of a blue laser having an emission wavelength of 420 nm to 460 nm. Among blue lasers, it is particularly preferable to use a blue semiconductor laser.

Specifically, as a laser light source, a blue semiconductor laser having a wavelength of 430 to 450 nm (announced by Nichia Chemical Co., Ltd. at the 48th Applied Physics Related Conference in March 2001), a semiconductor laser (oscillation wavelength: About 470 nm of blue laser and semiconductor laser (oscillation wavelength: about 1060 nm) extracted by converting the wavelength of LiNbO ₃ SHG crystal having a waveguide-like inversion domain structure into a waveguide-like inversion domain structure. A green laser with a wavelength of about 530 nm, a red semiconductor laser with a wavelength of about 685 nm (Hitachi type No. HL6738MG), a red semiconductor laser with a wavelength of about 650 nm (Hitachi type No. HL6501MG), etc., which are extracted by converting the wavelength with an SHG crystal of LiNbO ₃ is preferable. Used.

When such a scanning exposure light source is used, the spectral sensitivity maximum wavelength of the photosensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source to be used. In a solid laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be given to the usual three wavelength regions of blue, green, and red. When the exposure time in such scanning exposure is defined as the time for exposing the pixel size when the pixel density is 300 dpi, the preferable exposure time is 1 × 10 ⁻⁴ seconds or less, more preferably 1 × 10 ⁻⁶ seconds. It is as follows.

  The silver halide color photographic light-sensitive material of the present invention can be preferably used in combination with the exposure and development system described in the following known documents. Examples of the developing system include an automatic printing and developing system described in JP-A-10-333253, a photosensitive material conveying apparatus described in JP-A-2000-10206, and an image reading apparatus described in JP-A-11-215312. , An exposure system comprising a color image recording system described in JP-A-11-88619 and JP-A-10-202950, and a digital photo print including a remote diagnosis system described in JP-A-10-210206 And a photo print system including an image recording apparatus described in JP 2000-310822 A.

  Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the table above.

  In the processing of the photosensitive material of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column. The processing materials and processing methods described in the 17th line to the 18th page, lower right column, line 20 are preferably applicable. Further, as the preservative used in the developer, compounds described in the patents listed in the above table are preferably used.

  The photosensitive material of the present invention is preferably applied as a photosensitive material having rapid processing suitability. When rapid processing is performed, the color development time is preferably 30 seconds or shorter, more preferably 25 seconds or shorter and 6 seconds or longer, more preferably 20 seconds or shorter and 6 seconds or longer. Similarly, the bleach-fixing time is preferably 30 seconds or shorter, more preferably 25 seconds or shorter and 6 seconds or longer, more preferably 20 seconds or shorter and 6 seconds or longer. The washing or stabilizing time is preferably 60 seconds or shorter, more preferably 40 seconds or shorter and 6 seconds or longer.

  The color development time is the time from when the photosensitive material enters the color developer until it enters the bleach-fixing solution in the next processing step. For example, when processed by an automatic developing machine, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leaves the color developer and is bleach-fixed in the next processing step. The total of both the time during which air is conveyed toward the bath (so-called air time) is called color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until the next washing or stabilizing bath. The water washing or stabilization time refers to the time (so-called liquid time) that the photosensitive material is in the liquid for the drying process after entering the water washing or stabilizing liquid.

  In the light-sensitive material of the present invention, the color development time is particularly preferably 20 seconds or less (preferably 6 to 20 seconds, more preferably 6 to 15 seconds). Here, in the present invention, color development processing with a color development time of 20 seconds or less means that the color development time described above is 20 seconds or less (not the entire time of color development processing).

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Example 1]
(Preparation of blue-sensitive layer emulsion BH-1) (Comparative Example)
High silver chloride cubic particles were prepared by simultaneously adding silver nitrate and sodium chloride to deionized distilled water containing deionized gelatin and mixing. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from 60% to 80% addition of silver nitrate. From the 80% to 90% addition of silver nitrate, potassium bromide (1.5 mol% per mole of finished silver halide) and K ₄ [Fe (CN) ₆ ] were added. K ₂ [IrCl ₅ (5-methylthiazole)] and K ₂ [IrCl ₆ ] were added from 83% to 88% addition of silver nitrate. K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added from 92% to 98% addition of silver nitrate. When 94% of the addition of silver nitrate was completed, potassium iodide (0.27 mol% per mol of the finished silver halide) was added with vigorous stirring. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.54 μm and a coefficient of variation of 8.5%. This emulsion was subjected to precipitation desalting treatment, and gelatin, compounds Ab-1, Ab-2, Ab-3, and calcium nitrate were added thereto and redispersed.

The redispersed emulsion was dissolved at 40 ° C., and sensitizing dye Dye-1 was added so as to optimize spectral sensitization. Next, sodium benzenethiosulfate, triethylthiourea as a sulfur sensitizer, and compound-1 as a gold sensitizer were added and ripened so as to optimize chemical sensitization. Thereafter, 1- (5-methylureidophenyl) -5-mercaptotetrazole, Compound-2, Compound repeating units 2 or 3 Compounds of the main component represented by -3 (terminal _{X 1} and _{X 2} are hydroxyl groups), Compound -4 and potassium bromide were added to complete the chemical sensitization. The emulsion thus obtained was designated as Emulsion BH-1.

(Preparation of Blue Sensitive Layer Emulsion BL-1) Comparative Example In the preparation of emulsion BH-1, the temperature and the addition rate of the step of simultaneously adding and mixing silver nitrate and sodium chloride were changed, and during the addition of silver nitrate and sodium chloride. Emulsion grains were obtained in the same manner except that the amount of various metal complexes added was changed. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.44 μm and a coefficient of variation of 9.5%. After redispersing this emulsion, Emulsion BL-1 was prepared in the same manner except that the amount of various compounds added was changed from that of BH-1.

(Preparation of blue-sensitive emulsion BH-2 to 4) In the present invention, emulsion BH-1 is an equimolar amount of sensitizing dye Dye-1 added at the time of post-ripening to S-12, S-26 or S-38, respectively. (Total amount) Emulsions differing only in replacement were designated as emulsions BH-2, BH-3, or BH-4, respectively.

(Preparation of blue-sensitive emulsions BL-2 to 4) In the present invention, emulsion BL-1 is an equimolar amount of sensitizing dye Dye-1 added during post-ripening to S-12, S-26 or S-38, respectively. (Total amount) Emulsions that differed only in replacement were designated as emulsions BL-2, BL-3, or BL-4, respectively.

(Preparation of blue-sensitive emulsion BH-5) The emulsion BH-5 was different from the emulsion BH-1 of the present invention only in that inorganic sulfur was added instead of sodium benzenethiosulfate added during post-ripening.

(Preparation of Blue Sensitive Layer Emulsion BL-5) Emulsion BL-5 was different from emulsion BL-1 of the present invention only in that inorganic sulfur was added instead of sodium benzenethiosulfate added during post-ripening.

(Preparation of blue-sensitive emulsion BH-6) In the present invention, emulsion BH-6 was different from emulsion BH-1 except that 80 mol% of sodium benzenethiosulfate added during post-ripening was replaced with Z-8. .

(Preparation of Blue-Sensitive Layer Emulsion BL-6) The Emulsion BL-6 was different from Emulsion BL-1 except that 80 mol% of sodium benzenethiosulfate added during post-ripening was replaced with Z-8. .

(Preparation of blue-sensitive layer emulsion BH-7) In the present invention, emulsion BH-1 was prepared by adding 80 mol% of sensitizing dye Dye-1 added during post-ripening to S-12 and S-38 (S-12 and S- Emulsion BH-7 was obtained by changing the emulsion only in that 38 was used in an equimolar amount.

(Preparation of Blue Sensitive Layer Emulsion BL-7) In the Present Invention Further, Emulsion BL-1 is obtained by adding 80 mol% of sensitizing dye Dye-1 added during post-ripening to S-12 and S-38 (S-12 and S- Emulsion BL-7 was prepared in the same manner except that 38 was used in an equimolar amount).

(Preparation of green sensitive layer emulsion GH-1)
High silver chloride cubes by mixing silver nitrate, sodium chloride, and potassium bromide (0.5 mol% per mol of the finished silver halide) with deionized distilled water containing stirred deionized gelatin. Particles were prepared. In the course of this preparation, K ₄ [Ru (CN) ₆ ] was added from 80% to 90% addition of silver nitrate. K ₂ [IrCl ₆ ] and K ₂ [RhBr ₅ (H ₂ O)] were added from 83% to 88% addition of silver nitrate. The obtained emulsion grains were monodisperse cubic silver bromochloride grains having a side length of 0.45 μm and a coefficient of variation of 8.0%. This emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion was dissolved at 40 ° C. and sodium benzenethiosulfate, p-glutaramide phenyl disulfide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (bis (1,4,5-trimethyl-1) as a gold sensitizer. , 2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate) and ripened to optimize chemical sensitization. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4 and potassium bromide were added. Furthermore, spectral sensitization was performed by adding sensitizing dyes S-101, S-102, S-103 and S-104 as sensitizing dyes during the emulsion preparation process. The emulsion thus obtained was designated as Emulsion GH-1.

(Preparation of emulsion RH-1 for red-sensitive layer)
High silver chloride cubes by mixing silver nitrate, sodium chloride, and potassium bromide (0.5 mol% per mol of the finished silver halide) with deionized distilled water containing stirred deionized gelatin. Particles were prepared. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from 60% to 80% addition of silver nitrate. K ₄ [Ru (CN) ₆ ] was added from the time point when the addition of silver nitrate was 80% to 90%. K ₂ [IrCl ₆ ] was added from 83% to 88% addition of silver nitrate. The obtained emulsion grains were monodispersed cubic silver bromochloride emulsion grains having a cube side length of 0.40 μm and a coefficient of variation of 10%. The obtained emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion is dissolved at 40 ° C., and sensitizing dye S-105, compound-5, triethylthiourea as a sulfur sensitizer and compound-1 as a gold sensitizer are added to optimize chemical sensitization. Aged. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4, and potassium bromide were added. The emulsion thus obtained was designated as Emulsion RH-1.

(First layer coating solution preparation)
34 g of yellow coupler (Ex-Y), 1 g of color image stabilizer (Cpd-1), 1 g of color image stabilizer (Cpd-2), 8 g of color image stabilizer (Cpd-8), color image stabilizer (Cpd-18) ) 1 g, color image stabilizer (Cpd-19) 2 g, color image stabilizer (Cpd-20) 15 g, color image stabilizer (Cpd-21) 1 g, color image stabilizer (Cpd-23) 15 g, additives ( ExC-1) 0.1 g, color image stabilizer (UV-A) 1 g was dissolved in solvent (Solv-4) 23 g, solvent (Solv-6) 4 g, solvent (Solv-9) 23 g and ethyl acetate 60 ml, This solution was emulsified and dispersed in 270 g of a 20% by weight gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate with a high-speed stirring emulsifier (dissolver), and water was added to prepare 900 g of emulsified dispersion A.
On the other hand, the emulsified dispersion A and the emulsions BH-1 and BL-1 were mixed and dissolved to prepare a first layer coating solution having a composition described later. The emulsion coating amount indicates the silver coating amount.

(Second to seventh layer coating solution preparation)
The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. (H-1), (H-2), and (H-3) hardeners were used as gelatin hardeners for each layer. Also, Ab-1 to each layer, Ab-2, Ab-3 , and Ab-4 the total amount respectively ^{14.0mg / m 2, 62.0mg / m} 2, 5.0mg / m 2 and 10.0 mg / m It added so that it might become ² .

1- (3-Methylureidophenyl) -5-mercaptotetrazole was added to the second, fourth and sixth layers, 0.2 mg / m ² , 0.2 mg / m ² and 0.6 mg / m ^{2 respectively.} It added so that it might become. For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is respectively 1 × 10 ⁻⁴ mol, 2 ×, per mol of silver halide. ^10-4 mol was added. 0.05 g / m ² of a copolymer latex of methacrylic acid and butyl acrylate (weight ratio 1: 1, average molecular weight 200,000 to 400,000) was added to the red sensitive emulsion layer. The second layer, was added the fourth layer and the sixth layer in disodium catechol-3,5-disulfonate as respectively a ^{6mg / m 2, 6mg / m} 2, 18mg / m 2. Sodium polystyrene sulfonate was added to each layer as necessary to adjust the viscosity of the coating solution. In order to prevent irradiation, the following dyes were added (the amount in parentheses represents the coating amount).

(Layer structure)
The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.
Support Polyethylene resin-laminated paper [White pigment (TiO ₂ ; content: 16% by mass, ZnO; content: 4% by mass), polyethylene brightening agent (4,4′-bis (5- Methylbenzoxazolyl) stilbene (content 0.03% by mass) and bluish dye (ultraviolet, content 0.33% by mass) The amount of polyethylene resin is 29.2 g / m ² )
First layer (blue photosensitive emulsion layer)
Emulsion (5: 5 mixture of BH-1 and BL-1 (silver molar ratio)) 0.16
Gelatin 1.32
Yellow coupler (EX-Y) 0.34
Color image stabilizer (Cpd-1) 0.01
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-8) 0.08
Color image stabilizer (Cpd-18) 0.01
Color image stabilizer (Cpd-19) 0.02
Color image stabilizer (Cpd-20) 0.15
Color image stabilizer (Cpd-21) 0.01
Color image stabilizer (Cpd-23) 0.15
Additive (ExC-1) 0.001
Color image stabilizer (UV-A) 0.01
Solvent (Solv-4) 0.23
Solvent (Solv-6) 0.04
Solvent (Solv-9) 0.23

Second layer (color mixing prevention layer)
Gelatin 0.78
Color mixing inhibitor (Cpd-4) 0.05
Color mixing inhibitor (Cpd-12) 0.01
Color image stabilizer (Cpd-5) 0.006
Color image stabilizer (Cpd-6) 0.05
Color image stabilizer (UV-A) 0.06
Color image stabilizer (Cpd-7) 0.006
Solvent (Solv-1) 0.06
Solvent (Solv-2) 0.06
Solvent (Solv-5) 0.07
Solvent (Solv-8) 0.07

Third layer (green photosensitive emulsion layer)
Emulsion (GH-1) 0.12
Gelatin 0.95
Magenta coupler (ExM) 0.12
UV absorber (UV-A) 0.03
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-6) 0.08
Color image stabilizer (Cpd-7) 0.005
Color image stabilizer (Cpd-8) 0.01
Color image stabilizer (Cpd-9) 0.01
Color image stabilizer (Cpd-10) 0.005
Color image stabilizer (Cpd-11) 0.0001
Color image stabilizer (Cpd-20) 0.01
Solvent (Solv-3) 0.06
Solvent (Solv-4) 0.12
Solvent (Solv-6) 0.05
Solvent (Solv-9) 0.16

Fourth layer (color mixing prevention layer)
Gelatin 0.65
Color mixing inhibitor (Cpd-4) 0.04
Color mixing inhibitor (Cpd-12) 0.01
Color image stabilizer (Cpd-5) 0.005
Color image stabilizer (Cpd-6) 0.04
Color image stabilizer (UV-A) 0.05
Color image stabilizer (Cpd-7) 0.005
Solvent (Solv-1) 0.05
Solvent (Solv-2) 0.05
Solvent (Solv-5) 0.06
Solvent (Solv-8) 0.06

5th layer (red photosensitive emulsion layer)
Emulsion (RH-1) 0.10
Gelatin 1.11
Cyan coupler (ExC-1) 0.11
Cyan coupler (ExC-2) 0.01
Cyan coupler (ExC-3) 0.04
Color image stabilizer (Cpd-1) 0.03
Color image stabilizer (Cpd-7) 0.01
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-10) 0.001
Color image stabilizer (Cpd-14) 0.001
Color image stabilizer (Cpd-15) 0.18
Color image stabilizer (Cpd-16) 0.002
Color image stabilizer (Cpd-17) 0.001
Color image stabilizer (Cpd-18) 0.05
Color image stabilizer (Cpd-19) 0.04
Color image stabilizer (UV-5) 0.10
Solvent (Solv-5) 0.19

Sixth layer (UV absorbing layer)
Gelatin 0.34
Ultraviolet absorber (UV-B) 0.24
Compound (S1-4) 0.0015
Solvent (Solv-7) 0.11

Seventh layer (protective layer)
Gelatin 0.82
Additive (Cpd-22) 0.03
Liquid paraffin 0.02
Surfactant (Cpd-13) 0.02

  The sample prepared as described above was designated as Sample 001. Sample 001 was prepared by changing the silver halide emulsion of the blue light-sensitive emulsion layer as shown in Table 2 and designated as samples 002 to 007. The silver molar ratio of the two emulsions in the blue light-sensitive emulsion layer was the same as that of Sample 001.

Each of the above samples was processed into a 127 mm wide roll, and the processed product stored in roll form at 40 ° C. and 60% RH for 7 days was converted into a digital minilab Frontier 350 (Fuji Photo Film Co., Ltd.) using Gray uniform exposure was performed at the sub-scanning conveyance speed. Further, the sheet was passed through the conveyance section at the following sub-scanning conveyance speeds A and B without exposure. As the sub-scanning roller pair, the frontier 350 roller was used as it was.
A: Sub-scanning conveyance speed 80mm / sec
B: Sub-scanning conveyance speed 100 mm / sec
In this test, a digital minilab and a photosensitive material were brought into a constant temperature room at 35 ° C. and 80% RH, and the experiment was started when the environment was sufficiently constant.
Next, the drive roller of the sub-scan exposure part of the frontier 350 is a hard roller (drive side) having a thickness of about 50 μm containing resin beads on the surface of the metal shaft, and the nip roller side has a hardness of A55. A similar experiment was conducted using a modified machine that was different from the sub-scanning roller pair using a roller having a rubber layer (EPDM).

As a laser light source, a blue laser of about 470 nm and a semiconductor laser (oscillation wavelength of about 1060 nm) extracted by converting the wavelength of a semiconductor laser (oscillation wavelength of about 940 nm) with a LiNbO ₃ SHG crystal having a waveguide-like inversion domain structure are used. A green laser having a wavelength of about 530 nm and a red semiconductor laser having a wavelength of about 650 nm (Hitachi type No. HL6501MG) extracted by wavelength conversion using a LiNbO ₃ SHG crystal having a waveguide-like inversion domain structure were used. The laser beams of the three colors are moved in the direction perpendicular to the sub-scanning conveyance direction (main scanning direction) by the polygon mirror so that the scanning exposure can be sequentially performed on the sample. Variation in the amount of light due to the temperature of the semiconductor laser is suppressed by keeping the temperature constant using a Peltier element. The effective beam diameter was 80 μm, the scanning pitch was 42.3 μm (600 dpi), and the exposure time per pixel was 7 to 8 × 10 ⁻⁸ seconds. The temperature of the semiconductor laser was made constant by using a Peltier element in order to suppress the change in light quantity due to temperature.

  Using the sample 007, continuous processing (running test) was performed in the following processing steps until the volume of the color developer replenisher was twice the volume of the color developer tank. Each photosensitive material was processed in the following processing steps using this running processing solution.

Processing temperature Temperature Time Replenishment amount *
Color development 45.0 ℃ 17 seconds 35mL
Bleach fixing 40.0 ℃ 17 seconds 30mL
Rinse 1 45.0 ° C. 4 seconds −
Rinse 2 45.0 ° C. 4 seconds −
Rinse 3 ** 45.0 ° C 3 seconds-
Rinse 4 45.0 ° C 5 seconds 121mL
Drying 80 ° C 15 seconds (Note)
* Replenishment amount per 1 m ^{2 of} photosensitive material ** A rinsing screening system RC50D manufactured by Fuji Photo Film Co., Ltd. is attached to the rinsing 3, and the rinsing liquid is taken out from the rinsing 3 and sent to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse 4 and the concentrated solution is returned to the rinse 3. The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours a day. The rinsing was a 4-tank counterflow system from 1 to 4.

The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Optical brightener (FL-3) 4.0g 8.0g
Residual color reducing agent (SR-1) 3.0 g 5.5 g
Triisopropanolamine 8.8g 8.8g
Sodium p-toluenesulfonate 10.0 g 10.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.10g
Potassium chloride 10.0 g ―
Sodium 4,5-dihydroxybenzene-1,3-disulfonate
0.50g 0.50g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine
8.5g 14.0g
4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline, 3/2 sulfate, monohydrate
7.0g 19.0g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.25 12.6

[Bleaching fixer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Ammonium thiosulfate (750 g / L) 107 mL 214 mL
Succinic acid 29.5g 59.0g
Ethylenediaminetetraacetic acid iron (III) ammonium
47.0g 94.0g
Ethylenediaminetetraacetic acid 1.4 g 2.8 g
Nitric acid (67%) 17.5g 35.0g
Imidazole 14.6g 29.2g
Ammonium sulfite 16.0 g 32.0 g
Potassium metabisulfite 23.1g 46.2g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with 25 ° C, nitric acid and aqueous ammonia) 6.00 6.00

[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5μS / cm or less) 1000mL 1000mL
pH (25 ° C.) 6.5 6.5

<Evaluation of uneven exposure>
Output 10 uniform gray samples in 2L size continuously so that the R, G, and B densities determined by the X-rite densitometer (equipped with status A-R, G, and B filters) are 1.0, Exposure unevenness was determined. At this time, the sample 001 was exposed using a commercially available frontier 350 (manufactured by Fuji Photo Film Co., Ltd.) under the same uniform gray condition, and the processed product was used as a comparative sample. It was visually observed and expressed as ◯ in the case of being equivalent, Δ in the case of being slightly inferior, and × in the case of being inferior.
<Evaluation of muscle unevenness>
The sample was passed through a pair of sub-scanning rollers without exposure, and 100 consecutive white samples after the above processing were prepared in a 2L size for each sample, and yellow streaks occurred and the frequency was observed.
The evaluation rank is as follows.
；: Not seen at all ◯: Some samples are visible ×: Results of these tests in which many streaky irregularities are seen are shown in Table 3.

From Table 3, in the image forming method using the silver halide color photographic light-sensitive material of the present invention, even when the sub-scanning conveyance speed is increased (improvement of productivity), the occurrence of uneven exposure and streak is hardly observed, It can be seen that high quality prints can be obtained.

[Example 2]
(Preparation of blue-sensitive layer emulsion B-1)
Silver nitrate, sodium chloride and potassium bromide were simultaneously added to stirred deionized distilled water containing deionized gelatin at 40 ° C. while controlling the pAg and pH, and the silver chloride content was 99.8 mol%. High silver chloride cubic grains having a content of 0.2 mol% were prepared. In the course of this preparation, K ₂ [IrCl ₆ ] and K ₄ [Fe (CN) ₆ ] · 3H ₂ O were added from 3% to 92% addition of silver nitrate. Further, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution. The obtained emulsion grains were monodisperse cubic silver chlorobromide grains having a projected area circle diameter of 0.64 μm and a grain size distribution variation coefficient of 0.07.

  The obtained emulsion was dissolved, sodium thiosulfate, chloroauric acid, sensitizing dye Dye-2, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1-phenyl-5-mercaptotetrazole, 1- (4 -Ethoxyphenyl) -5-mercaptotetrazole was added, and chemical sensitization was performed at 60 ° C. The emulsion thus obtained was designated as Emulsion BH-11.

Emulsion BH-11 is the same as emulsion BH-11 except that the addition times of silver nitrate, sodium chloride and potassium bromide were changed, respectively. Projected area circle diameter 0.50 μm, grain size distribution variation coefficient 0.07, silver chloride contained Emulsion BL-11, a monodispersed cubic emulsion having a rate of 99.8 mol% and a silver bromide content of 0.2 mol%, was prepared. Emulsion BH-11 and Emulsion BL-11 were mixed in a silver ratio of 1: 1 to prepare a blue-sensitive layer emulsion B-1.

(Preparation of blue-sensitive emulsion B-2) The emulsion BH-11 is different from the emulsion BH-11 except that 80 mol% of the sensitizing dye Dye-2 added during post-ripening is changed to S-38. It was set to -22.

Furthermore, emulsion BL-22, which differs from emulsion BL-11 only in that 80 mol% of sensitizing dye Dye-2 added at the time of post-ripening was changed to S-38, was prepared. Emulsion BH-22 and Emulsion BL-22 were mixed at a silver ratio of 1: 1 to prepare blue-sensitive layer emulsion B-2.

(Preparation of green-sensitive layer emulsion G-1)
Silver nitrate, sodium chloride and potassium bromide were simultaneously added to stirred deionized distilled water containing deionized gelatin at 40 ° C. while controlling the pAg and pH, and the silver chloride content was 99.7 mol%. High silver chloride cubic grains having a content of 0.3 mol% were prepared. In the course of this preparation, K ₂ [IrCl ₆ ] and K ₄ [Fe (CN) ₆ ] · 3H ₂ O were added from 3% to 92% addition of silver nitrate. Further, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution. The obtained emulsion grains were monodisperse cubic silver chlorobromide grains having a projected area circle diameter of 0.50 μm and a coefficient of variation in grain size distribution of 0.08.

  The obtained emulsion was dissolved, sodium thiosulfate, chloroauric acid, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1-phenyl-5-mercaptotetrazole, 1- (4-ethoxyphenyl) -5- Mercaptotetrazole and sensitizing dye G-1 were added, and chemical sensitization was performed at 60 ° C. The emulsion thus obtained was designated as Emulsion GH-11.

  Emulsion GH-11 is the same as in emulsion GH-11 except that the addition times of silver nitrate, sodium chloride, and potassium bromide were changed, respectively. Projected area circle diameter 0.45 μm, grain size distribution variation coefficient 0.07, silver chloride contained Emulsion GL-11, a monodispersed cubic emulsion having a rate of 99.7 mol% and a silver bromide content of 0.3 mol%, was prepared. Emulsion GH-11 and Emulsion GL-11 were mixed at a silver ratio of 1: 1 to prepare a green sensitive layer emulsion G-1.

(Preparation of emulsion R-1 for red-sensitive layer)
Silver nitrate, sodium chloride and potassium bromide were simultaneously added to stirred deionized distilled water containing deionized gelatin at 40 ° C. while controlling the pAg and pH, and the silver chloride content was 99.8 mol%. High silver chloride cubic grains having a content of 0.2 mol% were prepared. In the course of this preparation, K ₂ [IrCl ₆ ] and K ₄ [Fe (CN) ₆ ] · 3H ₂ O were added from 3% to 92% addition of silver nitrate. Further, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution. The obtained emulsion grains were monodisperse cubic silver chlorobromide grains having a projected area circle diameter of 0.40 μm and a grain size distribution variation coefficient of 0.08.

  The obtained emulsion was dissolved, sodium thiosulfate, chloroauric acid, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1-phenyl-5-mercaptotetrazole, 1- (4-ethoxyphenyl) -5- Mercaptotetrazole, sensitizing dye R-1, sensitizing dye R-2, and stabilizer S-1 were added, and chemical sensitization was performed at 60 ° C. The emulsion thus obtained was designated as Emulsion RH-11.

  Emulsion RH-11 is the same as emulsion RH-11 except that the addition times of silver nitrate, sodium chloride and potassium bromide were changed, respectively. Projected area circle diameter 0.35 μm, grain size distribution variation coefficient 0.07, silver chloride contained Emulsion RL-11, a monodispersed cubic emulsion having a rate of 99.7 mol% and a silver bromide content of 0.3 mol%, was prepared. Emulsion RH-11 and Emulsion RL-11 were mixed at a silver ratio of 1: 1 to prepare a red-sensitive layer emulsion R-1.

(Preparation of sample 101)
The emulsion layer coated surface of paper pulp with a basis weight of 180 g / m ² is laminated with high-density molten polyethylene containing a surface-treated anatase-type titanium oxide dispersed at a content of 15% by mass, and the back surface has a high density. The reflective support on which polyethylene was laminated was subjected to corona discharge treatment to provide a gelatin subbing layer, and then each of the following photographic constituent layers was applied to prepare Sample 101 which is a silver halide color photographic light-sensitive material. In addition, the silver halide emulsion described in the table is represented by a value converted to silver.

Tetrakis (vinylsulfonylmethyl) methane and 2,4-dichloro-6-hydroxy-s-triazine sodium were added to the second layer, the fourth layer, and the seventh layer as hardeners. In addition, each layer has a surfactant sulfosuccinate di (2-ethylhexyl) · sodium and sulfosuccinate di (2,2,3,3,4,4,5) as coating aids for adjusting the surface tension. 5, -Octafluoropentyl) .sodium was added. Also, Ab-1, Ab-2 , Ab-3 and Ab-4 the total amount respectively 14.0 mg / m ² in each ^{layer, 62.0mg / m 2, 5.0mg /} m 2 and 10.0 mg / m ² It added so that it might become. Furthermore, in order to prevent irradiation, the following dyes were added (the amount in parentheses represents the coating amount).

First layer (blue-sensitive layer)
Gelatin 1.10
Emulsion (5: 5 mixture of BH-1 and BL-1 (silver molar ratio)) 0.24
Yellow coupler (Y-1) 0.45
Color image stabilizer (ST-1) 0.05
Color image stabilizer (ST-2) 0.05
Color image stabilizer (ST-5) 0.10
2,5-di-t-octylhydroquinone 0.005
Pt-octylphenol 0.08
Poly (t-butylacrylamide) 0.04
Dinonyl phthalate 0.05
Dibutyl phthalate 0.15

Second layer (intermediate layer)
Gelatin 1.20
2,5-di-t-octylhydroquinone 0.02
2,5-Di-sec-dodecyl hydroquinone 0.03
2,5-Di-sec-tetradecylhydroquinone 0.06
2-sec-dodecyl-5-sec-tetradecylhydroquinone
0.03
2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone
0.03
Di-i-decyl phthalate 0.04
Dibutyl phthalate 0.02

Third layer (green-sensitive layer)
Gelatin 1.30
Emulsion (G-1) 0.12
Magenta coupler (M-1) 0.20
Color image stabilizer (ST-3) 0.10
Color image stabilizer (ST-4) 0.02
Di-i-decyl phthalate 0.10
Dibutyl phthalate 0.10

Fourth layer (UV absorbing layer)
Gelatin 0.94
Ultraviolet absorber (UV-1) 0.17
Ultraviolet absorber (UV-2) 0.27
2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone
0.06

5th layer (red-sensitive layer)
Gelatin 1.00
Emulsion (R-1) 0.17
Cyan coupler (C-1) 0.22
Cyan coupler (C-2) 0.06
Color image stabilizer (ST-1) 0.06
2,5-di-t-octylhydroquinone 0.003
Dibutyl phthalate 0.10
Dioctyl phthalate 0.20

Sixth layer (UV absorbing layer)
Gelatin 0.40
Ultraviolet absorber (UV-1) 0.07
Ultraviolet absorber (UV-2) 0.12
2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone
0.02

Seventh layer (protective layer)
Gelatin 0.70
Di-i-decyl phthalate 0.002
Dibutyl phthalate 0.002
Silicon dioxide 0.003

  A sample 102 different from the sample prepared as described above and sample 101 only in that the silver halide emulsion of the blue photosensitive emulsion layer was changed to B-2 was prepared.

Each of the above samples was processed into a 127 mm wide roll, and the processed product stored in a roll at 35 ° C. and 55% RH for 14 days was subjected to an exposure test and a conveyance test under the same conditions as in Example 1.
In the development processing, the sample 102 was used, and the continuous processing (running test) was performed in the following processing steps until the capacity of the color developer replenisher was double the color developer tank capacity. Each photosensitive material was processed in the following processing steps using this running processing solution.

Processing temperature Temperature Time Replenishment amount *
Color development 45.0 ℃ 27 seconds 35mL
Bleach fixing 40.0 ℃ 27 seconds 30mL
Rinse 1 45.0 ° C. 7 seconds −
Rinse 2 45.0 ° C. 7 seconds −
Rinse 3 ** 45.0 ° C 5 seconds-
Rinse 4 45.0 ° C 8 seconds 121mL
Drying 80 ° C 24 seconds (Note)
* Replenishment amount per 1 m ^{2 of} photosensitive material ** A rinsing screening system RC50D manufactured by Fuji Photo Film Co., Ltd. is attached to the rinsing 3, and the rinsing liquid is taken out from the rinsing 3 and sent to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse 4 and the concentrated solution is returned to the rinse 3. The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours a day. The rinsing was a 4-tank counterflow system from 1 to 4.

The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Optical brightener (FL-1) 2.2g 5.1g
Optical brightener (FL-2) 0.35 g 1.75 g
Triisopropanolamine 8.8g 8.8g
Polyethylene glycol average molecular weight 300 10.0 g 10.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.20g
Potassium chloride 10.0 g −
Sodium 4,5-dihydroxybenzene-1,3-disulfonate
0.50g 0.50g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine
8.5g 14.0g
4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline, 3/2 sulfate, monohydrate
4.8g 14.0g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.15 12.40

[Bleaching fixer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Ammonium thiosulfate (750 g / L) 107 mL 214 mL
m-Carboxybenzenesulfinic acid 8.3 g 16.5 g
Ethylenediaminetetraacetic acid iron (III) ammonium 47.0 g 94.0 g
Ethylenediaminetetraacetic acid 1.4 g 2.8 g
Nitric acid (67%) 16.5g 33.0g
Imidazole 14.6g 29.2g
Ammonium sulfite 16.0 g 32.0 g
Potassium metabisulfite 23.1g 46.2g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with nitric acid and aqueous ammonia at 25 ° C.) 6.5 6.5

[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5μS / cm or less) 1000mL 1000mL
pH (25 ° C.) 6.5 6.5

From Table 4, in the image forming method using the silver halide color photographic light-sensitive material of the present invention, even when the sub-scanning conveyance speed is increased, the occurrence of uneven exposure and uneven stripe is hardly observed. It can be seen that high-quality prints without defects can be obtained .

[Example 3]
The sample produced in Example 1 was subjected to gray uniform exposure with the following exposure apparatus, and streak unevenness was evaluated in the same manner as in Example 1. As a light source, a blue semiconductor laser having a wavelength of about 440 nm was used instead of the blue laser of about 470 nm as the light source of Example 1 (Nichia Chemical Co., Ltd. announced at the 48th Applied Physics Related Conference in March 2001) A different light source was used. Also in this case, the image forming method using the silver halide color photographic light-sensitive material of the present invention can produce high-quality prints with no defects and no defects even though the sub-scanning conveyance speed is high. I understood.

1 is a schematic view showing an image forming apparatus of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Image forming apparatus 12 Scanner 13 Image processing apparatus 14 Printer 15 Processor 16 Development processing part 17 Drying process part 18 Return part 19 Sorter 20 Supply part 20a Magazine 20b Magazine 21a Pull-out roller pair 21b Pull-out roller pair 22 Back printing part 24 Registration part 26 Exposure unit 28 Sub-scanning receiving unit 30 Distribution unit 32 Unloading unit 34 Control unit 36 Exposure unit 40 Back print head 44 Registration roller pair 46 Sub-scanning roller pair 48 Sub-scanning roller pair 50 Position detection sensor 58 Position detection sensor 60 Conveyance Roller 70 Conveying roller 71 Conveying roller 72 Conveying roller 74 Conveying roller 76 Conveying roller 78 Conveying roller 80 Conveying roller 82 Exit 84 Exit 86 Accumulation tray 200 Developing tank 202 Fixing and bleaching tank 204 First washing tank 206 Second washing tank 20 Third washing tank 210 fourth water washing tank 302 transport unit 304 the unification unit 322 Tray A photosensitive material r exposure position L light beam α conveyance path β conveying path

Claims (4)

Halogenation having at least one blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, a magenta dye-forming green-sensitive silver halide emulsion layer, and a cyan dye-forming red-sensitive silver halide emulsion layer, respectively, on the support An image forming method for forming an image by starting color development after performing scanning exposure on a silver color photographic light-sensitive material while being transported by a pair of image exposure transport rollers, wherein the silver halide during scanning exposure The sub-scanning conveyance speed of the color photographic photosensitive material is 90 mm / sec or more, the scanning exposure is performed during horizontal conveyance, and the image exposure conveyance roller is formed by applying a urethane coat containing resin beads on a metal shaft. It was made from a hard roller, further silver halide emulsion of silver chloride content contained in the blue-sensitive silver halide emulsion layer of the silver halide color photographic light-sensitive material 0 mol% or more and a color image forming method, characterized by being spectrally sensitized by at least one dye represented by the following general formula (I).

In general formula (I), X ¹ and X ² each independently represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a nitrogen atom or a carbon atom. Y ¹ represents a furan ring, a pyrrole ring, a thiophene ring, or a benzene ring that may be condensed with another 5- to 6-membered carbon ring or heterocyclic ring or may have a substituent. Y ² represents an atomic group necessary for forming a benzene ring or a 5- to 6-membered unsaturated heterocyclic ring, and has a substituent even if it is condensed with another 5- to 6-membered carbocyclic or heterocyclic ring. You may do it. Note that the bond between two carbon atoms to which Y ¹ and Y ² are condensed may be a single bond or a double bond. One of R ¹ and R ² represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. L ¹ represents a methine group. M ¹ represents a counter ion, and m ¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule. The color image forming method according to claim 1, wherein the dye represented by formula (I) is a dye represented by the following general formula (II) or (III).

In the general formula (II), Y ¹¹ represents an oxygen atom, a sulfur atom or N—R ¹³ , and R ¹³ represents a hydrogen atom or an alkyl group. V ¹⁵ and V ¹⁶ each independently represents a hydrogen atom or a monovalent substituent. X ¹¹ and X ¹² each independently represents an oxygen atom or a sulfur atom. One of R ¹¹ and R ¹² represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. V ¹¹ , V ¹² , V ¹³ and V ¹⁴ each independently represents a hydrogen atom or a monovalent substituent. M ¹¹ represents a counter ion, and m ¹¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule.

In the general formula (III), Y ²¹ represents an oxygen atom, a sulfur atom or N—R ²³ , and R ²³ represents a hydrogen atom or an alkyl group. V ²⁵ and V ²⁶ each independently represents a hydrogen atom or a monovalent substituent. X ²¹ and X ²² each independently represent an oxygen atom or a sulfur atom. One of R ²¹ and R ²² represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. V ²¹ , V ²² , V ²³ and V ²⁴ represent a hydrogen atom or a monovalent substituent. M ²¹ represents a counter ion, and m ²¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule. The color image forming method according to claim 1 in which the dye represented by the general formula (I) is characterized in that it is a dye represented by the following general formula (IV).

In the general formula (IV), X ³¹ and X ³² represent an oxygen atom or a sulfur atom. One of R ³¹ and R ³² represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. V ³¹ , V ³² , V ³³ , V ³⁴ , V ³⁵ , V ³⁶ , V ³⁷ and V ³⁸ each independently represent a hydrogen atom or a monovalent substituent, and two adjacent substituents are linked to each other. A condensed ring may be formed. M ³¹ represents a counter ion, and m ³¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule. Halogenation having at least one blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, a magenta dye-forming green-sensitive silver halide emulsion layer, and a cyan dye-forming red-sensitive silver halide emulsion layer, respectively, on the support An image forming method for forming an image by starting color development after performing scanning exposure on a silver color photographic light-sensitive material while being transported by a pair of image-exposure transport rollers. The sub-scan transport speed is 90 mm / sec or more, the scanning exposure is performed at the time of horizontal transport, and the image exposure transport roller is a hard roller formed by applying a urethane coat containing resin beads on a metal shaft. Further, the silver halide emulsion contained in the blue-sensitive silver halide emulsion layer of the silver halide color photographic light-sensitive material has a silver chloride content of 90 mol% or more and is inorganic. Color image forming method characterized in that it contains at least one represented by the yellow or under following general formula (Z).
General formula (Z)
R ⁴¹ -S-S-R ⁴²
In the general formula (Z), R ⁴¹ and R ⁴² each independently represents an aliphatic group or an aromatic group. Here, R ⁴¹ and R ⁴² may be bonded to each other to form a ring.

Images