JP2003255482A - Color image forming method using silver halide color photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To ensure suitability to image output based on digital data for area modulation and to enhance image quality. <P>SOLUTION: In a color image forming method, a silver halide color photosensitive material having silver halide emulsion layers, a color mixture preventing layer and a protective layer is used, wherein the silver halide emulsion of at least one of the silver halide emulsion layers comprises grains of at least one silver halide selected from the group comprising silver chlorobromide, silver chloroiodide and silver chloroiodobromide having ≥95 mol% silver chloride content and the silver halide grains have a region whose silver bromide and/or silver iodide content is higher than that of the other region, the photosensitive material is exposed on the basis of digital image data for area modulation converted to digital data for exposure depending on an exposure device, and a processing solution used contains a compound having a sulfo group and having specified triazine rings at both ends of each molecule. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an image of a silver halide color light-sensitive material, and more specifically, it is suitable for image output based on digital image data for area modulation, and is capable of improving image quality, especially density unevenness and scratches, and sharpness. The present invention relates to an image forming method which is excellent in degree and has reduced yellow coloring on a white background. Furthermore, the present invention relates to an image forming method excellent in high-illuminance exposure suitability and rapid processing suitability. In particular, the present invention relates to a direct digital color proof image forming method using a silver halide color photosensitive material which forms a color image based on area-modulated image data (halftone image data).

[0002]

2. Description of the Related Art In recent years, with the progress of digitization of images, CTP (Computer To Plate)
It has become possible to print by a process that does not produce a squirrel plate. Along with this, the main purpose of proof making is changing from squirrel plate inspection to confirmation of print finish, and high quality and high speed are expected. Digital proofs are low-cost proofs, such as the inkjet method, which is low-cost, but cannot reproduce halftone dots, and high-cost productivity, such as the laser thermal method. High-quality proofs, which are low but can reproduce halftone dots and colors that are close to those of printed matter, and medium-quality proofs using a silver halide color light-sensitive material having a cost performance in between are being used.

Conventionally, the purpose of producing a color proof has been mainly to certify a lithographic plate before a printing plate is raised. For this reason,
In a proof using a silver halide light-sensitive material, a reversal light-sensitive material is generally used to obtain a positive image directly from a lith plate (positive image). The proof using the silver halide photosensitive material in the analog system before digitalization (contact exposure from the lith plate) had a certain level of dot reproducibility and color reproducibility. As a system using a conventional reversal type photosensitive material has been constructed (for example,
See Patent Document 1).

Since the plate data is digitized, the reversal becomes possible by calculation, and the reversal function is not necessarily required as the photosensitive material. Therefore, the construction of a proof system using a negative photosensitive material is considered. (For example, see Patent Document 2).

In a color proof system, a size (for example, A3) larger than that of an ordinary photographic print (density modulation) is used.
Exposure requires time, and since the image is represented by halftone dots, reproducibility of halftone dots and high image quality are required. In particular, the reproducibility of coexisting characters and fine characters in images is strongly required. In order to improve productivity, high-speed exposure by a multi-channel system consisting of multiple exposure light sources of the same wavelength, rapid processing of development, etc. are performed, but as productivity increases, image unevenness in printed images tends to occur. Become.

In order to improve the productivity of the system, it is preferable to use a silver halide emulsion having a high silver chloride content which is suitable for rapid processing of development, but a high silver chloride emulsion has a large illumination failure. It is known to have drawbacks. Low sensitivity and soft contrast at high illuminance impair suitability for laser scanning exposure and high-intensity light-emitting diode array scanning exposure, which are expected to have high image quality as a digital image information recording method. It was important to develop a means for improving the high illuminance failure of silver emulsion. Furthermore, if the processing time is shortened to perform a rapid processing, the passing speed of the photosensitive material through the processing equipment is generally increased, and the time of immersion in the processing liquid is shortened. At this time, there are problems such as streak and unevenness of increased density in the printed image, and white background is colored yellow. Therefore, it is necessary to address these problems.

As a result of diligent investigations by the present inventors, the above-described streaks and unevenness occurring during the development processing are more likely to occur in silver bromide and / or in the part or a plurality of parts of the surface from the center of the grain than others.
It was also found that the reduction can be achieved by providing a region having a high silver iodide content. However, this is not always sufficient when dealing with area-modulated image data, and the use of an emulsion containing such particles may further aggravate the yellow coloring of the above-mentioned white background or reduce the reproducibility of characters. all right.

[0008] Patent Documents 3 to 6 disclose that high sensitivity can be obtained by locally containing a phase having a high silver bromide content in various forms in an emulsion having a high silver chloride content. However, the means for reducing the yellow coloration on a white background when an emulsion containing a silver bromide-containing phase and / or a silver iodide-containing phase is used is not specified.

On the other hand, Patent Document 7 describes a method of removing residual color caused by a sensitizing dye, but does not deal with problems in handling area-modulated image data or problems of image streaks and unevenness. Not listed.

[0010]

[Patent Document 1] Japanese Patent Laid-Open No. 2000-147723

[Patent Document 2] Japanese Unexamined Patent Application Publication No. 2002-122969

[Patent Document 3] Japanese Patent Laid-Open No. 58-95736

[Patent Document 4] JP-A-63-89840

[Patent Document 5] US Pat. No. 4,820,624

[Patent Document 6] US Pat. No. 5,284,743

[Patent Document 7] Japanese Unexamined Patent Publication No. 2001-281823

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems in order to provide an image forming method which is suitable for image output based on digital data for area modulation and which is competitive in image quality. Specifically, there is little reduction in sensitivity or softening during exposure to high illuminance, excellent sharpness,
An object of the present invention is to construct an image forming method in which unevenness in density and yellow coloring on a white background during high-speed exposure or rapid development processing are reduced, and which is excellent in character reproducibility.

[0012]

Means for Solving the Problems As a result of intensive investigations by the inventors, the object of the invention was achieved by the following means. (1) In a color image forming method in which a silver halide color light-sensitive material is exposed and then treated with a processing liquid, the silver halide color photographic light-sensitive material has at least one yellow dye-forming coupler-containing silver halide emulsion layer on a support. A silver halide color light-sensitive material having at least one magenta dye-forming coupler-containing silver halide emulsion layer, at least one cyan dye-forming coupler-containing silver halide emulsion layer, and a color mixing prevention layer and a protective layer, At least one silver halide emulsion in the silver emulsion layer has at least one selected from the group consisting of silver chlorobromide grains, silver chloroiodide grains and silver chloroiodobromide grains having a silver chloride content of 95 mol% or more. A kind of silver halide grains having a region in which the silver bromide and / or silver iodide content is higher than others, The exposure is performed on the basis of area-modulating digital image data converted into exposure digital data depending on the exposure system device, and the treatment liquid has the following general formula (I) and / or the following general formula. A method for forming a color image, which comprises a compound represented by formula (II). General formula (I)

[0013]

[Chemical 6]

In the formula, R ₁₁ and R ₁₂ each independently represent a hydrogen atom or an alkyl group, and R ₁₃ and R ₁₄ each independently represent a hydrogen atom, an alkyl group or an aryl group,
R ₁₅ represents an alkyl group having at least one asymmetric carbon atom or a group represented by the following general formula (Ia),
R ₁₆ represents an alkyl group having at least one asymmetric carbon atom or a group represented by the following general formula (Ib),
M ₁ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or a pyridinium group.
R ₁₃ and R ₁₅ , and R ₁₄ and R ₁₆ may combine with each other to form a ring. General formula (Ia)

[0015]

[Chemical 7]

In the formula, n ₁₁ represents an integer of 1 to 3. General formula (Ib)

[0017]

[Chemical 8]

In the formula, n ₁₂ represents an integer of 2-4. General formula (II)

[0019]

[Chemical 9]

In the formula, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ each independently represent a hydrogen atom, an alkyl group or an aryl group, and R ₂₅ and R ₂₆ each independently represent an alkyl having at least one asymmetric carbon atom. Group or the following general formula (II-a)
R ₂₇ and R ₂₈ each independently represent an alkyl group having at least one asymmetric carbon atom, and M ₂ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or a pyridinium group. Represents R ₂₁ and R ₂₅ , R ₂₂ and R ₂₆ , R ₂₃ and R ₂₇ , R ₂₄ and R ₂₈
May combine with each other to form a ring. General formula (II-a)

[0021]

[Chemical 10]

In the formula, n ₂₁ represents an integer of 2-4. (2) A compound in which R ₁₅ and / or R ₁₆ in the general formula (I) has at least one hydroxyl group, and the general formula (II)
A color photographic processing composition was used, characterized in that at least one group selected from R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ in above contains at least one selected from compounds having at least one hydroxyl group ( The method for forming a color image according to item 1). (3) The color image forming method according to item (1) or (2), wherein the silver halide color light-sensitive material is for color proofing. (4) Scanning exposure using a gas laser, a light emitting diode, a semiconductor laser, a solid-state laser, or a second harmonic emission light source with them (1) to (3)
Item 6. The color image forming method according to any one of items. (5) The color image forming method as described in any one of (1) to (4), wherein the exposure is performed in a multi-channel having the same wavelength and including a plurality of exposure light sources. (6) The color image forming method as described in any one of (1) to (5), wherein the silver halide grains contain an iridium compound. (7) Any of (1) to (6), wherein the silver bromide-containing phase in the silver halide grains is a silver bromide-containing phase having a maximum silver bromide concentration inside the grain. Or the method of forming a color image according to item 1. (8) Any of (1) to (6), wherein the silver iodide-containing phase in the silver halide grains is a silver iodide-containing phase having a maximum silver iodide concentration on the grain surface. Or the method of forming a color image according to item 1. (9) The silver bromide localized phase in the silver halide grain is formed inside the grain rather than the silver iodide-containing phase, in any one of (1) to (6). The method for forming a color image according to item.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. The silver halide color light-sensitive material of the present invention comprises at least one yellow dye-forming coupler-containing silver halide emulsion layer, at least one magenta dye-forming coupler-containing silver halide emulsion layer, and at least one cyan dye-forming layer on a support. A silver halide color light-sensitive material having a coupler-containing silver halide emulsion layer, a color mixing prevention layer and a protective layer is used. Moreover, at least one silver halide emulsion in the silver halide emulsion layer is a group consisting of silver chlorobromide grains, silver chloroiodide grains, and silver chloroiodobromide grains having a silver chloride content of 95 mol% or more. It is composed of at least one kind of silver halide grains selected from the above, and the silver halide grains have a region in which the content of silver bromide and / or silver iodide is higher than that of other grains. Hereinafter, the silver halide emulsion will be referred to as the silver halide emulsion of the present invention, and the silver halide grains will be referred to as the silver halide grains of the present invention. The silver halide emulsion of the present invention is a negative type emulsion.
ve-working) Silver halide emulsions are preferred.

The silver halide emulsion of the present invention contains the above-described silver halide grains of the present invention. The particle shape of this particle is not particularly limited, but a cube having substantially {100} faces,
Tetradecahedral crystal grains (these have rounded vertices,
It may have a higher-order surface), octahedral crystal grains, and tabular grains having an aspect ratio of 2 or more in which the main surface is a {100} plane or a {111} plane. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of particles. In the present invention, cubic or tetradecahedral grains are more preferred.

Although the silver chloride content of the silver halide grains of the present invention is 95 mol% or more, from the viewpoint of rapid processability,
The silver chloride content is preferably 98 mol% or more, and 99 mol%
The above is more preferable. The silver bromide content is preferably 0.1 to 5 mol% and more preferably 0.5 to 5 mol% because it has a high contrast and excellent latent image stability. The silver iodide content is preferably 0.02 to 1 mol% because it has high sensitivity and high contrast at high illuminance exposure, and is 0.05 to
0.50 mol% is more preferable, and 0.07 to 0.40 mol% is most preferable. The silver halide grains of the present invention are preferably silver chloroiodobromide grains, and more preferably silver chloroiodobromide grains having the above halogen composition range.

The silver halide grain of the present invention has a region in which the content of silver bromide and / or silver iodide is higher than that of other regions. The silver halide grain of the present invention may have a region in which silver chloride, silver bromide and / or silver iodide are uniformly present in the entire grain and a high silver bromide and / or silver iodide content is partially present. However, as described later, it is preferable that most of the region is silver chloride only. In the present invention, a region having a higher silver bromide content than other regions is hereinafter referred to as a silver bromide-containing phase, and a region having a higher silver iodide content than other regions is referred to as a silver iodide-containing phase. 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 in a certain portion within the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing phase is preferably 5 mol% or more,
It is more preferably 80 mol% and most preferably 15 to 50 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%,
Most preferably, it is 5 mol%. Further, a plurality of such silver bromide- or silver iodide-containing phases may be layered in the grain, and in this case, the silver bromide- or silver iodide-content of each phase may be different. The silver halide grains of the present invention have at least one of a silver bromide-containing phase and a silver iodide-containing phase, but preferably at least one silver bromide-containing phase and at least one silver iodide-containing phase. Have a phase.

The silver bromide-containing phase or silver iodide-containing phase of the silver halide grain of the present invention may be present in a layer form so as to surround the grain, or may be completely isolated at a specific site (not a layer form). It is a non-layered, localized phase localized in the particles, and may exist, for example, isolated at the corners or edges of the particles, and when there are multiple of these phases,
A layered phase and a non-layered phase may be mixed. In the present invention, it is preferable that at least one of the silver bromide-containing phase and the silver iodide-containing phase exists in a layered form so as to surround the grain, and more preferably, both of these phases are layered so as to surround the grain. It exists. When there are a plurality of silver bromide-containing phases, it is preferable that at least one silver bromide-containing phase exists in a layered form and the remaining at least one silver bromide-containing phase be non-layered. One of the preferred embodiments is that the silver bromide-containing phase or the silver iodide-containing phase formed in a layer surrounding the grains has a uniform concentration distribution in the orbiting direction of the grains in each phase. However, in the silver bromide-containing phase or the silver iodide-containing phase that is layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the orbiting direction of the grain, and the concentration distribution May have. For example, when the layer has a silver bromide-containing phase or a silver iodide-containing phase near the surface of the grain so as to surround the grain, the concentration of silver bromide or silver iodide at the corner or edge of the grain is different from that on the main surface. There are cases. Further, apart from the silver bromide-containing phase and the silver iodide-containing phase which are layered so as to surround the grain, the silver bromide-containing phase which is completely isolated and exists 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 grain of the present invention contains a silver bromide-containing phase, it is preferable that the silver bromide-containing phase is formed in a layered form so as to have a maximum silver bromide concentration inside the grain. . When the silver halide grain of the present invention contains a silver iodide-containing phase, the silver iodide-containing phase is preferably formed in a layered form so that the surface of the grain has a maximum silver iodide concentration. Such a silver bromide-containing phase or a silver iodide-containing phase is composed of 3% or more and 30% or less of the grain volume in terms of increasing the local concentration with a smaller silver bromide or silver iodide content. Preferably 3% or more 1
It is more preferable that the amount of silver is 5% or less.

When both the silver bromide-containing phase and the silver iodide-containing phase, which are the preferred forms of the silver halide grains of the present invention, are contained, the silver bromide-containing phase and the silver iodide-containing phase are located at the same position on the grain. May be at different locations, but different locations are preferable in terms of facilitating control of particle formation. Further, the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide. In general,
The iodide added during the formation of high silver chloride grains is more likely to exude to the grain surface than bromide, so that the silver iodide-containing phase is likely to form near the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different positions in the grain, it is preferable that the silver bromide-containing phase is 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.

The silver bromide content or the silver iodide content necessary for exhibiting the effects of the present invention such as the enhancement of the sensitivity and the increase in the contrast is the silver bromide-containing phase or the silver iodide-containing phase within the grain. The more it is formed, the more it increases, and the silver chloride content may be unnecessarily reduced to impair the rapid processability. Therefore, it is preferable that the silver bromide-containing phase and the silver iodide-containing phase are adjacent to each other in order to concentrate these functions for controlling the photographic effect near the surface in the grain. From these points, the silver bromide-containing phase is 50% to 100% of the grain volume measured from the inside.
It is preferable that the silver iodide-containing phase is formed at any of positions from 85% to 100% of the grain volume. Further, it is preferable that the silver bromide-containing phase is formed anywhere from 70% to 95% of the grain volume, and the silver iodide-containing phase is formed anywhere from 90% to 100% of the grain volume. preferable.

The introduction of the bromide or iodide ion to contain silver bromide or silver iodide in the silver halide grains of the present invention is carried out by adding a solution of bromide salt or iodide salt alone or by adding a silver salt. A bromide salt or iodide salt solution may be added together with the addition of the solution and the high chloride salt solution. In the latter case, the bromide salt or iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of the bromide salt or iodide salt and the 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 ion or iodide ion from the organic molecule described in US Pat. No. 5,389,508. Fine silver bromide grains or fine silver iodide grains can also be used as another bromide or iodide ion source.

The addition of the bromide salt or iodide salt solution is
The particle formation may be concentrated in one period, or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in order to obtain an emulsion having high sensitivity and low fog. When the iodide ion is introduced inside the emulsion grains, the increase in sensitivity is small. Therefore, the addition of the iodide salt solution is preferably performed outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. The addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. When the addition of the iodide salt solution is completed slightly inside the grain surface, an emulsion having higher sensitivity and lower fog can be obtained. On the other hand, the bromide salt solution is preferably added to the outside of 50% of the grain volume, more preferably outside of 70%.

The distribution of the bromide or iodide ion concentration in the grain in the depth direction is determined by etching / TOF-SIMS.
(Time of Flight-Secondary
ryIon Mass Spectrometry) method, for example, TRIFT II manufactured by Phi Evans
Type TOF-SIMS can be used for measurement. TOF-SI
Regarding the MS method, specifically, “Surface Analysis Technology Selection Manual, Secondary Ion Mass Spectrometry” edited by The Surface Science Society of Japan, Maruzen Co., Ltd. (1
999). Etching / TOF
When the emulsion grains are analyzed by the SIMS method, it can be analyzed that the iodide ions are exuded toward the grain surface even after the addition of the iodide salt solution is completed inside the grains. In the emulsion of the present invention, it is preferable that the iodide ion has a maximum concentration on the surface of the grain and the iodide ion concentration is attenuated toward the inner side in the analysis by the etching / TOF-SIMS method. It is preferable to have a maximum concentration inside. The local concentration of silver bromide can also be measured by an X-ray diffraction method if the silver bromide content is high to some extent.

In the present specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to that of each particle. The emulsion of the present invention preferably comprises grains having a monodisperse grain size distribution. The variation coefficient of the spherical equivalent diameter of all particles of the present invention is 2
It is necessary to be 0% or less, more preferably 15% or less, and further preferably 10% or less.
The coefficient of variation of the sphere-equivalent diameter is expressed as a percentage of the standard deviation of the sphere-equivalent diameter of each particle with respect to the average of the sphere-equivalent diameters. At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating. In the case of cubic grains, the side length of the silver halide grains of the present invention is preferably 0.8 μm or less, more preferably 0.5 μm or less.
The shape other than the cubic particles is preferably a particle size having a sphere equivalent diameter corresponding to the above. The silver halide emulsion of the present invention may contain silver halide grains other than the silver halide grains of the present invention. However, in the silver halide emulsion defined in the present invention, 50% or more of the total projected area of all grains are preferably silver halide grains of the present invention, preferably 80% or more, and 90% or more. Is more preferable.

The sustained electron release time of the silver halide emulsion of the present invention is preferably between 10 ^-5 seconds and 10 seconds. Here, the term "electron sustained release time" refers to the time until a photoelectron generated in a silver halide crystal is trapped in an electron trap in the crystal and exposed again when the silver halide emulsion is exposed to light. . If the electronic controlled release time is shorter than 10 ^-5 seconds, it is difficult to obtain a high-sensitivity and high-contrast gradation in high-illuminance exposure. Cause The electron sustained release time is more preferably 10 ⁻⁴ to 10 seconds, most preferably 10 ⁻³ to 1 second.

The sustained electron release time can be measured by the double pulse photoconductivity method. A microwave photoconductivity method or a radio wave photoconductivity method is used to perform a first short-time exposure and then a second fixed short-time exposure. Electrons are trapped in the electron trap in the silver halide crystal by the first exposure, and when the second exposure is given immediately after that, the electron trap is clogged and the second photoconduction signal becomes large. If the two exposure intervals are set sufficiently and the electrons trapped in the electron trap have already been emitted in the first exposure, the photoconduction signal of the second emission returns to the original magnitude. When the exposure interval dependency of the second photoconductive signal intensity is taken by changing the exposure interval of two times, it can be measured that the exposure interval increases and the second photoconductive signal intensity decreases. This represents the sustained release time of photoelectrons from the electron trap. The sustained release of electrons may continue to occur for a certain period of time after the exposure, but it is preferable that the sustained release is observed within 10 ⁻⁵ seconds to 10 seconds. 10
More preferably, sustained release is observed between ^-4 and 10 seconds, even more preferably between 10 ^-3 and 1 second.

The silver halide grain of the present invention preferably contains an iridium compound. As the iridium compound, a hexacoordinated complex having six ligands and iridium as a central metal is preferable because it can be uniformly incorporated into the silver halide crystal. As one preferable embodiment of the iridium compound used in the present invention, a hexacoordination complex having Ir as a central metal and having Cl, Br or I as a ligand is preferable, and Ir in which all six ligands are Cl, Br or I. A hexacoordination complex having as a central metal is more preferable. In this case, Cl, Br or I in the hexacoordinated complex
May be mixed. It is particularly preferable that the hexacoordination complex having Cl, Br or I as a ligand and having Ir as a central metal is contained in the silver bromide-containing phase in order to obtain a hard gradation by exposure to high illuminance.

In the following, all six ligands are Cl, Br
Further, specific examples of the hexacoordinated complex of I having Ir as a central metal will be given, but the iridium compound in the present invention is not limited thereto. [IrCl ₆ ] ^2- [IrCl ₆ ] ^3- [IrBr ₆ ] ^2- [IrBr ₆ ] ^3- [IrI ₆ ] ^3-

As a different preferred embodiment of the iridium compound used in the present invention, a hexacoordination complex having Ir as a central metal and having at least one ligand other than halogen or cyan is preferable, and H ₂ O, OH, O, OCN, A hexacoordination complex having Ir as a central metal having a thiazole or a substituted thiazole as a ligand is preferable, and at least one H ₂ O, OH, O, OCN, a thiazole or a substituted thiazole as a ligand, and the remaining ligands are Cl, A hexacoordinated complex having Ir or Ir as a central metal, which is Br or I, is more preferable. Furthermore, one or two 5-
Methylthiazole as a ligand and the rest of the ligands are Cl, Br or I with Ir as a central metal 6
Coordination complexes are most preferred.

In the following, at least one H ₂ O, OH,
Specific examples of the hexacoordinated complex having O, OCN, thiazole or substituted thiazole as a ligand and the rest of the ligands consisting of Cl, Br or I and Ir as the central metal are shown below, but the iridium in the present invention is not limited thereto. .

[Ir (H ₂ O) Cl ₅ ] ^2- [Ir (H ₂ O) ₂ Cl ₄ ] ^- [Ir (H ₂ O) Br ₅ ] ^2- [Ir (H ₂ O) ₂ Br ₄ ] _{^{- [Ir (OH) Cl 5}} ] 3- [Ir (OH) 2 Cl 4] 3- [Ir (OH) Br 5] 3- [Ir (OH) 2 Br 4] 3- [Ir (O) Cl 5 ] ^4- [Ir (O) ₂ Cl ₄ ] ^5- [Ir (O) Br ₅ ] ^4- [Ir (O) ₂ Br ₄ ] ^5- [Ir (OCN) Cl ₅ ] ^3- [Ir (OCN)] Br _5] ^3- [Ir (thiazole) Cl _5] ^2- [Ir ^{_{(thiazole) 2 Cl 4] - [Ir}} ( thiazole) Br _5] ^2- [Ir ^{_{(thiazole) 2 Br 4] - [Ir}} (5- Methylthiazole) Cl ₅ ] ^2- [Ir (5-methylthiazole) ₂ Cl ₄ ] ^- [Ir (5-methylthiazole) Br ₅ ] ^2- [Ir (5-methylthiazole) ₂ Br ₄ ] ^-

The object of the present invention is that all 6 ligands are C
One of a hexacoordination complex containing 1, 1, Br or I as a central metal with Ir or a six coordination complex with an Ir as a central metal having at least one ligand other than halogen or cyan is used alone. This is preferably achieved. However, in order to further enhance the effect of the present invention, a hexacoordination complex in which all six ligands are Cl, Br, or I with Ir as the central metal, and Ir having at least one ligand other than halogen or cyan are used.
It is preferable to use a 6-coordination complex having as a central metal together. Furthermore, at least one H ₂ O, OH, O, OC
Ir having N, thiazole or substituted thiazole as a ligand and the rest of the ligands consisting of Cl, Br or I
A hexacoordination complex having a central metal of is one of two types of ligands (H ₂ O, OH, O, OCN, thiazole or substituted thiazole and Cl, Br or I to 1).
It is preferable to use a complex composed of (seed).

The above-mentioned metal complexes are anions,
When a salt is formed with a cation, a counter cation which is easily dissolved in water 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 suitable organic solvent that can be mixed with water (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.) before use. You can These iridium complexes are added at 1 x 1 per mole of silver during grain formation.
It is preferable to add 1 × 10 ^-3 mol from 0 ^-10 mol, 1 ×
Most preferably, it is added from 10 ⁻⁸ mol to 1 × 10 ⁻⁵ mol.

In the present invention, the above iridium complex is
By adding directly to the reaction solution at the time of silver halide grain formation, or in an aqueous solution of a halide for forming silver halide grains, or in a solution other than that, and then adding to the grain formation reaction solution, the halogen It is preferably incorporated into silver halide grains. Further, it is also preferable to physically ripen fine particles in which an iridium complex has been incorporated into the grains and incorporate them into the silver halide grains. Further, these methods may be combined and contained in the silver halide grains.

When these complexes are incorporated into silver halide grains, they may be made to exist uniformly inside the grains. JP-A-4-208936 and JP-A-2-12524
5, as disclosed in JP-A-3-188437, it is also preferable that the particles are present only in the particle surface layer,
It is also preferable that the complex is present only inside the particles and a layer not containing the complex is added to the surface of the particles. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical aging of fine particles in which a complex is incorporated to modify the surface phase of the particles. Is also preferable. Further, these methods may be used in combination, and plural kinds of complexes may be incorporated in one silver halide grain. There is no particular limitation on the halogen composition at the position where the above complex is contained, but all 6 ligands have Cl, Br, or I as the central metal 6
The coordination complex is preferably contained in the silver bromide concentration maximum part.

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

The combination of a metal ion and a ligand is preferably an iron ion or a ruthenium ion and a cyanide ion. In the present invention, it is preferable to use iridium and these compounds in combination. In these compounds, the cyanide ion preferably occupies a majority of the coordination numbers to the central metal iron or ruthenium, and the remaining coordination sites are thiocyan, ammonia, water, nitrosyl ion, dimethyl sulfoxide,
It is preferably populated with pyridine, pyrazine or 4,4'-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron or hexacyanoruthenium complex. It is preferable to add 1 × 10 ^-8 mol to 1 × 10 ^-2 mol per mol of silver of the complex having a cyanide ion as a ligand, and 1 × 10 ^-6 mol to 5 × 10 5 mol per 1 mol of silver. It is most preferable to add ^-4 mol. When ruthenium and osmium are the central metals, it is also preferable to use nitrosyl ion, thionitrosyl ion, or water molecule and chloride ion together as ligands.
It is more preferable to form a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex, and it is also preferable to form a hexachloro complex. These complexes are used during the grain formation
It is preferable to add 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻⁶ mol per mol, and more preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁶ mol.

Among the compounds of the present invention, the structures represented by the general formula (I) are described in JP-A-6-332127 and JP-A7-1.
No. 40625, Japanese Patent Application Laid-Open No. 10-104809, which is included in the scope of claims, there is no description of a specific compound corresponding to the compound of the present invention in the above specification, and therefore the above specification. It is impossible to predict the structure and performance of the compound of the present invention from the inside.

The general formula (I) and the general formula (II) will be described in detail. The alkyl group represented by R ₁₁ and R ₁₂ preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms,
Particularly preferred is a substituted or unsubstituted alkyl group of 1 to 4. Examples of the substituent include a hydroxyl group, an alkoxy group (eg, methoxy, ethoxy, etc.), a sulfonic acid group, an ethyleneoxy group, and the like, which may be further substituted with the above-mentioned substituent. Specific examples of the alkyl group represented by R ₁₁ and R ₁₂ include a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-octyl group, 2
-Hydroxyethyl group, 3-hydroxypropyl group, 2
-Hydroxypropyl group, 2-sulfoethyl group, 2-methoxyethyl group, 2- (2-hydroxyethoxy) ethyl group, 2- [2- (2-hydroxyethoxy) ethoxy]
Examples thereof include an ethyl group and a 2- (2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethyl group.
Preferred as R ₁₁ and R ₁₂ are a hydrogen atom and a methyl group,
Ethyl group, n-propyl group, n-butyl group and 2-sulfoethyl group are more preferable, hydrogen atom and methyl group, ethyl group and 2-sulfoethyl group are more preferable, and hydrogen atom and methyl group are particularly preferable. is there.

R₁₃, R₁₄, R_{twenty one}, R_{twenty two}, R_{twenty three}, R_{twenty four}Table
Preferred carbon number of the alkyl group, substituents, specific examples
Etc. are each R₁₁, R₁₂Is the same as that shown in. Was
But R_{twenty one}And R_{twenty two}Is -CH₂CH₂SO₃M₁(M₁Is one
It has the same meaning as in general formula (I)). R
₁₃, R₁₄, R_{twenty one}, R_{twenty two}, R_{twenty three}, R_{twenty four}Ally represented by
The group preferably has 6 to 20 carbon atoms, more preferably 6 carbon atoms.
-10, particularly preferably 6-8, substituted or unsubstituted
Is an aryl group. Substituents include hydroxyl groups and alkoxy groups.
Si group (eg, methoxy, ethoxy, etc.), carboxy
Groups, alkyl groups (eg methyl, ethyl, propyl
Etc.), sulfonic acid groups, amino groups, carbamoyl groups, etc.
And these are further substituted with the above substituents.
May be. R ₁₃, R₁₄, R_{twenty one}, R_{twenty two}, R_{twenty three}, R_{twenty four}Represented by
As the aryl group to be specifically exemplified, for example, a phenyl group,
Naphthyl group, 3,5-dicarboxyphenyl group, 4-me
Examples include toxyphenyl group and 3-isopropylphenyl group.
To be R₁₃, R₁₄, R_{twenty one}, R _{twenty two}, R_{twenty three}, R_{twenty four}Asso
Each is preferably a hydrogen atom, a methyl group, an ethyl group or n-
Propyl group, 2-hydroxyethyl group, 3-hydroxy
Propyl group, 2-hydroxypropyl group, 2-sulfoe
Chill group, 2- (2-hydroxyethoxy) ethyl group or
2- [2- (2-hydroxyethoxy) ethoxy] ethyl
Groups, more preferably hydrogen atom, methyl group, ethyl
Group, 2-hydroxyethyl group, 2-hydroxypropyl
Or a 2- (2-hydroxyethoxy) ethyl group.
And particularly preferably a hydrogen atom or a methyl group.

The alkyl group having at least one asymmetric carbon atom represented by R ₁₅ preferably has 1 to 20 carbon atoms,
It is more preferably 1 to 8, particularly preferably 1 to 4, and may be linear, branched or cyclic. Examples of the substituent include a hydroxyl group, an amino group and a carboxyl group, and a hydroxyl group is preferable. Specific examples of the alkyl group having at least one asymmetric carbon atom represented by R ₁₅ include the alkyl groups represented by the following formulas.

[0052]

[Chemical 11]

[0053]

[Chemical 12]

[0054]

[Chemical 13]

Of these, preferred as the alkyl group having at least one asymmetric carbon atom represented by R ₁₅ are 2), 3), 5), 8), 9) and 11), and more preferred is 2). 5) and 11). Further, when R ₁₅ is a group represented by the following general formula (Ia), preferable n ₁₁ is 1 or 2, and more preferably 1. General formula (Ia)

[0056]

[Chemical 14]

R₁₆, R_{twenty five}, R₂₆, R₂₇, R₂₈Represented by
An alkyl group having at least one asymmetric carbon group
The number of carbon atoms is preferably 1 to 20, more preferably 1 to 9,
Is preferably 1 to 5, and is linear, branched or cyclic.
May be R as a substituent₁₅Similar to the one given in
And hydroxyl groups are preferred. R₁₆, R_{twenty five},
R ₂₆, R₂₇, R₂₈At least one asymmetric coal represented by
Specific examples of the alkyl group having hydrogen are shown in the following formulas.
Alkyl groups may be mentioned.

[0058]

[Chemical 15]

[0059]

[Chemical 16]

[0060]

[Chemical 17]

Of these, preferred as alkyl groups having at least one asymmetric carbon atom represented by R ₁₆ , R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ are 17), 18), 20), 2
3), 24) and 26), more preferably 1
7), 20) and 26). When R ₁₆ is a group represented by the following general formula (Ib), n ₁₂ is preferably 2 or 3, and more preferably 2. General formula (Ib)

[0062]

[Chemical 18]

R_{twenty five}, R₂₆Is the following general formula (II-a)
In the case of the group represented by, preferable n _{twenty one}Is 2 or 3
And more preferably 2. General formula (II-a)

[0064]

[Chemical 19]

An alkali metal atom represented by M ₁ and M ₂ ,
Particularly preferred among the alkaline earth metal atoms are Na and K. As the ammonium group, a tetraalkylammonium group is preferable, and examples thereof include tetraethylammonium and tetrabutylammonium.
Most preferred as M ₁ and M ₂ are Na and K. A plurality of M ₁ or M ₂ may be the same or different.

Of the compounds represented by the general formula (I), R
₁₅And R₁₆Either, or both, are less
Those having one hydroxyl group are preferable. General formula
Also in (II), R_{twenty five}~ R₂₈At least one group of
However, those having at least one hydroxyl group are preferred.
Yes. Most preferred of compounds represented by general formula (I)
The compound is R₁₁, R₁₂, R ₁₃, R₁₄Are hydrogen atoms
Or a methyl group, R₁₅Is 2), 5) or 1 above
The alkyl group shown in 1) or the above general formula (Ia)
At n₁₁Is 1 and R is₁₆Is above 17), 2
0) or the alkyl group shown in 26), or one of the above.
In the general formula (I-b), n₁₂Is a group in which M is 2.₁But
A compound that is Na or K. Also, in the general formula (II)
Most preferred of the compounds represented are R_{twenty one},
R_{twenty two}, R_{twenty three}, R_{twenty four}Are each a hydrogen atom or a methyl group.
R _{twenty five}, R₂₆Are the above 17), 20) or
26) or the above general formula (II-
n in a)_{twenty one}Is 2 and R is₂₇, R₂₈Gazo
Al respectively shown in 17), 20) or 26) above
Is a kill group, M₂Is Na or K.

Since the compound used in the present invention has a plurality of asymmetric carbon atoms in the molecule, a plurality of stereoisomers exist for the same structure. However, in the present invention, all possible stereoisomers It is also possible to use only one of the stereoisomers or to use several of them as a mixture.

In the present invention, a plurality of other diaminostilbene compounds may be used in combination with the compounds represented by the general formulas (I) and (II). The diaminostilbene compound represented by the general formula [III] described in 6-329936 is preferable.

As the diaminostilbene compound that can be used in the present invention, a known or commercially available diaminostilbene compound optical brightener may be used. Examples of commercially available compounds include “Dyeing Note”, 19th edition (Color Sensha Co., Ltd.) 1
65-P. 168, among other products described herein, Blankophor BSUL
iq (trade name) or Hakkol BRK (trade name) is preferable.

The following are general formulas that can be used in the present invention.
Specific examples of typical compounds represented by formula (I) or general formula (II) will be given. In the formula, Me is a methyl group,
Et represents an ethyl group.

[0071]

[Chemical 20]

[0072]

[Chemical 21]

[0073]

[Chemical formula 22]

[0074]

[Chemical formula 23]

[0075]

[Chemical formula 24]

[0076]

[Chemical 25]

[0077]

[Chemical formula 26]

[0078]

[Chemical 27]

[0079]

[Chemical 28]

[0080]

[Chemical 29]

[0081]

[Chemical 30]

[0082]

[Chemical 31]

[0083]

[Chemical 32]

[0084]

[Chemical 33]

[0085]

[Chemical 34]

[0086]

[Chemical 35]

The compound represented by the general formula (I) or the general formula (II) is, for example, by Koji Matsui, Journal of Organic Synthetic Chemistry, No. 17
Volume 528 (published in 1959) and Patent No. 2,618,
It can be synthesized with reference to No. 748. That is, a method is preferred in which cyanuric chloride is first reacted with a diaminostilbene derivative and then sequentially reacted with amines. Alternatively, it is also preferable to react the dialkylaminostilbene derivative last. Examples of the solvent used in this reaction include water and organic solvents such as alcohols, ketones, ethers, and amides, but water and water-soluble organic solvents are preferable, and a mixed solvent thereof may be used. Of these, a mixed solvent system of water and acetone is most preferable. Examples of the base used include organic bases such as triethylamine, pyridine, and 1,8-diazabicyclo [5,4,0] -7-undecene, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and hydrogenation. Inorganic bases such as sodium are mentioned. Inorganic bases are preferable, and sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate are particularly preferable. The reaction temperature can be in the range of -20 ° C to 120 ° C, preferably -10 ° C to 90 ° C. More specifically, the first stage is preferably -10 ° C to 10 ° C, the second stage is preferably 0 ° C to 40 ° C, and the third stage is preferably 50 to 90 ° C.

Synthesis Example 1 Exemplified compound (I-1) of the present invention was synthesized based on the following formula.

[0089]

[Chemical 36]

(Synthesis of Compound (3)) 103.5 g of Compound (1) and 680 ml of acetone were placed in a three-necked flask, and the internal temperature was adjusted to -5 ° C. in an ice-acetone bath.
Compound (2) 101.9 g, sodium carbonate 58.3
An aqueous solution of g and 960 ml of water was added dropwise with stirring over 1 hour. At this time, the internal temperature rose to -1 ° C. After the dropwise addition was completed, the ice-acetone bath was removed, stirring was continued for 1 hour as it was, and the precipitated crystals were separated by suction filtration to obtain the target compound (3). This product was subjected to the next step as it was without being dried and purified.

(Synthesis of Compound (4)) The compound (3) obtained in the previous step and 1.9 liters of water were placed in a three-necked flask, and taurine 68. was added thereto while stirring in a water bath.
8 g was added, followed by 58.3 g sodium carbonate and 2 parts water.
An aqueous solution dissolved in 75 ml was added dropwise over 1 hour. After finishing the dropping, remove the water bath and continue stirring for 3 hours.
550 g of sodium chloride was added thereto, and the mixture was further stirred for 1 hour. The precipitated crystals were filtered by suction filtration to obtain the target compound (4). This product was subjected to the next step as it was without being dried and purified.

(Synthesis of Exemplified Compound (I-1)) The compound (4) obtained in the previous step and 825 m of water were placed in a three-necked flask.
l, and the compound (5) 1 was added here with stirring at room temperature.
25.3 g was added dropwise over 10 minutes. Inner temperature 8 after dropping
The mixture was stirred at 5 ° C for 3 hours, and the obtained reaction mixture was concentrated by a rotary evaporator. When the remaining amount became about 800 ml, crystals started to precipitate, so stop the concentration,
The mixture was stirred as it was under ice cooling, and the precipitated crystals were suction filtered. To the crystals thus obtained, 1.5 liter of methanol was added, and the mixture was stirred with heating under reflux for 1 hour. After cooling this to room temperature, suction filtration was performed to obtain 206.0 g of the desired exemplary compound (I-1) (yield 72%). λmax (H ₂ O) = 346.3 nm (ε = 4.83 × 10 ⁴ ) Further, when the purity of the obtained compound was examined by liquid chromatography, it was 96.0%. The conditions for liquid chromatography were as follows. Column: TSK-gel ODS-80TM (manufactured by Tosoh Corp.) Eluent: A liquid 20 ml of PIC A reagent (manufactured by Waters) was added to 1 liter of water B liquid 20 ml of PIC A reagent was added to a mixture of 800 ml of methanol and 200 ml of water. A gradient was applied so that A liquid / B liquid = 50/50 (0 min) → 0/100 (35 min). Detection wavelength: 346 nm Purity was determined by the area of the peak recorded in the chart under the above conditions.

Synthesis Example 2 The exemplified compound (I-20) of the present invention was synthesized based on the following formula.

[0094]

[Chemical 37]

(Synthesis of Exemplified Compound (I-20)) A three-necked flask was charged with the same scale as in Synthesis Example 1, the compound (4) obtained by the synthesis method, and 825 ml of water, and the mixture was stirred at room temperature. Compound (6) (144.4 g) was added dropwise over 10 minutes. After completion of dropping, the mixture was stirred at an internal temperature of 85 ° C. for 3 hours, the obtained reaction mixture was concentrated by a rotary evaporator until the residual amount was about 800 ml, and the mixture was stirred under ice-cooling as it was, and the precipitated crystals were suction filtered. did. To the crystals thus obtained, 1.5 liter of methanol was added, and the mixture was stirred with heating under reflux for 1 hour. After cooling this to room temperature, suction filtration was carried out to obtain the desired exemplified compound (I-20) 24.
9.7 g was obtained (yield 85%). λmax (H ₂ O) = 354.5 nm (ε = 4.92 × 10 ⁴ ) Further, when the purity of the obtained compound was examined by liquid chromatography, it was 97.3%. The conditions for liquid chromatography were the same as in Synthesis Example 1.

Synthesis Example 3 The exemplified compound (I-33) of the present invention was synthesized based on the following formula.

[0097]

[Chemical 38]

(Synthesis of Exemplified Compound (I-33)) A three-necked flask was charged with the same scale as in Synthesis Example 1, the compound (4) obtained by the synthesis method, and 825 ml of water, and the mixture was stirred at room temperature. Compound (7) 268.5 g was added to the above over 10 minutes. After completion of the addition, the mixture was stirred at an internal temperature of 85 ° C. for 3 hours, the obtained reaction mixture was concentrated by a rotary evaporator until the residual amount was about 900 ml, and the mixture was stirred under ice-cooling as it was, and the precipitated crystals were suction filtered. did. To the crystals thus obtained, 1.5 liter of methanol was added, and the mixture was stirred with heating under reflux for 1 hour. After cooling this to room temperature, suction filtration was performed to obtain the desired exemplified compound (I-33) 30.
2.4 g was obtained (88% yield). λmax (H ₂ O) = 348.6 nm (ε = 4.36 × 10 ⁴ ) Further, the purity of the obtained compound was 96.1% when examined by liquid chromatography. The conditions for liquid chromatography were the same as in Synthesis Example 1.

Synthesis Example 4 Exemplified compound (II-5) of the present invention was synthesized based on the following formula.

[0100]

[Chemical Formula 39]

(Synthesis of Exemplified Compound (II-5)) A three-necked flask was charged with the same scale as in Synthesis Example 1, the compound (3) obtained by the synthesis method, and 825 ml of water, and the compound was added thereto under water cooling. (5) 256.0 g was added dropwise over 30 minutes. After that, the mixture was stirred at room temperature for 3 hours and then at an internal temperature of 85 ° C.
The mixture was heated and stirred for an hour, and 500 ml of concentrated hydrochloric acid was added thereto while keeping the internal temperature at 15 ° C or lower in an ice bath. Further, 2 liters of acetone was added thereto, the ice bath was removed, the mixture was stirred for 2 hours, and the obtained crystals were collected by suction filtration. To the crystals thus obtained, 1 liter of methanol was added, and the mixture was stirred under heating under reflux for 1 hour, cooled to an internal temperature of 30 ° C., and the crystals obtained by suction filtration were dried to give the desired exemplary compound (II −
5) 216 g was obtained (yield 87%). λmax (H ₂ O) = 346.3 nm (ε = 4.86 × 10 ⁴ ) Further, the purity of the obtained compound was 93.5% when examined by liquid chromatography. The conditions of liquid chromatography were the same as in Synthesis Example 1.

Next, the processing composition for silver halide color light-sensitive material (hereinafter referred to as processing composition) in the present invention will be described in detail. The processing composition in the present invention refers to a processing composition required for processing for forming an image of a silver halide color photographic light-sensitive material, and specifically, a color developing composition, a bleaching composition and a bleaching composition. Fixing compositions, fixing compositions, washing compositions and stabilizing compositions,
Further, it may be a black-and-white developing composition, a reversal composition and a pre-bleaching composition. These treatment compositions may be prepared as a tank solution or a replenisher at a working solution concentration or as a concentrated solution. When the treatment composition of the present invention is a concentrated liquid, it is mixed with water in a predetermined ratio when used, and used as a replenishing liquid or a tank liquid. The compound of the present invention is characterized by being excellent in precipitation stability in a composition in a solution state, but the compound may be used in each processing composition in the form of granule, tablet, powder or slurry.

In the treatment composition of the present invention, the concentration of the compound of the general formula (I) and / or the compound of the general formula (II) is 0.05 to 20 mmol / L in the working solution, preferably 0.15 to It is 15 mmol / L, more preferably 0.2 to 10 mmol / L. When the treatment composition of the present invention is used after being diluted with water, the concentration in the treatment composition is a value obtained by multiplying the concentration in the use liquid by the concentration ratio.

The image forming method of the present invention uses the processing composition of the present invention in at least one of the processing steps. The treatment composition of the present invention may be used in multiple steps or all steps.

There are several methods for producing the treatment composition of the present invention, and the following three methods give good results. However, in carrying out the present invention, the manufacturing method is not limited to the following three methods. [Method A] A method in which a small amount of water is introduced into a mixing tank in advance, and constituent chemicals are sequentially added to the mixing tank while stirring. [Method B] A method in which the constituent chemicals are mixed in advance and a small amount of water is poured all at once into the mixing tank. [Method C] A method in which constituent chemicals are divided into appropriate groups in advance and each is dissolved in water or a hydrophilic organic solvent to form a concentrated solution, and then the concentrated solutions are mixed. A manufacturing method that partially incorporates each method can also be implemented.

Next, the processing composition of the present invention comprises a color developing composition, a bleaching composition, a bleach-fixing composition, a fixing composition,
The case where it is either a water-washing composition or a stabilizing composition will be described.

Although the color developing composition of the present invention contains a color developing agent, a known aromatic primary amine color developing agent is preferable, and a p-phenylenediamine derivative is particularly preferable. Typical examples are shown below, but the present invention is not limited thereto. Further, in recent years, in black-and-white light-sensitive materials, couplers have been added so as to develop a black color, and there are also those that form a black-and-white image using a general-purpose color developing solution, but the processing composition of the present invention It is also applied to some kinds of light-sensitive materials.

N-1) N, N-diethyl-p-phenylenediamine N-2) 4-amino-N, N-diethyl-3-methylaniline N-3) 4-amino-N- (β-hydroxyethyl) )
-N-methylaniline N-4) 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline N-5) 4-amino-N-ethyl-N- (β-hydroxyethyl) -3-methyl Aniline N-6) 4-amino-N-ethyl-N- (3-hydroxypropyl) -3-methylaniline N-7) 4-Amino-N-ethyl-N- (4-hydroxybutyl) -3-methyl Aniline N-8) 4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -3-methylaniline N-9) 4-amino-N, N-diethyl-3- (β-
Hydroxyethyl) aniline N-10) 4-amino-N-ethyl-N- (β-methoxyethyl) -3-methylaniline N-11) 4-amino-N- (β-ethoxyethyl)
-N-ethyl-3-methylaniline N-12) 4-amino-N- (3-carbamoylpropyl) -Nn-propyl-3-methylaniline N-13) 4-amino-N- (4-carbamoyl) Butyl) -N-n-propyl-3-methylaniline N-14) N- (4-amino-3-methylphenyl)
-3-Hydroxypyrrolidine N-15) N- (4-amino-3-methylphenyl)
-3-Hydroxymethylpyrrolidine N-16) N- (4-amino-3-methylphenyl)
-3-Pyrrolidine carboxamide

Of the above p-phenylenediamine derivatives, the exemplified compounds N-5), N-6), N-7), N-8) and N-12) are preferable, and N-5) and N-8) are preferable. Particularly preferred. These p-phenylenediamine derivatives are
In the solid state, it is usually a sulfate, a hydrochloride, a p-toluenesulfonate, a naphthalenedisulfonate, an N, N-bis (ethyl sulfonate) hydroxylamine salt or the like. Further, it may be added as a free form having no salt. The concentration of the aromatic primary amine developing agent is 4 to 100 mmol / L in the working solution, preferably 6 to
50 mmol / L, more preferably 8 to 25 m
It is mol / L.

A compound which prevents the precipitation of a color developing agent may be added to the color developing solution according to the present invention. Polyethylene glycols, aryl sulfonic acids, alkyl sulfonic acids or urea compounds described in JP-A No. 11-174643 are used. Can be mentioned. Of these, diethylene glycol, polyethylene glycol 300, p-toluenesulfonic acid and salts thereof, straight-chain alkylsulfonic acids having 5 to 9 carbon atoms or salts thereof, or ethyleneurea, which have a particularly small effect on photographic properties and exhibit good effects. Is particularly preferable.

The color developing composition of the present invention preferably contains a compound that prevents deterioration of the color developing agent due to air oxidation, that is, a preservative. As the inorganic preservative, sulfite and hydroxylamine are preferable, and these show a remarkable preservative action, and it is also preferable to use them together with an organic preservative. Sulfite and hydroxylamine may adversely affect the photographic characteristics in the color development process depending on the intended light-sensitive material.Therefore, either one may be included, or substantially no organic preservative may be included. Sometimes only one is used.

Examples of organic preservatives include hydroxyamine derivatives, hydroxamic acids, hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammoniums, Nitroxy radicals, alcohols,
Oximes, diamides, condensed amines, cyclic amides, salicylic acids, polyethyleneimines, alkanolamines and aromatic polyhydroxy compounds are effective. Among the above organic preservatives, JP-A-3-56456
Nos. 3,338,845 and hydroxylamine derivatives, and Nos. 3,33,846 and 6,148,881
Especially preferred are the compounds described under.

It is preferable to use the hydroxylamine derivative in combination with the alkanolamine from the viewpoint of improving the stability of the color developing solution in continuous processing. Particularly preferred compounds in combination with hydroxylamines include triisopropanolamine and triethanolamine.
It is also preferable to use it in combination with a cyclic amide compound, of which ε-caprolactam is particularly preferable.

The color developing composition of the present invention has a pH of 9.5.
.About.13.5 is preferred, and the color developer prepared therefrom has a pH of preferably 9.0 to 12.2, more preferably pH 9.9 to 11.2. In order to maintain the pH, it is preferable to add a buffering agent, and as the buffering agent, potassium salt or sodium salt of inorganic salt such as carbonate, bicarbonate, phosphate, borate, tetraborate is preferable. . Organic compounds such as 5-sulfosalicylic acid, β-alanine, proline, and trishydroxyaminomethane are also preferably used, but the present invention is not limited to these compounds. The concentration of the above buffer is preferably such that the concentration in the color developing replenisher is 0.1 mol / L or more, particularly 0.1 to 0.4 mol / L.

Various chelating agents which are precipitation inhibitors such as calcium and magnesium can be added to the color developing composition of the present invention. 2 kinds of chelating agents
You may use 1 or more types. Preferred compounds include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, ethylenediaminesuccinic acid (s, s body), 2
-Phosphonobutane-1,2,4-tricarboxylic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid, 1,2
-Dihydroxybenzene-4,6-disulfonic acid and the like can be mentioned. The amount of the chelating agent may be an amount sufficient to mask the metal ions in the color developing solution, and is usually 0.1 g.
/ L to 10 g / L.

If desired, any development accelerator can be added to the color developing composition of the present invention. Examples of the development accelerator include polyalkylene oxide, 1-phenyl-3-pyrazolidones, alcohols and carboxylic acids.

If desired, an optional antifoggant can be added to the color developing composition of the present invention. Examples of the antifoggants include metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants represented by nitrogen-containing heterocyclic compounds. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,
5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine, adenine and the like can be mentioned. Also other alkyl carboxylic acid,
Aryl carboxylic acids and sugars may be added as necessary.

In the case of a color print light-sensitive material in the color development applied to the present invention, the processing temperature is preferably 30.
To 55 ° C, more preferably 35 to 50 ° C, and further preferably 38 to 45 ° C. The development time is preferably 5 to 90 seconds, more preferably 8 seconds to 60 seconds, still more preferably 10 seconds to 45 seconds. It is preferable that the replenishment amount is small, but 15 to 200 mL per 1 m ^{2 of the} light-sensitive material
Is suitable, preferably 20 to 120 mL, more preferably 30 to 60 mL. In the case of a color negative film, the processing temperature is preferably 30 to 55 ° C,
The temperature is more preferably 35 to 50 ° C, and further preferably 38 to 45 ° C. Development time is preferably 45 seconds to 5
Minutes, more preferably 60 seconds to 4 minutes, still more preferably 90 seconds to 3 minutes 15 seconds. It is preferable that the replenishment amount is small, but 24 exp. (24 shots) 10 for each
~ 200 mL is suitable, preferably 12-60 m
L, more preferably 15 to 30 mL.

JP-A-11-174643 and JP-A-11-16443
The color developing compositions described in JP-A-194461 and JP-A-11-194462, which are concentrated replenishing solutions, are examples of preferred embodiments.

As the bleaching agent used in the bleaching composition and the bleach-fixing composition of the present invention, a known bleaching agent can be used. In particular, an organic complex salt of iron (III) (for example, aminopolycarboxylic acids or Preferred are complex salts of organic acids such as citric acid, tartaric acid and malic acid), persulfates and hydrogen peroxide. Further, two or more kinds of bleaching agents may be mixed and used.

Of these, organic complex salts of iron (III) are particularly preferable from the viewpoints of rapid processability and prevention of environmental pollution. The aminopolycarboxylic acids or salts thereof useful for forming an organic complex salt of iron (III) are listed. Biodegradable ethylenediamine succinic acid (s, s form), N- (2
-Carboxylate ethyl) -L-aspartic acid, β
-Alanine diacetic acid, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
1,3-propylenediaminetetraacetic acid, nitrilotriacetic acid,
Examples thereof include compounds such as cyclohexanediaminetetraacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid. These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, ethylenediamine succinic acid (s, s
Body), N- (2-carboxylate ethyl) -L-aspartic acid, β-alanine diacetic acid, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and 1,3-propylenediaminetetraacetic acid are iron (III) thereof. It is preferable because the salt has good photographic properties. These ferric ion complex salts may be used in the form of complex salts, and may be ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium nitrate, ferric phosphate. A ferric ion complex salt may be formed in a solution as a chelating agent of iron or the like and aminopolycarboxylic acid or the like. Further, the chelating agent may be used in excess of the amount necessary for forming the ferric complex salt. The concentration of the bleaching agent in the bleaching solution or the bleach-fixing solution is 0.01-
1.0 mol / L, preferably 0.05-0.5 mol
/ L, more preferably 0.1 to 0.5 mol / L.

It is also preferable to add a buffer to the bleaching solution or the bleach-fixing solution. The buffer is selected according to the intended pH, but preferred compounds include succinic acid, maleic acid,
Organic acids such as glycolic acid, malonic acid, fumaric acid, succinic acid, sulfosuccinic acid and acetic acid, organic bases such as imidazole and dimethylimidazole, or JP-A-9-2.
General formula (Aa) and general formula (B) described in 11819.
Examples thereof include compounds represented by -b). The amount of these compounds added is 0.005 mol / L to the used solution.
3.0 mol / L is preferable, and 0.0 is more preferable.
It is 5 mol / L-1.5 mol / L. PH of bleaching solution
The region preferably has a pH of 2 to 7, and particularly preferably a pH of 3 to 6. In the case of bleach-fixing, pH 3-8 is preferable, pH 4-7
Is more preferable.

In bleach-fixing of the color print light-sensitive material applied to the present invention, the processing temperature is preferably 30-5.
The temperature is 5 ° C, more preferably 35 to 50 ° C, and further preferably 38 to 45 ° C. The bleach-fixing time is preferably 5 to 90 seconds, more preferably 8 to 60 seconds, still more preferably 10 to 45 seconds. It is preferable that the replenishment amount is small, but ²⁰ to 200 mL per 1 m ^{2 of the} light-sensitive material
Is suitable, preferably 25 to 120 mL, more preferably 30 to 50 mL. In bleaching of a color negative film, the processing temperature is preferably 30 to 55 ° C.
Is more preferable, the temperature is more preferably 35 to 50 ° C, and further preferably 38 to 45 ° C. Bleaching time is preferably 1
2 seconds to 2 minutes, more preferably 15 seconds to 1 minute 15
Seconds, more preferably 18 to 60 seconds. It is preferable that the replenishment amount is small, but 24 exp. 2.5 per piece
˜50 mL is suitable, preferably 3 to 25 mL, more preferably 4 to 12 mL.

The bleach-fixing composition of the present invention and the fixing agent used in the fixing composition are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, sodium thiocyanate and ammonium thiocyanate. Thiocyanate, ethylenebisglycolic acid, 3,6-dithia-1,8-octanediol, thioether compounds described in JP-A-4-317055, thioureas or JP-A-4-143757 and JP-A-4-143757. It is a water-soluble silver halide dissolving agent such as a mesoionic compound described in No. 230749, and these can be used alone or in combination of two or more. As the fixing agent, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The concentration of the fixing agent in the fixer or the bleach-fixer is 0.3 to
2 mol / L is preferable, and more preferably 0.5 to
It is 1.5 mol / L.

A buffering agent is preferably added to the bleach-fixing composition or the fixing composition. Preferred buffering agents include heterocyclic organic bases such as imidazole and dimethylimidazole, aminoalkylene sulfonic acids such as taurine, and dibasic acids such as succinic acid, maleic acid and malonic acid. The pH is preferably 3 to 8, more preferably pH 4 to
7 is preferable.

The bleach-fixing composition and fixing composition of the present invention preferably contain, as a preservative, a compound capable of releasing sulfite ion, that is, sulfite, bisulfite, metabisulfite and the like. Is preferably added as a potassium salt, sodium salt or ammonium salt. It is also preferable to contain an arylsulfinic acid such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid, p-aminobenzenesulfinic acid.
These compounds are 0.02-1.0mo in the liquid used.
It is preferable to contain 1 / L. As the preservative, in addition to the above, ascorbic acid, carbonyl bisulfite adduct, or carbonyl compound may be added.

The bleach-fixing composition and fixing composition of the present invention include a mercapto nitrogen-containing heterocyclic ring such as mercaptotriazole, aminomercaptotriazole and N-methylmercaptoimidazole which form stable silver ions for improving image storability. The bisamidines and bisguanidines or monoamidines described in JP-A-5-303185 may be added to accelerate washing out of the compound and the developing agent. In addition, polymers such as polyethylene glycol and poly (vinylpyrrolidone), chelating agents, defoaming agents and antifungal agents may be added to the bleach-fixing composition and fixing composition of the present invention as required.

It is advantageous that the processing composition of the present invention has a form in which all the components contained in the liquid to be used are contained in one composition, that is, a one-component composition. However, a color developing composition or a bleach-fixing composition is used. When it is not desirable to keep the constituents in contact with each other for a long period of time, the constituents may be separated into two or more liquid agents to prepare a two- or three-part treatment composition.
It is usually called a 1, 2 or 3 part structure according to the international standard ISO5989. The effect and characteristics of the invention are not lost by dividing the treatment composition of the present invention into parts. Among them, the color developing composition is particularly 1
Part structure is desirable.

The container of the treatment composition of the present invention may be a known material depending on the content, and even if the container is made of a single material, a composite material such as a material having high gas permeability may be used. It may be made of a composite material composed of a material highly stable to alkali. From the viewpoint of reuse and recyclability, it is preferable that the container is made of a single material.
The material used for the container is polyester resin, polyolefin resin, acrylic resin, ABS resin, epoxy resin, polyamide resin such as nylon, polyurethane resin, polystyrene resin, polycarbonate resin, PV.
A, polyvinyl chloride, polyvinylidene chloride, and polyethylene resins, among which polyester resins such as polyethylene terephthalate and polyethylene naphthalate,
A container made of a polyolefin resin such as polyethylene or polypropylene as a single material is preferable, and among them, a polyethylene resin is preferable, and a high-density polyethylene resin (HDPE) is more preferable as a container material.

The material of the container used in the present invention may contain carbon black, titanium white, pigment, calcium carbonate, a plasticizer compatible with the material, etc., as long as it does not affect the treatment composition. As the material of the container, preferably, the proportion of polyethylene in the material is 85% or more and no plasticizer is contained, and more preferably, the proportion of polyethylene in the material is 95% or more and no plasticizer is contained.

The shape and structure of the container filled with the treatment composition of the present invention can be arbitrarily designed according to the purpose.
In addition to the fixed-size bottles, the expandable / contractible type described in JP-A-1-235950 and the container with a flexible partition described in JP-A-62-134626 can also be used. The container described in JP-A No. 11-282148 is particularly preferable as the container for the treatment composition of the present invention in terms of capacity, space efficiency, self-sustaining property, shape preservation property, reuse and recycling. A preferred embodiment is a kit in which a plurality of compositions of the present invention are filled in a container made of a single constituent material having the same shape and volume, and the containers are assembled in a single cartridge, The cartridge described in JP-A-2000-3014 can be mentioned as an example. The combination of treatment compositions in the cartridge can be arbitrarily selected. The cartridges described in JP-A Nos. 11-295858 and 11-288068 are preferred embodiments in which a developing composition, a bleaching composition and a fixing composition are incorporated.

In order to prevent fading of dyes and formation of stains due to residual magenta couplers, formalin, acetaldehyde, pyruvaldehyde, and formaldehyde compounds described in US Pat. Sulfite adducts or N-methylol compounds described in JP-A-5-34889 may be added. Further, it is preferable to contain an arylsulfinic acid such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid and p-aminobenzenesulfinic acid. Further, a surfactant as a draining agent, a chelating agent as a water softener, a buffering agent for pH adjustment, an antifoaming agent, a fungicide, a bactericide, etc. may be added as required. The preferred pH is 4 to 10, and more preferably 5 to 8.
Although the temperature can be set variously depending on the use and characteristics of the light-sensitive material, it is generally 20 ° C to 50 ° C, preferably 25 ° C to 45 ° C.

The exposure device in the present invention means a group of devices for irradiating the photosensitive material with exposure light in the image forming system, and includes a light source, an optical system, a modulation means,
An exposure apparatus having a scanning unit and a control apparatus for controlling these operations. The exposure digital data depending on the exposure system device is a digital system data converted by a so-called driver of the exposure system device so that a desired halftone dot density is reproduced at a desired place after development processing. . Area modulation means expressing the density of image density by the size of the area of a region having a constant density, and more specifically, the dots (dots) of an ink or coloring pigment having a constant density and a white background. The macro observation density is modulated by the area ratio of. Also, the digital image data for area modulation is a raster image processor (RI
P) and other halftone images and thin lines, characters,
It means vector data such as a figure and is data that does not depend on the exposure system device. Therefore, among the image forming methods of the present invention, in the image forming method in which the exposure is performed based on the area modulation digital image data converted into the exposure digital data that depends on the exposure system device, at least the density modulation (grayscale expression) is performed. , A method of performing area-modulated exposure in one step like an image setter is characterized in that at least two steps of data conversion are performed from a document represented by modulating the amount of ink or coloring pigment for gradation reproduction. Not included. Further, in the case of a silver halide light-sensitive material for color proof which is one of the preferable embodiments of the present invention, it is preferable that scanning exposure is carried out based on the above area modulation digital image data.

In the present invention, a silver halide color light-sensitive material (hereinafter sometimes simply referred to as "light-sensitive material") includes a silver halide emulsion layer containing a yellow dye-forming coupler and a magenta dye-forming coupler on a support. A silver halide color light-sensitive material having at least one silver halide emulsion layer containing at least one and a silver halide emulsion layer containing a cyan dye-forming coupler is preferably used. In the present invention, the silver halide emulsion layer containing the yellow dye-forming coupler as a yellow color-forming layer,
The silver halide emulsion layer containing the magenta dye-forming coupler functions as a magenta coloring layer and the silver halide emulsion layer containing the cyan dye-forming coupler functions as a cyan coloring layer. The silver halide emulsion contained in each of the yellow coloring layer, the magenta coloring layer and the cyan coloring layer is
It is preferable to have photosensitivity to light in different wavelength regions (for example, light in blue region, green region, and red region).

The light-sensitive material of the present invention may have a hydrophilic colloid layer, an antihalation layer, an intermediate layer and a coloring layer, which will be described later, if desired, in addition to the yellow coloring layer, the magenta coloring layer and the cyan coloring layer. Good. The silver halide light-sensitive material preferably used in the present invention will be described in detail below.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 01 μm to 2 μm is preferable. Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less, more preferably 10% or less. . At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating.

The silver halide emulsion used in the present invention includes various compounds or precursors thereof for the purpose of preventing fogging during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of the specification of Japanese Patent No. 15272 are preferably used. Furthermore, the 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (wherein the aryl residue has at least one electron-withdrawing group) are also preferably used.

In the present invention, in order to improve the storage stability of the silver halide emulsion, the hydroxamic acid derivatives described in JP-A-11-109576 and JP-A-11-32709.
A cyclic ketone having a double bond in which both ends are substituted with an amino group or a hydroxyl group adjacent to the carbonyl group described in No. 4 (particularly represented by the general formula (S1), paragraphs 0036 to 0071) Can be incorporated into the specification of the present application), and sulfo-substituted catechols and hydroquinones described in JP-A No. 11-143011 (for example,
4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,
3-dihydroxybenzene sulfonic acid, 2,5-dihydroxybenzene sulfonic acid, 3,4,5-trihydroxybenzene sulfonic acid and salts thereof), and general formulas (I) to (III) of JP-A No. 11-102045. The water-soluble reducing agent represented by is also preferably used in the present invention.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the light-sensitive material of the present invention, blue, green,
Examples of spectral sensitizing dyes used for spectral sensitization in the red region include, for example, Heterocyclic compounds-Cyanine by FM Harmer.
dyes andrelated compounds (John Wiley & Sons [New
York, London] 1964). As specific examples of compounds and the spectral sensitization method, those described in JP-A-62-215272, page 22, upper right column to page 38 are preferably used. Further, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, JP-A-3-12 is known.
The spectral sensitizing dye described in No. 3340 is very preferable from the viewpoint of stability, strength of adsorption, temperature dependence of exposure and the like.

The addition amount of these spectral sensitizing dyes is wide depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ^-6 mol to 5.0 × 10 ^-3
It is in the molar range.

The silver halide emulsion used in the present invention is usually chemically sensitized. In the chemical sensitization method, sulfur sensitization typified by the addition of an unstable sulfur compound, noble metal sensitization typified by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used. Of these, gold-sensitized ones are particularly preferable. By performing gold sensitization, it is possible to further reduce fluctuations in photographic performance when scanning and exposing with laser light or the like.

To perform gold sensitization on the silver halide emulsion used in the present invention, various inorganic gold compounds and gold (I) complexes having inorganic ligands and gold (I) compounds having organic ligands are used. Can be used. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and examples of the gold (I) complex having an inorganic ligand include a gold dithiocyanate compound such as potassium gold (I) dithiocyanate and gold (I) 3 dithiosulfate. It is preferable to use a compound such as sodium dithiosulfate compound such as sodium.

As the gold (I) compound having an organic ligand, bis gold (I) mesoionic heterocycles described in JP-A-4-267249, for example, gold (I) tetrafluoroborate bis (1,4) , 5-Trimethyl-1,2,4-triazolium-3-thiolate), an organic mercapto gold (I) complex described in JP-A-11-218870, such as potassium bis (1- [3- (2-sulfonate benzamide) ) Phenyl] -5-mercaptotetrazole potassium salt) Aurate (I) pentahydrate, a gold (I) compound coordinated with a nitrogen compound anion described in JP-A-4-268550, for example, bis (1-methylhydan) Toinato) gold (I) sodium salt tetrahydrate can be used. Further, gold (I) thiolate compounds described in U.S. Pat.
-69074, JP-A-8-69075, JP-A-9-2
69554 gold compounds, US Pat. No. 56208
The compounds described in No. 41, No. 5912112, No. 5620841, No. 5939245, and No. 5912111 can also be used. The addition amount of these compounds may be varied over a wide range depending on the case, but 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ⁻⁶ mol, per mol of silver halide.
Is about 5 × 10 ⁻⁴ mol.

It is also possible to use colloidal gold sulfide, and its manufacturing method is Research Disclosure (37154), Solid State Ionics, Vol. 79, No. 6.
0-66 pages, 1995, Compt.Rend.Hebt.Seances
Acad. Sci. Sect. B Volume 263, p. 1328, 1966
It is described in annual publications. Various sizes of colloidal gold sulfide can be used, and particles having a particle size of 50 nm or less can also be used. The addition amount can be varied over a wide range depending on the case, but it is 5 as gold atom per mol of silver halide.
× 10 ^{-7 to} 5 × 10 ^-3 mol, preferably 5 × 10 ^{-6 to} 5
It is × 10 ^-4 mol. In the present invention, gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, and noble metal sensitization using a compound other than a gold compound. The silver halide color light-sensitive material of the present invention may be any color light-sensitive material, but is preferably a color paper, a silver halide color light-sensitive material for color proof, and a color light-sensitive material for display. Among them, it is preferably applied to a silver halide color light-sensitive material having a reflective support, and particularly preferably a silver halide color light-sensitive material for color proof.

The light-sensitive material according to the present invention has a hydrophilic colloid layer for the purpose of preventing irradiation and halation and improving safety of safelight. It is preferable to add the dyes which can be decolorized by the treatment (in particular, oxonol dyes and cyanine dyes) described above. Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes may deteriorate color separation and safelight safety when the amount used is increased. Examples of dyes that can be used without deteriorating color separation include JP-A-5-127324 and 5-1.
The water-soluble dyes described in No. 27325 and No. 5-216185 are preferable.

In the present invention, instead of the water-soluble dye,
Alternatively, a colored layer that can be decolorized by treatment with a water-soluble dye is used. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with the emulsion layer via an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to selectively install only a part of them. It is also possible to install a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is in the wavelength range used for exposure (400 nm for ordinary printer exposure).
It is preferable that the optical density value is 0.2 or more and 3.0 or less at a wavelength having the highest optical density in the visible light region of up to 700 nm, the wavelength of the scanning exposure light source used in the case of scanning exposure). It is more preferably 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

To form the colored layer, a conventionally known method can be applied. For example, Japanese Patent Laid-Open No. 2-282244-3
The dyes described on page 8 from the upper right column of the page, and JP-A-3-79
No. 31, page 3, upper right column to page 11, lower left column, a method of incorporating a solid fine particle dispersion in a hydrophilic colloid layer, a method of mordanting an anionic dye with a cationic polymer, a method of halogenating the dye Examples thereof include a method of adsorbing to fine particles such as silver and fixing in a layer, a method of using colloidal silver as described in JP-A-1-239544, and the like. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye that is substantially water-insoluble at a pH of 6 or less but is substantially water-soluble at a pH of 8 or more is disclosed. 2-30824
No. 4, pages 4-13. Also, for example,
A method of mordanting an anionic dye on a cationic polymer is described in JP-A-2-84637, pages 18 to 26. For the preparation method of colloidal silver as a light absorber, see US Pat. Nos. 2,688,601 and 3,45.
No. 9,563. Among these methods, the method of incorporating a fine powder dye and the method of using colloidal silver are preferable.

The light-sensitive material of the present invention preferably comprises at least one yellow color forming silver halide emulsion layer, at least one magenta color forming silver halide emulsion layer and at least one cyan color forming silver halide emulsion layer, Generally, these silver halide emulsion layers are a yellow color-forming silver halide emulsion layer, a magenta color-forming silver halide emulsion layer and a cyan color-forming silver halide emulsion layer in order from the support.

However, a layer structure different from this may be adopted. The silver halide emulsion layer containing a yellow coupler may be arranged at any position on the support, but when the yellow coupler-containing layer contains silver halide tabular grains, a magenta coupler-containing silver halide It is preferably coated at a position farther from the support than at least one of the emulsion layer and the cyan coupler-containing silver halide emulsion layer. Also, color development acceleration,
From the viewpoint of accelerating desilvering and reducing the residual color due to the sensitizing dye, the yellow coupler-containing silver halide emulsion layer is coated at a position farthest from the support, as compared with other silver halide emulsion layers. preferable. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably a central layer of the other silver halide emulsion layers, and from the viewpoint of reducing photofading, the cyan coupler-containing silver halide emulsion layer is The bottom layer is preferred. Further, each of the yellow, magenta and cyan color forming layers may be composed of two layers or three layers. For example, JP-A-4-75055 and 9-114.
035, 10-246940, US Pat. No. 5,5.
As described in JP-A No. 76,159, it is also preferable to provide a coupler layer containing no silver halide emulsion adjacent to the silver halide emulsion layer to form a color forming layer.

The silver halide emulsion and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied in the present invention, and the processing method and processing addition applied for processing the photographic material. As the agent, JP-A-62-21
5272, JP-A-2-33144, European Patent EP
Those described in 0,355,660A2, particularly those described in European Patent EP0,355,660A2 are preferably used. Furthermore, JP-A-5-34
No. 889, No. 4-359249, No. 4-313753
No. 4, No. 4-270344, No. 5-66527, No. 4
-34548, 4-145433, 2-854.
Issue 1, 1-158431, 2-90145, 3
The silver halide color photographic light-sensitive materials and their processing methods described in JP-A-194539, JP-A-2-93641, European Patent Publication No. 0520457A2 and the like are also preferable.

In particular, in the present invention, the above-mentioned reflection type support, silver halide emulsion, different metal ion species doped in silver halide grains, storage stabilizer for silver halide emulsion or antifoggant. , Chemical sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and its emulsion dispersion method, color image storability improving agent (anti-staining agent or anti-fading agent), As for the dye (colored layer), the type of gelatin, the layer structure of the light-sensitive material and the coating pH of the light-sensitive material, those described in each part of the publications shown in the following table are particularly preferably applicable.

[0152]

[Table 1]

[0153]

[Table 2]

Other cyan, magenta and yellow couplers used in the present invention are described in JP-A-62-62.
-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6, line 3 of JP-A-2-33144, upper right column 1
Line 4 to page 18, upper left column, end line and page 30, upper right column, line 6 to
Page 35, lower right column, line 11 and EP 0355,660A2, page 4, lines 15 to 27, page 5, lines 30 to 28, last line, page 45, lines 29 to 31, line 47, page 23 Line 63
The couplers described on page 50, line 50 are also useful. The present invention also relates to general formulas (II) and (II) of WO-98 / 33760.
I), a compound represented by the general formula (D) of JP-A-10-221825 may be added, which is preferable.

As the cyan dye-forming coupler which may be used in the present invention (simply referred to as "cyan coupler"), a pyrrolotriazole type coupler is preferably used, and a general formula (I) of JP-A-5-313324 or (I
The coupler represented by I), the coupler represented by formula (I) of JP-A-6-347960, and the exemplified couplers described in these patents are particularly preferable. Also,
Phenol-type and naphthol-type cyan couplers are also preferable, and for example, the cyan coupler represented by the general formula (ADF) described in JP-A-10-333297 is preferable. As a cyan coupler other than the above, European Patent EP048
8248 and EP0491197A1 described above, pyrroloazole type cyan couplers, 2,5-diacylaminophenol couplers described in US Pat. No. 5,888,716, and US Pat. No. 4,873,183.
Nos. 4,916,051 and pyrazoloazole type cyan couplers having an electron-withdrawing group and a hydrogen bonding group at the 6-position, particularly JP-A-8-171185 and 8-31.
Pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in Nos. 1360 and 8-339060 are also preferable.

In addition to the diphenylimidazole type cyan couplers described in JP-A-2-33144, 3-hydroxypyridine type cyan couplers (in particular, the couplers listed as specific examples) described in European Patent EP 0333185A2. (42) 4-equivalent couplers having a chlorine-releasing group to make them 2-equivalent, couplers (6) and (9) are particularly preferable) and JP-A-64-322.
Cyclic active methylene-based cyan couplers described in JP-A No. 60 (specifically, coupler example 3 listed as a specific example,
8, 34 are particularly preferred), European Patent EP 0456622.
It is also possible to use the pyrrolopyrazole type cyan couplers described in 6A1 and the pyrroloimidazole type cyan couplers described in European Patent EP0484909.
Among these cyan couplers, JP-A-11-28
Particularly preferred are the pyrroloazole-based cyan couplers represented by the general formula (I) described in Japanese Patent No. 2138. It is applied as is and is preferably incorporated as part of the specification of the present application.

The magenta dye-forming coupler used in the present invention (may be simply referred to as "magenta coupler")
As the 5-
Pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers are used. Among them, secondary or tertiary alkyl groups such as those described in JP-A-61-65245 are used in terms of hue, image stability, color developability and the like. Pyrazolotriazole couplers directly linked to the 2, 3 or 6 position of the pyrazolotriazole ring, pyrazoloazole couplers containing sulfonamide group in the molecule as described in JP-A-61-65246, JP-A-61. Pyrazoloazole couplers having alkoxyphenyl sulfonamide ballast groups as described in US Pat.
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 49A and No. 294,785A. Particularly, as the magenta coupler, a pyrazoloazole coupler represented by the general formula (MI) described in JP-A-8-122984 is preferable, and paragraph numbers 0009 to 0026 of the patent are directly applied to the present application. Incorporated as part of the specification. In addition to these, the pyrazoloazole couplers having steric hindrance groups at both the 3-position and the 6-position described in European Patent Nos. 854384 and 884640 are also preferably used.

Further, as the yellow dye-forming coupler (in this specification, sometimes referred to simply as "yellow coupler"), in addition to the compounds described in the above table, the acyl group described in European Patent EP0447969A1 is used. Acylacetamide type yellow couplers having a 3- to 5-membered cyclic structure, malondianilide type yellow couplers having a cyclic structure described in European Patent No. EP 0482552A1, European Patent Nos. 953870A1, 953871A1 and 953871A1. 953872A1 and 9th
No. 53873A1, No. 953874A1, No. 95
Pyrrole-2 or 3-yl or indol-2 or 3-ylcarbonylacetic acid anilide type couplers described in 3875A1 and the like, acylacetamide type yellow having a dioxane structure described in US Pat. No. 5,118,599. A coupler is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

The couplers used in the present invention are loadable latex polymers in the presence (or absence) of the high boiling organic solvents described in the table above (see, for example, US Pat. No. 4,20,20).
No. 3,716) or dissolved with a water-insoluble polymer and an organic solvent-soluble polymer to emulsify and disperse in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in US Pat. No. 4,857,449, column 7,
The homopolymers or copolymers described in column 15 and pages 12 to 30 of WO88 / 00723 are mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, especially an acrylamide-based polymer in terms of color image stability and the like.

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, WO98 / 33
760, phenidone and hydrazine compounds described in U.S. Pat. No. 4,923,787 and the like, JP-A-5-2496.
37, Japanese Patent Laid-Open No. 10-282815 and German Patent No. 1
White couplers described in 9629142A1 and the like can be used. Further, in particular, when the pH of the developer is raised to accelerate the development, German Patent No. 19618786
A1, European Patent No. 839623A1, European Patent No. 8
It is also preferable to use the redox compounds described in 42975A1, German Patent 1980846A1 and French Patent 2760460A1.

In the present invention, it is preferable to use a compound having a triazine skeleton having a high molar extinction coefficient as the ultraviolet absorber. For example, the compounds described in the following patents can be used. These are preferably added to the photosensitive layer and / or the non-photosensitive layer. For example, JP-A-46-3
No. 335, No. 55-152776, JP-A-5-197.
074, 5-232630, 5-307232.
No. 6, No. 6-211813, No. 8-53427, No. 8
-234364, 8-239368, 9-31
067, 10-15898 and 10-1475.
77, 10-182621, German Patent 1973.
The compounds described in 9797A, EP 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, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As preferable gelatin, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably 5 ppm.
Or less, and 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, most preferably 5 mg / m ² or less.

In the present invention, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, a bactericidal / mold-proofing agent as described in JP-A-63-271247 is used. It is preferable to add it. Further, the film pH of the light-sensitive material is preferably 4.0 to 7.0, and more preferably 4.0 to 6.5.

In the present invention, a surfactant can be added to the light-sensitive material from the viewpoints of improving the coating stability of the light-sensitive material, preventing the generation of static electricity, adjusting the charge amount, and the like. Examples of the surfactant include anionic surfactants, cationic surfactants, betaine surfactants and nonionic surfactants, 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. Particularly, 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 preferably 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 , and preferably 1 × 10 ⁻⁴ to 1 × 10 ^{−. 1} g / m ² , more preferably 1 ×
It is 10 ⁻³ to 1 × 10 ⁻² g / m ² .

The light-sensitive material of the present invention can form an image by an exposure step of irradiating light according to image information and a developing step of developing the light-irradiated light-sensitive material. The light-sensitive material of the present invention is used in a cathode ray (CR) in addition to being used in a printing system using an ordinary negative printer.
It is also suitable for the scanning exposure method using T). A cathode ray tube exposure apparatus is simpler and more compact than an apparatus using a laser, and is low in cost. Moreover, the optical axis and color can be easily adjusted. For the cathode ray tube used for image exposure, various light-emitting bodies that emit light in the spectral region are used as necessary. For example, any one of a red light emitting body, a green light emitting body, and a blue light emitting body, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a fluorescent substance that emits light in a yellow, orange, violet, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used. When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode tube also has a phosphor that emits light in a plurality of spectral regions, a plurality of colors are exposed at once, that is, a plurality of cathode ray tubes are exposed. It is also possible to input an image signal of this color and cause the tube surface to emit light. A method of sequentially inputting image signals for each color to sequentially emit light of each color and exposing through a film that cuts colors other than that color (area sequential exposure) may be adopted. Generally, area sequential exposure is used. However, since a high resolution cathode ray tube can be used, it is preferable for high image quality.

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

When such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention can be arbitrarily set depending on the wavelength of the scanning exposure light source used.
A solid-state 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 can halve the oscillation wavelength of the laser (that is, a second harmonic emission light source), so blue light, green light Light is obtained. Therefore, the spectral sensitivity maximum of the light-sensitive material can be provided in the normal three wavelength regions of blue, green and red. These semiconductor lasers have, for example, a wavelength of 4
30-450nm blue semiconductor laser (2001 March
Mon Announced by Nichia Corporation at the 48th Joint Lecture Meeting on Applied Physics), semiconductor lasers (oscillation wavelength: about 940n)
m) LiNbO having a waveguide-like inverted domain structure
Approximately 470 wavelength was taken out by SHG crystal of ₃
nm blue laser, semiconductor laser (oscillation wavelength about 1
L having a waveguide-like inversion domain structure
530 nm green laser and semiconductor laser GaAl, which are wavelength-converted and taken out by SHG crystal of iNbO _3.
Y using As (oscillation wavelength 808.7 nm) as the excitation light source
A VO ₄ solid state laser (oscillation wavelength 1064 nm) was wavelength-converted by a LiNbO ₃ SHG crystal having an inversion domain structure to obtain a green laser of 532 nm, and as a red semiconductor laser, AlGaInP (oscillation wavelength of about 680 nm: manufactured by Matsushita Electric Industrial Co., Ltd. Type No. LN9
R20), (oscillation wavelength about 650 nm: Hitachi type N
o. HL6501MG), (oscillation wavelength about 685 nm:
In addition to the Mitsubishi ML101J10), a red semiconductor laser with a wavelength of about 685 nm (Hitachi Type No. HL6738M)
G) and the like. Especially, the blue exposure wavelength is 420 ~
The use of a 460 nm blue semiconductor laser is preferable because the exposure apparatus is compact. The exposure time in such scanning exposure is set to a pixel density of 400 dp.
When the pixel size when i is defined as the exposure time, the preferable exposure time is 10 ⁻⁴ seconds or less, and more preferably 10 ⁻⁶ seconds or less. In the case of a color proof application, as will be described later in detail, it is preferable to expose at a high density of about 2400 dpi and within a range of 10 ⁻⁴ to 10 ⁻⁷ seconds per pixel, but the present invention is not limited to this. Not something.

The silver halide color light-sensitive material of the present invention comprises
It can be preferably used in combination with the exposure and development system described in the following publicly known materials. Examples of the developing system include an automatic printing and developing system described in JP-A-10-333253, and JP-A-2000-102.
No. 06, a photosensitive material conveying device, JP-A-11-215
A recording system including the image reading device described in Japanese Patent No. 312, JP-A-11-88619 and JP-A-10-20295.
No. 0, an exposure system comprising a color image recording system, a digital photo print system including a remote diagnosis system described in JP-A-10-210206, and Japanese Patent Application No.
A photo print system including the image recording device described in JP-A No. 0-159187 can be used. Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table. When exposing the light-sensitive material of the present invention to a printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved. In the present invention, a European patent EP0789
As described in 270A1 and EP0789480A1, a yellow microdot pattern may be pre-exposed and copy regulation may be applied in advance before image information is added.

The present invention is preferably applied to a light-sensitive material having rapid processing suitability. In the case of rapid processing, the color development time is preferably 60 seconds or less, more preferably 50 seconds.
Seconds or less 6 seconds or more, more preferably 30 seconds or less 6 seconds or more. Similarly, the bleach-fixing time is preferably 60 seconds or less,
More preferably 50 seconds or less and 6 seconds or more, more preferably 3
0 seconds or less and 6 seconds or more. The washing or stabilizing time is preferably 150 seconds or less, more preferably 130 seconds or less and 6 seconds or more. The color developing time means the time from the time when the light-sensitive material enters the color developing solution to the time when it enters the bleach-fixing solution in the next processing step. For example, in the case of processing with an automatic processor, etc., the time during which the light-sensitive material is immersed in the color developing solution (so-called in-liquid time) and the light-sensitive material leaves the color developing solution, and bleaching in the next processing step occurs. The total of the time during which it is transported in the air toward the fixing bath (so-called aerial time) is called the color development time. Similarly, the bleach-fixing time refers to the time from when the light-sensitive material enters the bleach-fixing solution until it enters the next washing or stabilizing bath. The washing or stabilizing time is the time during which the light-sensitive material is in the washing or stabilizing liquid and is in the liquid for the drying step (so-called in-liquid time).
Say. The method of developing the light-sensitive material of the present invention after exposure includes a conventional method of developing with a developer containing an alkaline agent and a developing agent, an activator such as an alkali solution containing no developing agent in which the developing agent is contained in the light-sensitive material. In addition to a wet method such as a method of developing with a beta solution, a heat developing method without using a processing solution can be used. In particular, the activator method is a preferable method because the processing solution does not contain a developing agent, so that the processing solution can be easily managed and handled, and that the load at the time of processing the waste solution is small and the environment can be preserved. In the activator method, the developing agent or its precursor incorporated in the light-sensitive material is, for example, JP-A-8-234388.
The hydrazine type compounds described in Nos. 9-152686, 9-1522693, 9-212814 and 9-160193 are preferred.

Further, a developing method in which the amount of silver coated on the light-sensitive material is reduced and an image amplification process (intensification process) using hydrogen peroxide is also preferably used. In particular, it is preferable to use this method as an activator method. Specifically, JP-A-8
The image forming method using an activator solution containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152695 is preferably used. In the activator method, after processing with an activator solution, desilvering is usually performed, but in the image amplification processing method using a light-sensitive material having a low silver content,
The desilvering process can be omitted and a simple method such as washing with water or stabilization can be performed. Further, in the method of reading image information from a light-sensitive material with a scanner or the like, it is possible to adopt a processing form which does not require desilvering processing even when a light-sensitive material having a high silver content such as a light-sensitive material for photographing is used. The activator solution, the desilvering solution (bleaching / fixing solution), the washing and stabilizing solution used in the present invention may have any known processing materials and processing methods. Preferably, Research Disclosure Item 36544 (September 1994)
Mon) pp. 536-541, JP-A-8-234388
It is possible to use those described in No. The present invention is particularly preferably applicable to a color photosensitive material for digital direct color proof (hereinafter referred to as a color proof photosensitive material), a digital direct color proof system, and an image forming method thereof. The proof light-sensitive material is generally a silver halide color light-sensitive material having a silver halide light-sensitive layer that forms at least a yellow dye, a magenta dye, and a cyan dye on a support, and has a hue similar to that of a printing ink. Exposure is performed using three or more light source units having different wavelengths based on the halftone dot image information, and an area-modulated image is formed. Black (chromaticity and Dmax) and solid solid (chromaticity and D
It is also possible to provide a fourth photosensitive layer for the purpose of satisfying both max (improvement of color reproducibility) and discrimination of black plate. In this case, the exposure light source uses three or four light sources having different wavelengths. The exposure light source often has a plurality of light source units of each color (preferably 8 or more and 500 or less), and it is possible to use LEDs or LDs or other devices. As the exposure light source, it is possible to use light sources of all wavelengths in the visible region and infrared region such as blue, green and red, and the combination thereof is also free. In the present invention, the number of light source units for each color of the exposure light source is 2 in particular.
0 to 200 is preferable.

As the system, the photosensitive material is automatically pulled out from the magazine, cut into a sheet, wound around the outer drum for exposure and rotated, and halftone dot image information is emitted from three or more light sources of different wavelengths. 8 units each
Scanning exposure is performed by using an array light source for exposure, which is a combination of two or more pieces, and after recording a halftone dot image of an area gradation with dots having a resolution of 2000 dpi or more, the exposed color photosensitive material is automatically processed by an automatic developing machine. Development process,
A direct digital color proof system and an image forming method for outputting a halftone dot color proof image of A3 size or more (a B1 size system is also possible if necessary) are preferable, but the present invention is applied to color proof. This is not limited to the color proof light-sensitive material, system and image formation described above.

Resolution of 2400 dpi or higher, exposure beam diameter of 1 dot is 0.5 μm or more and 50 μm in half width of light intensity
m, the exposure time when at least one exposure light source exposes one dot is 10 ^-8 seconds or more and 10 ^-2 seconds or less, and the rotation number of the outer drum is 100 rpm or more and 4000 rpm or less, at least The wavelength of one exposure light source is 700 nm or more, the exposure amount of at least one exposure light source is two or more steps, and the exposure energy of the longest-wavelength exposure light source is 1.1 times or more of the other exposure energy. After exposure, the photosensitive material should be peeled off from the outer drum and conveyed so that the exposed surface faces downward.The emulsion surface should be exposed in the color developing solution of the automatic processor, the bleach-fixing solution and the washing bath. It is conveyed so as to turn downward, and the time from the end of exposure of the photosensitive material to the leading edge of the color developing solution is 20 seconds or more and 3 minutes or less, The difference between the time from the end of light to the time when the leading end of the exposed photosensitive material in the transport direction enters the color developing solution and the time from the trailing end of the transport direction entering the color developing solution in the range of 1 minute to 10 minutes, The processing time of the color developing solution and the bleach-fixing solution is 10 seconds or more and 100 seconds or less and the processing time difference is 30 seconds or less, and the capacity of the processing tank for the color developing solution and the bleach-fixing solution is 8 L or more and 20 L or more.
The following items are required, the number of washing tanks is 2 or more and 5 or less, the color developing and bleach-fixing solution are supplied in an integrated kit, and the replenishing amount of color developing is 1 m ^{2 of the} light-sensitive material, 50 ml or more and 300 ml or less, and the replenishing amount of the bleach-fixing solution is 3 per 1 m ^{2 of the} light-sensitive material.
0 ml or more and 250 ml or less, and the replenishing amount of the washing water is 50 ml or more and 1000 ml or less in total of the washing water, and the area of the photosensitive material to be processed is automatically known and replenished. The air-turning transport roller has a mechanism for automatically washing with water, at least one guide plate in contact with the emulsion surface of the light-sensitive material uses Teflon (registered trademark) material, during proof printing, or another output. Difference between lots of photosensitive material by writing a specific image on the print and measuring this image density or chromaticity or by visual comparison with the target image,
It has a calibration function to correct changes in sensitivity due to changes over time, temperature and humidity during exposure, changes in processing liquid state, etc., and calibration can be performed using continuous-tone images with a density lower than Dmax of the photosensitive material. It has a function, can perform calibration by visual judgment or density measurement or color difference colorimetry of 20% or more and 80% or less of a halftone image, photosensitive material of the same size is supplied to two or more magazines, and one magazine When the photosensitive materials of the other are exhausted, the photosensitive materials of other magazines are automatically supplied, and the photosensitive materials of two or more sizes are simultaneously supplied by different magazines, and the size is automatically switched. The length of the photosensitive material is 30 m or more and 100 m or less, and the photosensitive material is pulled out from the magazine and pulled out. Time to the start of the end after exposure 1
0 seconds or more and 100 seconds or less, the black plate image is formed of yellow, magenta, and cyan, the difference in dot gain of each color forming the halftone dots of the black plate is 5% or less, and the photosensitive material The total thickness of the support used for
m or more and 150 μm, the thickness of the front laminate of the support used for the photosensitive material is 10 μm or more and 50 μm, the thickness of the back laminate of the support used for the photosensitive material is 10 μm or more and 50 μm, It has a back layer of 0.1 μm or more and 30 μm or less on the surface opposite to the surface on which the photosensitive layer is coated, and the total film thickness of the surface of the photosensitive material having the photosensitive silver halide is 3 μm or more and 30 μm or less.
m or less, the difference between the total thickness of the surface of the photosensitive material having the photosensitive silver halide and the total thickness of the back surface is within 10 μm, and the difference of the photosensitive silver halide used for the photosensitive material is Characterized by having a silver chloride content of 90% or more, using a photosensitive material processed into a roll with the emulsion surface facing outward, and having a peak wavelength of at least one of the maximum spectral sensitivities of 700 nm or more. And a direct digital color proof system and an image forming method having one or more features selected from such features as automatically winding a photosensitive material cut into a sheet by a squeeze roller on a drum. Also, the effect of the present invention can be applied to a color proof light-sensitive material.

The shape of the spot is circular, elliptical,
Any of rectangular shapes may be used. The light intensity distribution of one spot may be a Gaussian distribution or a trapezoid with a relatively constant intensity. In particular, one light source may be used, but a multi-channel array in which a plurality of light sources of the same wavelength (preferably 10 to 100, more preferably 40 to 80) are arranged is preferable. Regarding an exposure method and an image forming method using a laser, an LED and an array thereof as a light source, JP-A-10-142752 and JP-A-11-2
No. 42315, JP-A 2000-147723, JP-A 2
000-246958, JP-A-2000-354174.
No. 2000-206654, European Patent EP-1
It is described in detail in No. 048976A and the like and can be preferably used in the present invention.

More specifically, it is as follows. A preferred embodiment of the exposure light source is JP-A 2000-147.
No. 723 of Japanese Patent Laid-Open No. 723 or JP 2000-2066.
No. 54, paragraph numbers 0053, 0059 to 0061, 00
64 to 0067 and are preferably applied to the present invention. Preferable modes of the beam of the exposure light source and the array of the exposure light source are described in paragraph Nos. 0022 to 0023 of JP-A-2000-147723 and JP-A-2000-206.
No. 654 to paragraphs 0025 to 0030, which are preferably applied to the present invention. In order to improve the productivity at the time of exposure, a method of winding a photosensitive material around a drum and performing scanning exposure is excellent. The aspect of the preferable light source is
An LED array described in JP-A-2000-246958, and JP-A-2000-2469 having the LED array.
The image recording apparatus described in No. 58 is preferably applied according to the present invention. Regarding the method of winding the drum, it is described in paragraph Nos. 0057 to 00 of JP-A-2000-206654.
58, 0062 to 0063, and likewise preferably applied to the present invention.

Further, it is also preferable to perform calibration by the method described in European Patent EP-1048976A to stably form an image, which is applied to the present invention. Regarding the method for converting digital image data into image data for exposure and the exposure processing method, which is preferably adopted in the present invention for producing a color proof, there is disclosed in JP-A-2000-3.
The materials described in JP-A No. 54174 and JP-A No. 2000-147723 can be used as they are. More specifically,
1 is a color proof manufacturing apparatus of FIG. 1 described in Japanese Patent Application Laid-Open No. 2000-354174, including FIG. 1 and FIG. The described portions of 0034 to 0057 are preferably incorporated as part of the specification of the present invention.

[0176]

EXAMPLES The present invention will be described below in greater detail by giving Examples, but the present invention is not limited thereto.

[Example 1] (Preparation of color paper) (Preparation of blue sensitive layer emulsions A-1 and A-2 of the invention) 5.7% by mass
41.0 ml of 10% NaCl solution was added to 1.06 liters of deionized distilled water containing deionized gelatin, and 46.4 ml of H ₂ SO ₄ (1N) was added, and 0.012 g of compound (X) was added. When the liquid temperature was adjusted to 60 ° C. after the addition, 0.1 mol of silver nitrate and 0.1 mol of NaCl were immediately added to the reaction vessel over 10 minutes while performing high-speed stirring. Subsequently, 1.5 mol of silver nitrate and NaCl solution were added over 60 minutes by a flow rate acceleration method so that the final addition rate was 4 times the initial addition rate.
Next, 0.2 mol% silver nitrate and NaCl solution were added at a constant addition rate over 6 minutes. At this time, K ₃ IrCl ₅ (H ₂ O) was added to the NaCl solution at 5 × with respect to the total amount of silver.
An amount of 10 ⁻⁷ mol was added to dope the particles with iridium acoide. Furthermore, 0.2 mol of silver nitrate and 0.18
Molar NaCl and 0.02 molar KBr solution were added over 6 minutes. At this time in the aqueous halide solution, K ₄ Ru (C corresponding to 0.5 × 10 ^-5 mol, based on total silver
N) ₆ and K ₄ Fe (CN) ₆ were each dissolved and added to the silver halide grains. During the grain growth at the final stage, 0.001 mol of the KI aqueous solution was added to the reaction vessel over 1 minute with respect to the total amount of silver. The position of the addition start is
It started when 93% of the total particle formation was completed. Thereafter, a compound (Y) precipitant was added at 40 ° C. to adjust the pH to 3.
It was adjusted to around 5 and desalted and washed with water.

[0178]

[Chemical 40]

Deionized gelatin, an aqueous solution of NaCl and an aqueous solution of NaOH were added to the emulsion after washing with demineralized water, and the mixture was heated to 50 ° C.
The temperature was raised to pAg 7.6 and pH was adjusted to 5.6. In this way, silver chloride 98.9 mol% silver bromide 1 mol%
A gelatin containing silver halide cubic grains having a halogen composition of 0.1 mol% silver iodide and an average side length of 0.70 μm and a side length variation coefficient of 8% was obtained.

The above emulsion grains were maintained at 60 ° C. and the spectral sensitizing dyes-1 and 2 were added at 2.5 × 10 ^-4 mol / A, respectively.
g mol and 2.0 × 10 ⁻⁴ mol / Ag mol were added. Furthermore, 1 × 10 ⁻⁵ mol / A of thiosulfonic acid compound-1 was added.
Then, a fine grain emulsion in which iridium hexachloride was doped with 90 mol% of silver bromide and 10 mol% of silver chloride having an average grain size of 0.05 μm was added and ripened for 10 minutes. Further, fine particles of 40 mol% silver bromide and 60 mol% silver chloride having an average particle diameter of 0.05 μm were added and ripened for 10 minutes. The fine particles are dissolved, whereby the silver bromide content of the cubic particles of the host is
Increased to 1.3 mol. Iridium hexachloride is 1x
Doped with 10 ⁻⁷ mol / Ag mol.

Subsequently, sodium thiosulfate 1 × 10 ^-5
Mol / Ag mol and 2 × 10 ^-5 mol of gold sensitizer-1 were added. Immediately thereafter, the temperature was raised to 60 ° C., followed by aging for 40 minutes, and then the temperature was lowered to 50 ° C. Immediately after cooling, 6 × 10 ^-4 mol / A of mercapto compounds-1 and 2 respectively
It was added so as to have g mol. Then, after aging for 10 minutes, an aqueous KBr solution was added so as to be 0.008 mol with respect to silver, and after aging for 10 minutes, the temperature was lowered and stored.
Thus, Emulsion A-1 on the high sensitive side for the blue sensitive layer was prepared.

Cubic grains having an average side length of 0.55 μm and a side length variation coefficient of 9% were formed in exactly the same manner except for the above emulsion preparation method and the temperature during grain formation. The temperature during particle formation was 55 ° C. Spectral sensitization and chemical sensitization were corrected by matching specific surface areas (side length ratio 0.7 / 0.55 = 1.
27 times) to prepare Emulsion A-2 on the low sensitivity side for the blue sensitive layer.

[0183]

[Chemical 41]

(Preparation of Emulsions C-1 and 2 for Green Sensitive Layer of the Present Invention)
Emulsion A-1 and high-sensitivity side emulsion C-1 for the green-sensitive layer were prepared in the same manner as in Emulsions A-1, 2 except that the temperature during grain formation was lowered and the sensitizing dye type was changed as follows. A low-sensitivity side emulsion C-2 for the green sensitive layer was prepared. Regarding the grain size, the emulsion C-1 on the high sensitivity side had an average side length of 0.40 μm, and the emulsion C-2 on the low sensitivity side had an average side length of 0.30 μm, and the variation coefficients thereof were all 8%.

[0185]

[Chemical 42]

(The sensitizing dye D was added per mol of silver halide:
3.0 × for large size emulsion (high sensitivity emulsion C-1)
10 ^-4 mol, 3.6 × 10 ^-4 mol for small size emulsion (low sensitive emulsion C-2), and sensitizing dye E per mol of silver halide for large size emulsion. Is 4.0 × 10
^-5 mol, and 7.0 × 10 ^-5 mol was added to the small size emulsion. )

(Preparation of Emulsions E-1 and 2 for Red Sensitive Layer of the Invention)
Emulsion A-1 and the high-sensitivity side emulsion E-1 for the red-sensitive layer were prepared in the same manner as in Emulsions A-1 and 2 except that the temperature at the time of grain formation and the type of sensitizing dye were changed as follows. A low-sensitivity emulsion E-2 for the red sensitive layer was prepared. Regarding the grain size, the high-sensitivity emulsion E-1 had an average side length of 0.38 μm and the low-sensitivity emulsion E-2 had an average side length of 0.32 μm. The side length variation coefficients were 9% and 10%, respectively. It was

[0188]

[Chemical 43]

(Sensitizing dyes G and H were added to a large-sized emulsion (high-sensitivity emulsion E-1) per mol of silver halide, respectively.
Was added in an amount of 8.0 × 10 ⁻⁵ mol, and to a small size emulsion (low-sensitivity emulsion E-2), 10.7 × 10 ⁻⁵ mol was added. Further, the following compound I was added to the red-sensitive layer as silver halide 1
3.0 × 10 ⁻³ mol was added per mol. )

[0190]

[Chemical 44]

These emulsions A-1, A-2, C-
1, C-2, E-1 and E-2 show the iodide ion concentration distribution and the bromide ion concentration distribution by etching / T
When analyzed by the OF-SIMS method, in each case, the iodide ion has a maximum concentration on the surface of the grain, the concentration decreases toward the inside, and a silver iodide-containing phase is formed in layers in the center of the grain. It was found that the silver bromide-containing phase was layered below the silver iodide-containing phase with respect to the center of the grain. (Preparation of coating liquid for first layer) Yellow coupler (ExY) 57
g, color image stabilizer (Cpd-1) 7 g, color image stabilizer (Cp
d-2) 4 g, color image stabilizer (Cpd-3) 7 g, and color image stabilizer (Cpd-8) 2 g as solvent (Solv-1) 21
g, and dissolved in 80 ml of ethyl acetate, and the solution was added with 23.5 g of sodium dodecylbenzenesulfonate to give 23.5 g.
Emulsified and dispersed in 220 g of a mass% gelatin aqueous solution by a high-speed stirring emulsifier (dissolver), and water was added to prepare 900 g of an emulsified dispersion A. On the other hand, the emulsified dispersion A and the emulsions A-1 and A-2 were mixed and dissolved to prepare a coating solution for the first layer having the composition described below. The emulsion coating amount indicates a coating amount equivalent to silver.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used as a gelatin hardening agent for each layer. Further, Ab-1, Ab-2, Ab-3, and Ab-4 were added to each layer in a total amount of 15.0 mg / m ² , 60.
0 mg / m ² , 5.0 mg / m ² and 10.0 mg / m ²
Was added.

[0193]

[Chemical formula 45]

[0194]

[Chemical formula 46]

Further, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to each of the second layer, the fourth layer, the sixth layer and the seventh layer in an amount of 0.2 mg /
m ² , 0.2 mg / m ² , 0.6 mg / m ² , 0.1 mg
/ M ² was added. Further, 4-hydroxy-6-methyl- was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
1,3,3a, 7-Tetrazaindene was added at 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol, respectively, per mol of silver halide. Further, a copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200,000-400000) is added to the red-sensitive emulsion layer in an amount of 0.05 g /
m ² was added. 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. Also, to prevent irradiation,
The following dyes (the amount in parentheses represents the coating amount) were added.

[0196]

[Chemical 47]

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). Silver halide emulsion,
Indicates the coating amount in terms of silver. Support Polyethylene resin laminated paper [the first layer side contained a white pigment polyethylene resin (TiO _2; content 16 wt%, Z nO; content of 4 mass%) and a fluorescent whitening agent (4,4'-bis (5 -Methylbenzoxazolyl) stilbene, which contains 0.03 mass% of the content, and bluish dye (ultra-blue, content of 0.33 mass%). The amount of polyethylene resin is 29.2 g / m ² ] First layer (blue-sensitive emulsion layer) Silver chloroiodobromide emulsion A (gold sulfur sensitized cube, large size emulsion A-1 and small size emulsion A-2) 3: 4 mixture (silver molar ratio) with 0.24 gelatin 1.25 yellow coupler (ExY) 0.57 color image stabilizer (Cpd-1) 0.07 color image stabilizer (Cpd-2) 0 .04 color image stabilizer (Cpd-3) 0.07 color image stabilizer (Cpd-8) 0.02 solvent (Solv-1) 0.21

[0198]   Second layer (color mixing prevention layer)     Gelatin 1.15     Color mixing inhibitor (Cpd-4) 0.10     Color image stabilizer (Cpd-5) 0.018     Color image stabilizer (Cpd-6) 0.13     Color image stabilizer (Cpd-7) 0.07     Solvent (Solv-1) 0.04     Solvent (Solv-2) 0.12     Solvent (Solv-5) 0.11

[0199]   Third layer (green sensitive emulsion layer)   Silver chloroiodobromide emulsion C (gold sulfur sensitized cube, large size emulsion C-1 and small size emulsion 1: 3 mixture with Emulsion C-2 (silver molar ratio). )                                                           0.14     Gelatin 1.21     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.14     Color image stabilizer (Cpd-2) 0.003     Color image stabilizer (Cpd-4) 0.002     Color image stabilizer (Cpd-6) 0.09     Color image stabilizer (Cpd-8) 0.02     Color image stabilizer (Cpd-9) 0.01     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.09     Solvent (Solv-4) 0.18     Solvent (Solv-5) 0.17

[0200]   Fourth layer (color mixing prevention layer)     Gelatin 0.68     Color mixing inhibitor (Cpd-4) 0.06     Color image stabilizer (Cpd-5) 0.011     Color image stabilizer (Cpd-6) 0.08     Color image stabilizer (Cpd-7) 0.04     Solvent (Solv-1) 0.02     Solvent (Solv-2) 0.07     Solvent (Solv-5) 0.065

[0201]   Fifth layer (red sensitive emulsion layer)   Silver chloroiodobromide emulsion E (gold sulfur sensitized cube, large size emulsion E-1 and small size emulsion E-1) 5: 5 mixture with Emulsion E-2 (silver molar ratio). )                                                           0.16     Gelatin 0.95     Cyan coupler (ExC-1) 0.023     Cyan coupler (ExC-2) 0.05     Cyan coupler (ExC-3) 0.17     Ultraviolet absorber (UV-A) 0.055     Color image stabilizer (Cpd-1) 0.22     Color image stabilizer (Cpd-7) 0.003     Color image stabilizer (Cpd-9) 0.01     Color image stabilizer (Cpd-12) 0.01     Solvent (Solv-8) 0.05

[0202]   Sixth layer (UV absorption layer)     Gelatin 0.46     Ultraviolet absorber (UV-B) 0.35     Compound (S1-4) 0.0015     Solvent (Solv-7) 0.18   Seventh layer (protective layer)     Gelatin 1.00     Acrylic modified copolymer of polyvinyl alcohol     (Degree of denaturation 17%) 0.4     Liquid paraffin 0.02     Surfactant (Cpd-13) 0.02

[0203]

[Chemical 48]

[0204]

[Chemical 49]

[0205]

[Chemical 50]

[0206]

[Chemical 51]

[0207]

[Chemical 52]

[0208]

[Chemical 53]

[0209]

[Chemical 54]

[0210]

[Chemical 55]

[0211]

[Chemical 56]

[0212]

[Chemical 57]

Sample 101 (A
A sample 102 was prepared by making the following changes to an emulsion that was gold-sulfur sensitized with high silver chloride grains having a high gI content region and a high AgBr content region.

-Preparation of Sample 102- (Using an emulsion sensitized by gold-sulfur with high silver chloride grains having a high AgBr region) For Sample 101, the first layer, the third layer and the fifth layer were prepared. Sample 102 was prepared in exactly the same manner as Sample 101, except that the silver halide emulsion was changed as follows. Silver halide emulsion for the first layer Silver chloride emulsion B (in the preparation of emulsion A, KI corresponding to 0.001 mol for both large size emulsion and small size emulsion)
An aqueous solution of KBr equivalent to 0.02 mol was added in place of the aqueous solution.) Silver halide emulsion for the third layer Silver chlorobromide emulsion D (in the preparation of emulsion C, both large size emulsion and small size emulsion were adjusted to 0.001 mol) Equivalent K
An aqueous solution of KBr corresponding to 0.05 mol is added in place of the aqueous solution I.) Silver halide emulsion for the fifth layer Silver chlorobromide emulsion F (in the preparation of Emulsion E, 0.001 mol of both large-sized emulsion and small-sized emulsion) Equivalent to K
An aqueous solution of KBr corresponding to 0.01 mol is added in place of the aqueous solution I.) Each of these emulsions is based on silver chloride of the core.
The first shell (silver bromide-containing phase) and the second shell (silver bromide-containing phase on the grain surface side) were formed in layers.

[Example 2] Using the light-sensitive material described in Example 1, the following scanning exposure was performed based on the digital information obtained by reading the negative information with a scanner. as a result,
According to the present invention, a light-sensitive material excellent in white background was obtained, and the subject as a whole also obtained favorable evaluation as the entire image.

The scanning exposure apparatus shown in FIG. 1 of JP-A-8-16238 was used for the scanning exposure. A semiconductor laser is used as a light source, and a 688 nm light source (R light), and a semiconductor laser combined with SHG, a 532 nm light source (G light)
Light), and a 473 nm light source (B light) was obtained. The amount of light was modulated using an external modulator, reflected by a rotating polyhedron, and scan-exposed on a sample moving orthogonal to the scanning direction. This scanning exposure was performed at 400 dpi, and the average exposure time per pixel was 8 × 10 ⁻⁸ seconds. The semiconductor laser uses a Peltier device to keep the temperature constant in order to suppress the change in light quantity due to temperature.

Treatment Process A The treatment using the following running treatment liquid was designated as Treatment A. Treatment process Temperature Time Replenishment amount ^* Color development 38.5 ° C. 45 seconds 45 mL Bleach-fix 38.0 ° C. 45 seconds 35 mL Rinse 1 38.0 ° C. 20 seconds-Rinse 2 38.0 ° C. 20 seconds-Rinse 3 ^** 38.0 ℃ 20 seconds-rinse 4 ^** 38.0 ℃ 20 seconds 121mL dry 80 ℃ (Note) * Replenishment amount per 1 m ^{2 of the} light-sensitive material ** Rin screening system RC50D manufactured by Fuji Photo Film Co., Ltd. was attached to the rinse 3. The rinse liquid is taken out from the rinse 3 and is pumped by a reverse osmosis module (RC
50D). The permeated water sent in the same tank is supplied to the rinse 4, and the concentrated liquid 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 rinse was a 4-tank countercurrent system from 1 to 4.

The composition of each processing solution is as follows. [Color developer] [Tank liquid] [Replenisher] Water 800mL 800mL Fluorescent brightener (FL-1) 2.2 g 5.1 g Optical brightener (FL-2) 0.35g 1.75g 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 10.0g- 4,5-dihydroxybenzene-   Sodium 1,3-disulfonate 0.50 g 0.50 g Disodium-N, N-bis (sulfonate   Ethyl) hydroxylamine 8.5 g 14.0 g 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 to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with sulfuric acid and KOH) 10.15

[0219] [Bleaching fixer] [Tank solution] [Replenisher] Water 800mL 800mL Ammonium thiosulfate (750 g / L) 107 mL 214 mL m-Carboxybenzenesulfinic acid 8.3 g 16.5 g Ethylenediaminetetrairon acetate (III)                 Ammonium 47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g Nitric acid (67%) 16.5g 33.0g Imidazole 14.6g 29.2g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Add water to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with nitric acid and aqueous ammonia) 6.5 6.5

[0220]  [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL pH (25 ° C) 6.5 6.5

Processing Step B Sample 101 was processed into a roll having a width of 127 mm, and the processing time and the processing temperature were changed so that Fuji Photo Film Co., Ltd. minilab printer processor PP350 was used.
Using a modified experimental processor, the photosensitive material was exposed imagewise from a negative film of average density, and continuous processing was performed until the volume of the color developing replenisher used in the following processing steps became twice the capacity of the color developing tank. (Running test) was performed. The treatment using this running treatment liquid was designated as treatment B.

Processing Step Temperature Time Replenishment Amount ^* Color development 45.0 ° C. 20 seconds 45 mL Bleach-fix 40.0 ° C. 20 seconds 35 mL Rinse 1 40.0 ° C. 8 seconds-Rinse 2 40.0 ° C. 8 seconds-Rinse 3 ^** 40.0 ° C 8 seconds-rinse 4 ^** 38.0 ° C 8 seconds 121mL dry 80 ° C 15 seconds (Note) * Replenishment amount per 1 m ^{2 of} photosensitive material ** Rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. 3), remove the rinse liquid from the rinse 3 and use a pump to reverse osmosis module (RC
50D). The permeated water sent in the same tank is supplied to the rinse 4, and the concentrated liquid 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 rinse was a 4-tank countercurrent system from 1 to 4.

The composition of each processing solution is as follows. [Color developer] [Tank liquid] [Replenisher] Water 800mL 800mL Optical brightener (FL-3) 4.0 g 8.0 g Residual color reducing agent (SR-1) 3.0 g 5.5 g Triisopropanolamine 8.8g 8.8g Sodium p-toluenesulfonate 10.0g 10.0g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium sulfite 0.10g 0.10g Potassium chloride 10.0g- 4,5-dihydroxybenzene-   Sodium 1,3-disulfonate 0.50 g 0.50 g Disodium-N, N-bis (sulfonate   Ethyl) hydroxylamine 8.5 g 14.0 g 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 to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with sulfuric acid and KOH) 10.25 12.6

[0224] [Bleaching fixer] [Tank solution] [Replenisher] Water 800mL 800mL Ammonium thiosulfate (750 g / L) 107 mL 214 mL Succinic acid 29.5g 59.0g Ethylenediaminetetrairon acetate (III)   Ammonium 47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g Nitric acid (67%) 17.5g 35.0g Imidazole 14.6g 29.2g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Add water to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with nitric acid and aqueous ammonia) 6.00 6.00

[0225]  [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL pH (25 ° C) 6.5 6.5

Processing Step C A concentrated liquid form of the formulation processor for color development was prepared as shown below. (1) Preparation of color developer composition Compound P-3 25 mmol Compound S-3 35 mmol Triisopropanolamine 40.0 g Ethylenediaminetetraacetic acid 15.0 g Sodium sulfite 0.80 g 4,5-Dihydroxybenzene-1,3-disulfonic acid Sodium 2.0 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 55.0 g 4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline 3/2 sulfate -Monohydrate 70.0 g Potassium hydroxide 34.5 g Sodium hydroxide 25.0 g Potassium carbonate 100.0 g Water was added to make the total amount 1000 mL pH 13.2 In the processing step B, the replenisher for the color developing solution was added to the above concentrated solution. Process step B and all except dilution to 3.84 times It was performed in the same manner as in processing. (This is referred to as processing step C)

[0227]

[Chemical 58]

[0228]

[Chemical 59]

Treatment Process D Treatment was carried out in the same manner as Treatment Process A except that both of the fluorescent whitening agents FL-1 and FL-2 were removed in Treatment Process A. (This is referred to as processing step D)

Photosensitive materials 101 and 10 described in Example 1
2 was used to evaluate the whiteness of the practical image and the unexposed portion. The practical skill is Frontier 350 manufactured by Fuji Photo Film Co., Ltd.
Light sensitive material 10
After printing 500 sheets using each of 1 and 102, 10 prints of a pattern in which red, blue, and green balls are arranged with a gray background of 1.0 are arranged, and the degree of unevenness or scratches is sensory evaluated. The whiteness was measured by CIELAB color measurement (L ^* ). In addition, for character reproduction, a 6-point Mincho type blank character "Todoroki" was subjected to a visual sensory evaluation. The exposure apparatus described in Example 3 was used to perform halftone dot exposure with a resolution of 60 lines, and 10 prints of the same pattern were prepared and evaluated by the area modulation method.

The sensory evaluation of practical skill is 10 in the following three-level evaluation.
The average value of responses from human panelists was used as the evaluation value. 3: No unevenness or scratch is recognized. 2: There is no problem although slight unevenness and scratches are recognized. 1: I am worried about unevenness and scratches. In addition, the character reproduction was evaluated in the following evaluation with the highest number of answers from 10 panelists. ○: Can be fully recognized. Δ: It is difficult to see, but it can be recognized. X: There is a possibility that it is mistaken for another character. The results are shown in Table 3.

[0232]

[Table 3]

[0233]

[Chemical 60]

By carrying out the development treatments (A to C) using the compound used in the present invention, the whiteness is excellent and the character recognition is good, and these tendencies become more remarkable in the case of area modulation. .

[Example 3] (Preparation of color photosensitive material for color proof) A paper support (107 μm) laminated on both sides with polyethylene.
m) (base paper basis weight 81 g / m ² front polyethylene laminate 15 μm back polyethylene laminate 13 μm total thickness 107 μm) After corona discharge treatment on the front side, a gelatin undercoat layer containing sodium dodecylbenzene sulfonate was provided, and further various A photographic constituent layer was applied to prepare a sample 001 having the following layer structure. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Third Layer Coating Liquid Yellow coupler (ExY-1) 600 g, cyan coupler (ExC-2) 2 g, color mixture inhibitor (Cpd-4) 2
0 g, 40 g of color image stabilizer (Cpd-11), and 40 g of color image stabilizer (Cpd-12) were added to a high-boiling organic solvent (Sol
v-3) 300 g, high boiling organic solvent (Solv-4) 6
00g, high-boiling organic solvent (Solv-5) 300g and ethyl acetate 700ml were dissolved in 80% surfactant (W-3) 80g emulsified and dispersed in 5000% 20% gelatin, and then water was added to make the total amount. To prepare 12,000 g of an emulsified dispersion A. On the other hand, silver chlorobromide emulsion G (cubic, average grain size 0.60 μm, variation coefficient of grain size distribution is 0.10, and 0.3 mol% of silver bromide is part of grain surface based on silver chloride) Was localized at
The portion where silver bromide is localized is doped with iridium hexachloride at 1 × 10 ⁻⁷ mol / Ag mol with respect to the total silver amount of the silver halide grains. ) Was prepared. a) Blue-sensitive emulsion In this emulsion, the sensitizing dyes A and C were 0.50 × 10 ⁻⁴ mol per mol of silver halide, and the sensitizing dye B was 4.1 × per mol of silver halide. 10 ⁻⁴ mol is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion G were mixed to prepare a coating solution for the third layer having the composition described below. The emulsion coating amount indicates a coating amount equivalent to silver.

-Preparation of coating solutions for the first layer, the second layer and the fourth to eighth layers-The coating solutions for the first layer, the second layer and the fourth to seventh layers are also the third layer coating solutions. Prepared in a similar manner. As the gelatin hardener for each layer, H-1, H-2 and H-3 represented by the following formula were used. In addition, Ab-1, Ab-2, Ab-3 and Ab-4
Respectively, the total amount is 15.0 mg / m ² , 60.0 mg / m ² ,
It was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

[0238]

[Chemical formula 61]

[0239]

[Chemical formula 62]

For the silver chlorobromide emulsion in each photosensitive emulsion layer, the indicated amount of the spectral sensitizing dye and the optimum amount of the crystal habit controlling agent 1 shown below were used, respectively.

[0241]

[Chemical formula 63]

B) Emulsion H was prepared in the same manner as Emulsion G except that the conditions for forming green-sensitive emulsion grains were changed and the types of sensitizing dyes were changed as follows.

[0243]

[Chemical 64]

Sensitizing dye D was added per mol of silver halide,
3.6 × 10 ^-4 mol, sensitizing dye E was 7.0 × 10 ^-5 mol per mol of silver halide, and sensitizing dye F was 2.8 × 10 4.
^-4 mol was added. In the portion where silver bromide is localized, 1 part of iridium hexachloride is contained in the total amount of silver halide grains.
× 10 ⁻⁷ mol / Ag mol is doped. For the chemical ripening of this emulsion, a sulfur sensitizer and a gold sensitizer were added. c) Emulsion I was prepared in the same manner as Emulsion G except that the conditions for forming red-sensitive emulsion grains were changed and the types of sensitizing dyes were changed as follows.

[0245]

[Chemical 65]

Sensitizing dyes G and H were added in an amount of 1.1 × 10 ^-4 mol per mol of silver halide. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10 ⁻³ mol per mol of silver halide. The portion where silver bromide is localized is doped with 1 × 10 ⁻⁷ mol / Ag mol of iridium hexachloride with respect to the total amount of silver in the silver halide grains. For the chemical ripening of this emulsion, a sulfur sensitizer and a gold sensitizer were added.

[0247]

[Chemical formula 66]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (3-methylureidophenyl) -5-
Mercaptotetrazole was added to 3.3 × 10 ⁻⁴ , 1.0 × 10 ⁻³ , and 3.0 × per mol of silver halide, respectively.
10 ⁻⁴ mol was added. Also, further, the first layer, the fourth layer, fifth layer, each 3.0 mg / m ² in the sixth layer, 0.2 mg / m ^2,
0.2 mg / m ² and 0.2 mg / m ² were additionally added.

For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene was added at 1 × 10 ⁻⁴ and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively.

Catechol-3,5-in the fourth and sixth layers
Disodium disulfonate, 44 mg / m ² and 3, respectively
9 mg / m ² was added in each.

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support polyethylene laminated paper [white pigment (TiO ₂ content 17
Mass%) is included. The whiteness on the first layer side is L ^* = 96.5,
a ^* = 0.1 and b ^* = 0.8. ]

[0252] First layer (anti-halation layer)      Black colloidal silver 0.11      Gelatin 1.04      Color mixing inhibitor (Cpd-1) 0.047      Color image stabilizer (Cpd-2) 0.003      Color image stabilizer (Cpd-3) 0.030      Color mixing inhibitor (Cpd-4) 0.003      High boiling organic solvent (Solv-1) 0.044      High boiling organic solvent (Solv-2) 0.077

Second layer (intermediate layer) Gelatin 1.40 Irradiation prevention dye (A-I) 0.007 Irradiation prevention dye (A-II) 0.004 Third layer (blue-sensitive emulsion layer) Salt Silver bromide emulsion G (cubic, average grain size 0.60 μm, variation coefficient of grain size distribution 0.10, and 0.3 mol% of silver bromide localized on a part of grain surface based on silver chloride) Here, in the portion where silver bromide is localized, 1 × 10 ⁻⁷ mol / Ag mol of iridium hexachloride is doped with respect to the total amount of silver halide grains.) ( (As silver) 0.26 Gelatin 1.19 Yellow coupler (ExY-1) 0.34 Cyan coupler (ExC-2) 0.001 High boiling organic solvent (Solv-4) 0.34 High boiling organic solvent (Solv-5) ) 0.34 Color mixing inhibitor (Cpd-4) 0.01 Color image stabilizer (Cpd-11) 0.02 Color image stabilizer Cpd-12) 0.02

Fourth Layer (Color Mixing Prevention Layer) Gelatin 1.04 Color mixing inhibitor (Cpd-1) 0.13 Color image stabilizer (Cpd-2) 0.008 Color image stabilizer (Cpd-3) 0.10 Color mixing inhibitor (Cpd-4) 0.009 High boiling point organic solvent (Solv-1) 0.13 High boiling point organic solvent (Solv-2) 0.22 Anti-irradiation dye (A-III) 0.003 Anti-irradiation Dye (A-IV) 0.011 Fifth layer (green-sensitive emulsion layer) Silver chlorobromide emulsion H (cube, average grain size 0.39 μm, variation coefficient of grain size distribution 0.08 each. 0.7 mol% of silver bromide was locally contained in a part of the surface of the grain based on silver chloride, in which silver bromide was localized in the total silver amount of the silver halide grain. In contrast, iridium hexachloride is doped at 1 × 10 ⁻⁷ mol / Ag mol.) (As silver) 0.25 gelatin 1.24 Magenta coupler (ExM-1) 0.11 Yellow coupler (ExY-2) 0.05 High boiling point organic solvent (Solv-3) 0.40 Color mixture inhibitor (Cpd-1) 0.02 Color image stabilizer (Cpd-9) 0.014 Color image stabilizer (Cpd-10) 0.023 Color image stabilizer (Cpd-8) 0.04 Color image stabilizer (Cpd-11) 0.004 Color mixture inhibitor (Cpd-) 4) 0.02 Color image stabilizer (Cpd-3) 0.045 UV absorber (UV-1) 0.01 UV absorber (UV-2) 0.05 UV absorber (UV-3) 0.06 Additive (Cpd-14) 0.001

[0255] Sixth layer (color mixing prevention layer)      Gelatin 0.91      Color mixing inhibitor (Cpd-1) 0.12      Color image stabilizer (Cpd-2) 0.007      Color image stabilizer (Cpd-3) 0.07      Color mixing inhibitor (Cpd-4) 0.008      High boiling organic solvent (Solv-1) 0.12      High boiling organic solvent (Solv-2) 0.19      Irradiation prevention dye (A-III) 0.002      Irradiation prevention dye (A-IV) 0.010

Seventh Layer (Red Sensitive Emulsion Layer) Silver Chlorobromide Emulsion I (cubic, average grain size 0.50 μm, variation coefficient of grain size distribution 0.09, silver bromide 0.8 mol% is chlorinated The silver was locally contained in a part of the surface of the grain, where iridium hexachloride was 1 × 10 6 with respect to the total amount of silver in the silver halide grain. ^-7 mol / Ag mol Doped.) (As silver) 0.19 gelatin 0.76 cyan coupler (ExC-1) 0.11 high boiling organic solvent (Solv-6) 0.16 color image stabilizer ( Cpd-3) 0.03 Color image stabilizer (Cpd-5) 0.05 Color image stabilizer (Cpd-6) 0.05 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd- 13) 0.01 Color image stabilizer (Cpd-8) 0.02 Color mixture inhibitor (Cpd-4) 0.02 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.13 Color mixing prevention (Cpd-1) 0.03

[0257] Eighth layer (protection layer)      Acid-treated gelatin 1.67      Acrylic modified copolymer of polyvinyl alcohol (Modification degree 17%)                                                         0.04      Polymethylmethacrylate 0.05      Surfactant (W-1) 0.009      Surfactant (W-2) 0.009

[0258] First layer on back (protective layer)     Gelatin 5.5 Second layer on back side (protective layer)     Gelatin 1.2     Polymethylmethacrylate 0.05

The compounds used are shown below.

[0260]

[Chemical formula 67]

[0261]

[Chemical 68]

[0262]

[Chemical 69]

[0263]

[Chemical 70]

[0264]

[Chemical 71]

[0265]

[Chemical 72]

[0266]

[Chemical formula 73]

[0267]

[Chemical 74]

[0268]

[Chemical 75]

The sample 001 obtained as described above was suction-adhered to a rotating drum having a diameter of 30 cm and wound around it 270.
Rotating at rotation / minute, R (699 nm), G (525n
m) and B (465 nm) LED array (64 LEDs each) light was used for exposure. Each light source uses a 30 μm wide spot with a trapezoidal intensity distribution.
The exposure time per beam was 30 μs. Multiple exposure was performed by shifting the beams by 10 μm so that the overlapping of the exposure beams on the photosensitive surface of the photosensitive material was 20 μm. After exposure,
Color development processing was performed according to the following processing steps.

Treatment process Temperature Time Replenishment amount * Tank capacity Color development 38.5 ℃ 73 seconds 320ml 17L Bleach-fix 38 ℃ 74 seconds 88ml 17L Rinse 38 ℃ 33 seconds --- 7.5L Rinse 38 ℃ 33 seconds --- 7.5L Rinse 38 ℃ 41 seconds 385ml 7.9L Dry 60 ～ 80 ℃ 57 seconds * Replenishment amount per 1m ² of light-sensitive material (rinse is a 3-tank countercurrent method to →)

The composition of each processing liquid is as follows. Color developer Tank solution Replenisher Water 700ml 700ml Optical brightener (FL-1 below) 5.0g 7.5g Triisopropanolamine 8.8g 8.8g Sodium paratoluene sulfonate 10.0g 18.0g Sodium paratoluenesulfinate 5.0g 6.0g Ethylenediaminetetraacetic acid 4.0g 4.0g Sodium sulfite 0.10g 0.10g Potassium chloride 8.6g −   4,5-dihydroxybenzene-1,3- Sodium disulfonate 0.50g 0.50g Disodium-N, N-bis (sulfonate Ethyl) hydroxylamine 12.1g 14.8g 4-amino-3-methyl-N-ethyl-N- (Β-methanesulfonamidoethyl) aniline ・ 3/2 Sulfate ・ Monohydrate 4.8g 8.5g   Potassium carbonate 26.3g 26.3g   Add water 1000ml 1000ml   pH (25 ℃) 10.15 11.95

[0272]

[Chemical 76]

[0273] Bleach-fix solution [tank solution] [replenisher]   800 ml of water 800 ml Ammonium thiosulfate (750g / l) 140ml 187ml m-Carboxybenzenesulfinic acid 20.4g 27.2g Ethylenediaminetetraacetic acid iron (III) ammonium 71.4g 95.4g Ethylenediaminetetraacetic acid 1.4g 1.4g Nitric acid (67%) 20.8g 41.7g Imidazole 14.6g 19.7g Ammonium sulfite 27.3g 36.4g Ammonium bromide 30.0 g 40.0 g   Add water to make 1000ml 1000ml pH (25 ° C) (adjusted with acetic acid / ammonia water) 6.13 5.5

[0274] Rinse solution [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5μS / cm or less) 1000ml 1000ml   pH (25 ° C) 6.5 6.5

Example 4 Next, the same processes as in Example 3 were carried out except that the fluorescent whitening agent FL-1 contained in the color developing solution was removed, and the whiteness of the unexposed area was evaluated. A 4-point sensual evaluation was performed on the white character “Todoroki” of Mincho type. In the following evaluation, the highest number of answers from 10 panelists was evaluated. ○: Can be fully recognized. Δ: It is difficult to see, but it can be recognized. X: There is a possibility that it is mistaken for another character. The results are shown in Table 4.

[0276]

[Table 4]

As is clear from the results shown in Table 4, the image forming method of the present invention has excellent whiteness and high visibility of small characters.

[Embodiment 5] When evaluating Embodiments 3 and 4, the emulsions A, C and E prepared in Embodiment 1 were compared with the corresponding emulsions G, H and I in the amounts added. The samples prepared by using the emulsions A ′, C ′, and E ′, which were changed to have the same content, were evaluated. As a result, the whiteness and the visibility after color development with FL-1 were determined from the above examples. Was also excellent.

[0279]

The color image forming method of the present invention is suitable for image output based on digital data, and is suitable for high illuminance exposure. In particular, according to the method of the present invention, the image quality is improved and it is possible to prevent uneven density and coloring of a white background during rapid development processing.

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) // G03C 7/00 540 G03C 7/00 540 (72) Inventor Yasushi Nakai 2 26-30 Nishiazabu, Minato-ku, Tokyo Fuji Shashin Film Co., Ltd. F-term (reference) 2H016 AA00 AC00 AE00 2H023 BA02 CA02

Claims (3)

[Claims] 1. After exposing a silver halide color light-sensitive material,
In a color image forming method of processing with a processing liquid, the silver halide color light-sensitive material comprises a support having at least one yellow dye-forming coupler-containing silver halide emulsion layer and at least one magenta dye-forming coupler-containing silver halide emulsion layer. And a silver halide color light-sensitive material having at least one cyan dye forming coupler-containing silver halide emulsion layer, a color mixing prevention layer and a protective layer, wherein at least one silver halide emulsion of the silver halide emulsion layer comprises:
The silver halide comprises at least one silver halide grain selected from the group consisting of silver chlorobromide grains having a silver chloride content of 95 mol% or more, silver chloroiodide grains and silver chloroiodobromide grains. Based on digital image data for area modulation, which has a region having a higher content of silver bromide and / or silver iodide than others in the grain, and the exposure is converted into exposure digital data depending on the exposure system device A method for forming a color image, which is exposed to light and the processing liquid contains a compound represented by the following general formula (I) and / or the following general formula (II). General formula (I) In the formula, R ₁₁ and R ₁₂ each independently represent a hydrogen atom or an alkyl group, R ₁₃ and R ₁₄ each independently represent a hydrogen atom, an alkyl group or an aryl group, and R ₁₅ represents at least one asymmetric carbon atom. Represents an alkyl group having or a group represented by the following general formula (Ia), R ₁₆ represents an alkyl group having at least one asymmetric carbon atom or a group represented by the following general formula (Ib), M ₁ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or a pyridinium group. R ₁₃ and R ₁₅ , and R ₁₄ and R ₁₆ may combine with each other to form a ring. General formula (Ia): In the formula, n ₁₁ represents an integer of 1 to 3. General formula (Ib): In the formula, n ₁₂ represents an integer of 2 to 4. General formula (II): In the formula, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ each independently represent a hydrogen atom, an alkyl group or an aryl group, and R ₂₅ , R ₂₆
Each independently represents an alkyl group having at least one asymmetric carbon atom or a group represented by the following general formula (II-a), and R ₂₇ and R ₂₈ each independently represent an alkyl group having at least one asymmetric carbon atom. And M ₂ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or a pyridinium group. R ₂₁ and R ₂₅ ,
R ₂₂ and R ₂₆ , R ₂₃ and R ₂₇ , and R ₂₄ and R ₂₈ may combine with each other to form a ring. General formula (II-a): In the formula, n ₂₁ represents an integer of 2 to 4. 2. The color image forming method according to claim 1, wherein the exposure is performed in multi-channels having a plurality of exposure light sources of the same wavelength. 3. The color image forming method according to claim 1, wherein the silver halide grains contain an iridium compound.