JP2007079419A - Processing method for silver halide color photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a processing method for a silver halide color photosensitive material for a wide proof which improves unevenness in a white background and has production suitability as a proof. <P>SOLUTION: In the processing method for the silver halide color photosensitive material in which the silver halide color photosensitive material for a proof of ≥450 mm width having on a support at least one photosensitive silver halide layer containing a silver halide emulsion spectrally sensitized with a sensitizing dye is processed through at least a color developing process, a desilvering process and a washing process or a stabilizing process, a processing solution in at least one of processing tanks constituting the processing processes contains a compound which shifts the maximum spectral absorption wavelength (λmax) of an aqueous solution of the sensitizing dye by ≥±5 nm. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for processing a silver halide color light-sensitive material for wide proofs with improved white background unevenness and suitability for production as a proof.

  In general, silver halide color photosensitive materials are actively used today because of their high sensitivity, excellent color reproducibility, and suitability for continuous development processing. In the method of printing negative images taken with a color negative film, which has been widely used in the past, using an optical system, if the printing conditions are set in advance, the printing conditions are easily adjusted from the results of measuring the density of the color negative film. It was possible to continuously obtain a full-color color print image with excellent image quality by one exposure, and had extremely high productivity.

  In addition, silver halide color photosensitive materials have recently been used for digital image formation in which the amount of light from an exposure light source such as a laser or LED is modulated by digital image data taken with a digital camera or the like. Yes. Also in digital image exposure, normally, modulated three-color light of B, G, and R is mixed and an image is formed by one scan, and high productivity similar to the conventional one is shown.

  In addition, recording materials using silver halide color light-sensitive materials are known to have little noise, particularly at low densities, and have a feature that enables very smooth gradation reproduction. From this, when the exposure apparatus has a sufficient gradation reproduction capacity, it has a feature that it is particularly excellent in highlight drawing. Because of these features, silver halide color photosensitive materials are widely used not only in the photographic field, but also in the field of printing, in the field of so-called proofs for checking the state of the finished printed matter in the middle of printing. ing.

  In the field of proofing, an image edited on a computer is output to a printing film, and the developed film is subjected to separation exposure while appropriately replacing the developed film, so that yellow (Y), magenta (M), and cyan (C) Each image is formed, and an image of the final printed matter is formed on color photographic paper, thereby determining the suitability of the layout and color of the final printed matter.

  For such purposes, various methods such as a sublimation type / melting heat transfer method, an electrophotographic method, and an ink jet method have been tried. However, a method capable of obtaining a high-quality image is expensive and inferior in productivity. There is a drawback, and the cost is low, and the method with excellent productivity has the disadvantage that the image quality is inferior. A system using a silver halide light-sensitive material can form a high-quality image such as an accurate halftone image due to excellent sharpness and the like, while being capable of continuous processing as described above. In addition, since it is possible to simultaneously write images in a plurality of color image forming units, high productivity can be realized.

  In recent years, digitization has progressed also in the field of printing, and there is an increasing demand for obtaining an image directly from data in a computer. For the reasons described above, silver halide color photosensitive materials have begun to be used advantageously in this field. .

  At the time of developing the photographic silver halide color light-sensitive material described above, an automatic processor is widely used, and more specifically, a color development process, a desilvering process (bleaching, fixing, or bleach-fixing process). A plurality of processing tanks such as a washing step or a stabilization step are provided, and development processing is performed while sequentially passing the exposed silver halide color photosensitive material. At this time, a multi-stage counter-current treatment tank having three or more stages is widely used as the washing treatment tank or the stabilization treatment tank used in the color proof treatment.

  In recent years, a silver halide color light-sensitive material widely used as a color proof is one of important characteristics particularly in a color proof because it is composed mainly of the above-described processing tanks and performs liquid development processing. The white background has a problem that it tends to cause a change in color tone, and has always been an obstacle to obtaining a stable quality.

  One of the factors causing the color tone fluctuation of the white background as described above, that is, the so-called white background unevenness, is that the sensitizing dye used in the silver halide color photosensitive material is not removed even after the development processing, and the silver halide color photosensitive material. There is a known phenomenon (hereinafter also referred to as “dye stain”) that remains inside. Another factor is that the sensitizing dye that has flowed out of the silver halide color photographic material into the processing solution during the processing step does not reach decoloration and is re-adsorbed on the silver halide color photographic material to be processed thereafter. May cause stain. The phenomenon as described above is more prominent particularly when continuous processing is performed for a long time using an automatic processor or the like.

  In recent years, silver halide color photosensitive materials using silver halide grains having a high aspect ratio (diameter / thickness of silver halide grains), so-called tabular silver halide grains, are becoming mainstream for the purpose of increasing sensitivity. is there. This tabular silver halide grain has a high specific surface area, and allows more sensitizing dyes to be adsorbed on the surface than ordinary silver halide grains, resulting in higher sensitivity. Yes.

  However, in the silver halide color light-sensitive material using the tabular silver halide grains as described above and containing more sensitizing dyes, the residual amount of the sensitizing dye in the silver halide color light-sensitive material or in the processing solution The amount of the sensitizing dye flowing out to the surface increases, and stains resulting from the above-described dye are likely to occur. In addition to these, from the viewpoint of speeding up the development process and reducing the amount of processing waste liquid, the development process has become mainstream in a shorter time at a higher temperature or a lower replenisher. In this situation, the generation of stain due to the sensitizing dye as described above is spurred. In particular, with regard to color tone fluctuations in image areas formed by development processing, some correction can be performed using a color management system (CMS) or calibration used for proofing applications, but color tone fluctuations in white areas are corrected. The current situation is that it cannot be done, and this is a fatal defect in a color proof that is often stored under various environmental conditions as a color sample.

  For example, Research Disclosure No. No. 20733 discloses a method using a bistriazinylaminostilbene disulfonic acid compound as an example of a method for removing stains caused by a sensitizing dye, and this method is widely used in the processing of silver halide color light-sensitive materials. Has been. Japanese Patent Application Laid-Open No. 6-329936 discloses a bistriazinylaminostilbene disulfonic acid compound that is excellent in solubility and can reduce stain even by treatment with reduced time reduction. US Pat. No. 6,153,364 proposes a stain reduction method using a 2,6-diarylaminotriazine compound. However, in these proposed and disclosed methods, it is difficult to say that the stain prevention effect is sufficient for the high temperature rapid processing or the low replenishment liquefaction processing which is currently mainstream, and in the processing tank. At present, no effect can be expected for preventing precipitation and sludge.

  Based on the current situation as described above, various treatment methods using a residual color reducing agent have been proposed.

  For example, using a spectral sensitizing dye stain reducing agent that is a colorless or yellow compound having a π system, has no diaminostilbene fragment or condensed triazole nucleus, and has a specific solubility in water at room temperature, A treatment method for reducing the generated contamination is disclosed (for example, see Patent Document 1). Further, it contains a bis [2,6-diaminotriazin-4-yl] arylenediamine derivative having at least one of a sulfonic acid group, a carboxyl group and a hydroxyl group in the molecule, resulting from a residual sensitizing dye in the processed photosensitive material. A processing composition for a silver halide color photographic material is disclosed in which stain reduction is achieved and no precipitate is formed when the processing composition is stored at a low temperature (see, for example, Patent Document 2). In addition, it contains at least a diaminotriazine compound with a specific structure, and the ammonium cation ratio to the total cation is 40 mol% or less, and prevents sticking matter from adhering to the drive gear and transport roller of the automatic processor during low replenishment processing In addition, a fixing processing solution for a photosensitive material that prevents the occurrence of scratches and foreign matter adhesion on the photosensitive material is disclosed (for example, see Patent Document 3). Further, a silver halide color light-sensitive material containing a silver halide emulsion having a silver chloride content of 95 mol% or more is a processing solution containing a compound having a sulfo group and having specific triazine rings at both ends of the molecule. A color image forming method that can reduce yellowing of a white background by processing is disclosed (for example, see Patent Document 4). Further, the reflection density (λ) of the white portion after color development is 0.08 or less at 450 nm, 0.10 or less at 550 nm, and 0.08 or less at 650 nm, and the chromaticity satisfies a specific condition. A silver halide color photosensitive material and a color image forming method using the same are disclosed (for example, see Patent Document 5).

  In recent years, silver halide color light-sensitive materials having a large width are used for proofing applications, and the area ratio of the white background part (unexposed area) is high with respect to the image forming part (color image part). Although the white background unevenness tends to increase or become more apparent, none of the methods proposed above has been able to sufficiently improve the white background unevenness of wide-sized silver halide color photosensitive materials. It is.

  On the other hand, proof recording materials, especially proofs using silver halide light-sensitive materials, and printed materials differ in the color materials and base materials (paper, etc.) used, so even when the colorimetric values are matched, Image reproduction is not always optimal, and fine adjustment of conditions is necessary. For example, in general, so-called process ink is used for printing, but in the case of high-quality paper that has low gloss and the printing paper soaks with ink, reproduction with a low density is performed. Thus, since the printed matter is an image having a low density such as high-quality paper, the printed image and the proof image are different in quality due to differences in paper quality, surface gloss, and the like. As a result, since the proof image is reproduced at a higher density, the proof image density is currently set low. However, simply matching the final density does not eliminate the difference in glossiness due to the difference in the base material, and when the two images are compared and observed, the visual impression of the texture, color tone, etc. differs. The state of discomfort still remains.

  For example, Japanese Patent Application Laid-Open No. 11-38566 defines the 60 ° specular gloss Gs (60 °) of the print surface and the maximum reflection density of each color image as specific conditions. Color photographic prints with a profound feeling and colorful print quality have been proposed. However, it is difficult to obtain image coincidence when observing a printed matter with low gloss such as high-quality paper only by means of adjusting the 60-degree specular gloss Gs (60 °) of the print surface. Japanese Patent Application Laid-Open No. 10-104794 discloses a silver halide photographic light-sensitive material in which at least one non-photosensitive hydrocolloid layer contains porous fine particle powder and latex, water-insoluble organic compound dispersion oil, and the like. Is disclosed. In the silver halide light-sensitive material as described above, the solid content of the outermost layer is set high in order to control the surface glossiness, but the silver halide color light-sensitive material having such a design, in particular, It has been found that the white background unevenness becomes more prominent in the above-described silver halide color photosensitive material having a wide white area.

Further, as another method for improving the white background, in the development processing step of the silver halide color photosensitive material having a width of 350 mm or more, the liquid replenishment to the stabilization processing tank is from the suction port through which the stabilization processing tank is circulated to the discharge port. An image forming method is disclosed in which an inline replenishment method is used to obtain an image excellent in white background and having little in-plane variation (see, for example, Patent Document 6). However, the method described in Patent Document 6 is an attempt to improve the development processing apparatus, and no reference is made to the processing solution composition used there.
JP 2001-201831 A JP 2002-139822 A JP 2003-207876 A JP 2003-255482 A JP 2002-351525 A JP 2003-121975 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for processing a silver halide color light-sensitive material for wide proof use with improved white background unevenness and suitability for production as a proof. There is.

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

  (1) A proof silver halide color light-sensitive material having a width of 450 mm or more and having a light-sensitive silver halide layer containing a silver halide emulsion spectrally sensitized with at least one sensitizing dye on a support, In a processing method of a silver halide color light-sensitive material in which development processing is performed through at least each processing step of a color development processing step, a desilvering processing step, a water washing processing step, or a stabilization processing step, a processing tank constituting each processing step A method for processing a silver halide color photographic material, wherein at least one processing solution contains a compound that shifts the maximum spectral absorption wavelength (λmax) of the aqueous solution of the sensitizing dye by ± 5 nm or more.

  (2) In the above item (1), the compound that shifts the maximum spectral absorption wavelength (λmax) of the aqueous solution of the sensitizing dye by ± 5 nm or more is a compound represented by the following general formula (I): A method for processing a silver halide color light-sensitive material as described.

[Wherein, X ₁ , X ₂ , Y ₁ and Y ₂ are each independently —N (R ₁ ) R ₂ , —OR ₃ , —SR ₃ , a heterocyclic group, a hydroxyl group, a hydroxylamino group or a halogen atom. Z ₁ and Z ₂ each represent —NR ₄ —, —O— or —S—, L represents an arylene group, an alkylene group, an alkenylene group or a heterocyclic group, and R ₁ and R ₂ each represent hydrogen. An atom, an alkyl group, an aryl group or a heterocyclic group; R ₃ represents an alkyl group, an aryl group or a heterocyclic group; and R ₄ represents a hydrogen atom, an aryl group, a heterocyclic group or an alkyl group. R ₁ and R ₂ may combine to form a nitrogen-containing heterocycle. However, the molecule represented by the general formula (I) does not have an azo group or a diaminostilbene structure. ]
(3) The compound represented by the general formula (I) is at least one selected from compounds represented by the following general formulas (I-1) to (I-4): The processing method of the silver halide color photosensitive material as described in the item 2).

[Wherein, R _{11 to} R ₁₈ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. L ₁ represents a phenylene group or a naphthylene group. Three or more of R _{11 to} R ₁₈ are aryl groups. R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , R ₁₇ and R ₁₈ may be bonded to each other to form a ring. However, the molecule represented by the general formula (I-1) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by the general formula (I-1) does not contain a group represented by -N = N- or a diaminostilbene structure in the molecule. ]

[Wherein, R _{21 to} R ₂₈ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. L ₂ represents a phenylene group, a naphthylene group, an alkylene group or a heterocyclic group. Ra represents an alkyl group, an aryl group or a heterocyclic group, and Rb represents a hydrogen atom, an alkyl group or an aryl group. R ₂₁ and R ₂₂ , R ₂₃ and R ₂₄ , R ₂₅ and R ₂₆ , R ₂₇ and R ₂₈ may be bonded to each other to form a ring. However, the compound represented by the general formula (I-2) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by general formula (I-2) does not contain -N = N- or a diaminostilbene structure in the molecule. ]

[Wherein, R _{31 to} R ₃₄ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. L ₃ represents a phenylene group, a naphthylene group, an alkylene group or a heterocyclic group. A ₃₁ and A ₃₂ each independently represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group or a hydroxylamino group. R ₃₅ and R ₃₆ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ₃₁ and R ₃₂ , R ₃₃ and R ₃₄ may be bonded to each other to form a ring. However, the compound represented by the general formula (I-3) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by general formula (I-3) does not contain the group represented by -N = N- in the molecule. ]

[Wherein L ₄ represents a phenylene group, a naphthylene group or an alkylene group. X ₁ represents an oxygen atom or a sulfur atom, and X ₂ represents an oxygen atom, a sulfur atom or —NH—. A ₄₁ , A ₄₂ , A ₄₃ and A ₄₄ are each independently an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a hydroxylamino group, or —NR ₄₁ R ₄₂ (R ₄₁ And R ₄₂ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₄₁ and R ₄₂ may be bonded to each other to form a ring). However, the compound represented by the general formula (I-4) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by the general formula (I-4) does not contain a group represented by —N═N— or a diaminostilbene structure in the molecule. ]
(4) The silver halide color light-sensitive material has at least one silver halide emulsion layer on the support, and a non-photosensitive colloid layer located farthest from the support. 60 degree specular gloss measured in accordance with JIS-Z 8741 on the surface side where the conductive colloid layer contains irregular porous fine particles and has the silver halide emulsion layer after the development processing is 2.0 or more The method for processing a silver halide color photosensitive material as described in any one of (1) to (3) above, which is 9.0 or less.

(5) The white background after the development processing of the silver halide color light-sensitive material has an L ^* in the CIE1976Lab color space of 91 to 96, a ^* of 0 to 2.0, and b ^* of −2.0 to +2.0. The method for processing a silver halide color photographic material as described in any one of (1) to (4) above, wherein

  (6) The treatment liquid containing a compound that shifts the maximum spectral absorption wavelength (λmax) of the aqueous solution of the sensitizing dye by ± 5 nm or more is the washing water or the stabilizing liquid used in the washing treatment process or the stabilization treatment process. The method for processing a silver halide color photosensitive material as described in any one of (1) to (5) above, wherein:

  According to the present invention, it is possible to provide a method for processing a silver halide color photographic material for wide proof use with improved white background unevenness and suitability for production as a proof.

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

  As a result of intensive studies in view of the above problems, the present inventor has found that the support has a photosensitive silver halide layer containing a silver halide emulsion spectrally sensitized with at least one sensitizing dye and having a width of 450 mm. The silver halide color photographic material for proofing described above is subjected to development processing through at least each of the color development processing step, the desilvering processing step, the water washing processing step or the stabilization processing step. In the method, the treatment liquid in at least one of the treatment tanks constituting each treatment step contains a compound that shifts the maximum spectral absorption wavelength (λmax) of the aqueous solution of the sensitizing dye by ± 5 nm or more. Silver halide color sensitization for wide proof applications with improved unevenness of white background and processing suitability as a proof by processing method of silver halide color light-sensitive material As soon as the present inventors have found that a method for processing an optical material can be realized, the present invention has been achieved.

  As a result of studying a method for suppressing white background unevenness in a silver halide color light-sensitive material for proofing, particularly a silver halide color light-sensitive material having a wide width of 450 mm or more and a large area, the present inventor has developed a silver halide color light-sensitive material. A processing solution containing a compound capable of shifting the maximum spectral absorption wavelength (λmax) by ± 5 nm or more when the sensitizing dye used for spectral sensitization of the silver halide emulsion constituting the material is an aqueous solution. It has been found that the white background unevenness in a white background area having a large area can be drastically reduced by using and developing.

  In general, as one of the causes of white background unevenness that occurs after development processing, as described above, the sensitizing dye adsorbed on the silver halide emulsion completely flows out of the silver halide color light-sensitive material during the development processing. And the sensitizing dye that has flowed out may be re-adsorbed to the silver halide color light-sensitive material without being completely decolored. The detailed effect of adding a compound having the ability to shift the maximum spectral absorption wavelength (λmax) of an aqueous solution of a sensitizing dye to ± 5 nm or more is not known at present.

  Details of the present invention will be described below.

  First, a compound (hereinafter referred to as compound A) that shifts the maximum spectral absorption wavelength (λmax) of the sensitizing dye aqueous solution according to the present invention by ± 5 nm or more will be described.

  In the present invention, the effect of shifting the maximum spectral absorption wavelength (λmax) of the sensitizing dye aqueous solution by ± 5 nm or more is preferably such that the maximum spectral absorption wavelength (λmax) is ± 5 nm by adding to the unadded state. The compound to be shifted is preferably, more preferably from ± 5 nm to ± 100 nm, and still more preferably from ± 5 nm to ± 60 nm.

  The measurement of the maximum spectral absorption wavelength (λmax) of the sensitizing dye aqueous solution in the present invention is performed in a state where the sensitizing dye is dissolved in water, for example, a UV-1600PC spectrophotometer manufactured by Shimadzu Corporation, 330 manufactured by Hitachi, Ltd. Spectral absorption using Hitachi Hitachi spectrophotometer, U-3210 self-recording spectrophotometer, U-3410 self-recording spectrophotometer, V-570 ultraviolet-visible near-infrared spectrophotometer manufactured by JASCO Corporation A curve is generated, and the wavelength having the maximum absorbance is defined as the maximum spectral absorption wavelength (λmax).

  Further, in the present invention, the sensitizing dye aqueous solution referred to in the present invention is a molecular state in which the sensitizing dye is completely dissolved, and by allowing Compound A to coexist therewith, for example, the association state of the sensitizing dye is The maximum spectral absorption wavelength of the sensitizing dye aqueous solution is shifted ± 5 nm or more. Further, the sensitizing dye aqueous solution referred to in the present invention is in a state in which the sensitizing dye is dispersed as fine particles, and the compound A is coexisted in the sensitizing dye aqueous solution, for example, in a fine particle state. Even if the sensitizing dye particles are solubilized and, as a result, the maximum spectral absorption wavelength of the sensitizing dye aqueous solution is shifted by ± 5 nm or more, the compound A has the maximum spectral absorption wavelength of the sensitizing dye aqueous solution referred to in the present invention. It is defined as a compound that shifts ± 5 nm or more.

  The compound (compound A) that shifts the maximum spectral absorption wavelength of the sensitizing dye aqueous solution according to the present invention by ± 5 nm or more is not particularly limited as long as it is a compound exhibiting the maximum spectral absorption wavelength shifting effect of the sensitizing dye aqueous solution. However, it is preferably a compound represented by the general formula (I) from the viewpoint of further achieving the object effect of the present invention.

  Hereafter, the detail is demonstrated about the compound represented by general formula (I) based on this invention.

In the general formula (I), X ₁ , X ₂ , Y ₁ and Y ₂ are each independently —N (R ₁ ) R ₂ , —OR ₃ , —SR ₃ , a heterocyclic group, a hydroxyl group, hydroxylamino Represents a group or a halogen atom, Z ₁ and Z ₂ each represent —NR ₄ —, —O— or —S—, L represents an arylene group, an alkylene group, an alkenylene group or a heterocyclic group, and R ₁ and R ₂ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ₃ represents an alkyl group, an aryl group or a heterocyclic group, and R ₄ represents a hydrogen atom, an aryl group, a heterocyclic group or an alkyl group. . R ₁ and R ₂ may combine to form a nitrogen-containing heterocycle. However, the molecule represented by the general formula (I) does not have an azo group or a diaminostilbene structure.

  The compound represented by formula (I) will be described in more detail.

The alkyl group represented by R ₁ , R ₂ , R ₃ or R ₄ includes those having a substituent, preferably those having 1 to 20 carbon atoms, more preferably 1 to 8, particularly preferably 1 to 4. For example, methyl group, ethyl group, i-propyl group, n-propyl group, n-octyl group, sulfomethyl 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] ethyl group, 2- (2- [2- (2-hydroxyethoxy) ) Ethoxy] ethoxy) ethyl group, 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group, 2,3,4,5,6-pentahydroxyhexyl group.

The aryl group represented by R ₁ , R ₂ , R ₃ or R ₄ includes those having a substituent, preferably those having 6 to 20 carbon atoms, more preferably 6 to 10 and particularly preferably 6 to 8. For example, phenyl group, naphthyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 3,5-dicarboxyphenyl group, 4-methoxyphenyl group, 2-sulfophenyl group, 4-sulfophenyl group A 2,4-disulfophenyl group may be mentioned.

The heterocyclic group represented by R ₁ , R ₂ , R ₃ or R ₄ includes those having a substituent, preferably those having 2 to 20 carbon atoms, more preferably those having 2 to 10 carbon atoms, particularly preferably carbon. A compound in which one hydrogen atom is removed from a 5- or 6-membered aromatic or non-aromatic heterocyclic compound of 3 to 8, for example, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, A 2-benzothiazolyl group may be mentioned.

R ₁ and R ₂ are preferably a hydrogen atom, an alkyl group and an aryl group, more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, a sulfomethyl group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group. Group, 2-hydroxypropyl group, 2-sulfoethyl group, 2-methoxyethyl group, 2- (2-hydroxyethoxy) ethyl group, 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group, 2,3- Dihydroxypropyl group, 3,4-dihydroxybutyl group, phenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 3,5-dicarboxyphenyl group, 4-methoxyphenyl group, 2-sulfophenyl group, 4- A sulfophenyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, a sulfomethyl group, a 2-hydroxy group; Til group, 2-sulfoethyl group, 2- (2-hydroxyethoxy) ethyl group, 2,3-dihydroxypropyl group, phenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 2-sulfophenyl group, 4- Sulfophenyl group, more preferably hydrogen atom, methyl group, sulfomethyl group, 2-hydroxyethyl group, 2-sulfoethyl group, 2- (2-hydroxyethoxy) ethyl group, 2,3-dihydroxypropyl group, phenyl group 4-sulfophenyl group.

The nitrogen-containing heterocycle formed by combining R ₁ and R ₂ is preferably a 5-membered ring or a 6-membered ring. Examples of the ring include pyrrolidine ring, piperidine ring, piperazine ring and morpholine ring.

The alkyl group represented by R ₄ includes those having a substituent, preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, an i-propyl group, and an n-propyl group.

When X ₁ , X ₂ , Y ₁ or Y ₂ is a heterocyclic group, including those having a substituent, preferably bonded to a nitrogen atom from a 5- or 6-membered aromatic or non-aromatic nitrogen-containing heterocyclic compound A monovalent 5-membered or 6-membered ring group from which one hydrogen atom has been removed. Examples of the ring include a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.

When X ₁ , X ₂ , Y ₁ and Y ₂ are all —N (R ₁ ) R ₂ , it is preferable that the number of aryl groups is 4 or less among the four R ₁ and the four R ₂ .

  The arylene group represented by L includes those having a substituent, preferably a phenylene group or a naphthylene group, preferably those having 6 to 20 carbon atoms, more preferably 6 to 15 and particularly preferably 6 to 11 phenylene groups or A naphthylene group, for example, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, 1,8-naphthylene, 4-carboxy-1,2-phenylene, 5-carboxy -1,3-phenylene, 3-sulfo-1,4-phenylene, 5-sulfo-1,3-phenylene, 2,5-dimethoxy 1,4-phenylene, 2,6-dichloro-1,4-phenylene It is done. Among these, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, 5-carboxy-1,3-phenylene, and 5-sulfo-1,3-phenylene are preferable. More preferred are 1,4-phenylene and 1,3-phenylene. The heterocyclic group represented by L includes those having a substituent, and preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 2 to 8 carbon atoms. 1,2,4-triazole) -diyl group, 3,5-isothiazole diyl group, 2,6-pyridinediyl group, 2,6-pyrazinediyl group, 2,6-pyrimidinediyl group, 3,6-pyridazinediyl Group, and 1,4-phthalazinediyl group.

  The alkylene group and alkenylene group represented by L include those having a substituent, and those having 1 to 10 carbon atoms are preferred, and 2 to 5 are more preferred. For example, ethylene, triethylene, propylene, vinylene, propylene, etc. are mentioned.

  Hereinafter, although the specific example of the compound of this invention is given, this invention is not limited to these.

  In the present invention, among the compounds represented by the general formula (I), more preferable compounds are the compounds represented by the general formulas (I-1) to (I-4).

  First, the compound represented by formula (I-1) will be described.

In the general formula (I-1), R _{11 to} R ₁₈ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. L ₁ represents a phenylene group or a naphthylene group. Three or more of R _{11 to} R ₁₈ are aryl groups. R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , R ₁₇ and R ₁₈ may be bonded to each other to form a ring. However, the molecule represented by the general formula (I-1) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by the general formula (I-1) does not contain a group represented by -N = N- or a diaminostilbene structure in the molecule.

  The compound represented by the general formula (I-1) will be described in detail.

R _{11 to} R ₁₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, including those each having a substituent. The alkyl group represented by R _{11 to} R ₁₈ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 8, particularly preferably 1 to 4, and examples thereof include a methyl group, an ethyl group, and i-propyl. Group, n-propyl group, n-octyl group, sulfomethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-sulfoethyl group, 2-methoxyethyl group, 2- (2-hydroxy Ethoxy) ethyl group, 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group, 2- (2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethyl group, 2,3-dihydroxypropyl group, Examples include 3,4-dihydroxybutyl group and 2,3,4,5,6-pentahydroxyhexyl group.

The aryl group represented by R _{11 to} R ₁₈ preferably has 6 to 20 carbon atoms, more preferably 6 to 10 and particularly preferably 6 to 8 and includes, for example, a phenyl group, a naphthyl group, 3- Examples thereof include a carboxyphenyl group, a 4-carboxyphenyl group, a 3,5-dicarboxyphenyl group, a 4-methoxyphenyl group, a 2-sulfophenyl group, and a 4-sulfophenyl group.

The heterocyclic group represented by R ₁₁ to R _18, 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably an aromatic or non-5 or 6-membered having 3 to 8 carbon atoms A monovalent group obtained by removing one hydrogen atom from an aromatic heterocyclic compound, and examples thereof include a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group.

R _{11 to} R ₁₈ are preferably a hydrogen atom, an alkyl group, and an aryl group, and more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, a sulfomethyl group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group. Group, 2-hydroxypropyl group, 2-sulfoethyl group, 2-methoxyethyl group, 2- (2-hydroxyethoxy) ethyl group, 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group, 2,3- Dihydroxypropyl group, 3,4-dihydroxybutyl group, phenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 3,5-dicarboxyphenyl group, 4-methoxyphenyl group, 2-sulfophenyl group, 4- A sulfophenyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, a sulfomethyl group, a 2-hydroxy group; Til group, 2-sulfoethyl group, 2- (2-hydroxyethoxy) ethyl group, 2,3-dihydroxypropyl group, phenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 2-sulfophenyl group, 4- A sulfophenyl group, and more preferably a hydrogen atom, methyl group, sulfomethyl group, 2-hydroxyethyl group, 2-sulfoethyl group, 2- (2-hydroxyethoxy) ethyl group, 2,3-dihydroxypropyl group, phenyl Group, 4-sulfophenyl group.

Three or more of R _{11 to} R ₁₈ are aryl groups.

L ₁ represents a phenylene group or a naphthylene group. The phenylene group or naphthylene group represented by L ₁ preferably has 6 to 20 carbon atoms, more preferably 6 to 15 and particularly preferably 6 to 11 substituted or unsubstituted phenylene group or naphthylene group. , 4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, 1,8-naphthylene, 4-carboxy-1,2-phenylene, 5-carboxy-1,3-phenylene, 3 -Sulfo-1,4-phenylene, 5-sulfo-1,3-phenylene, 2,5-dimethoxy 1,4-phenylene, 2,6-dichloro-1,4-phenylene.

L ₁ is preferably 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, 5-carboxy-1,3-phenylene, 5-sulfo-1,3-phenylene. More preferred are 1,4-phenylene and 1,3-phenylene.

R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , R ₁₇ and R ₁₈ may be bonded to each other to form a ring. The ring formed by combining R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , and R ₁₇ and R ₁₈ , including those having a substituent, is a 5-membered or 6-membered ring. Preferably there is. Examples of the ring include a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.

The compound represented by the general formula (I-1) according to the present invention contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium group. Of the alkali metals and alkaline earth metals represented by M, Na and K are particularly preferable. Examples of the ammonium group include an ammonium group, a triethylammonium group, a tetrabutylammonium group, and a pyridinium group. Most preferred as M is Na and K.

  Furthermore, the compound represented by the general formula (I-1) according to the present invention does not contain —N═N— or a diaminostilbene structure in the molecule.

  Specific examples of the compound represented by formula (I-1) according to the present invention are given below, but the present invention is not limited thereto.

  Next, the compound represented by formula (I-2) according to the present invention will be described.

In the general formula (I-2), R _{21 to} R ₂₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. L ₂ represents a phenylene group, a naphthylene group, an alkylene group or a heterocyclic group.

  Ra represents an alkyl group, an aryl group or a heterocyclic group, and Rb represents a hydrogen atom, an alkyl group or an aryl group.

R ₂₁ and R ₂₂ , R ₂₃ and R ₂₄ , R ₂₅ and R ₂₆ , R ₂₇ and R ₂₈ may be bonded to each other to form a ring. However, the compound represented by the general formula (I-2) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by general formula (I-2) does not contain -N = N- or a diaminostilbene structure in the molecule.

  The compound represented by formula (I-2) according to the present invention will be described in more detail.

R _{21 to} R ₂₈ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and include those having a substituent. Specific examples and preferred groups of the alkyl group, aryl group and heterocyclic group represented by R _{21 to} R ₂₈ include the same groups as R _{11 to} R ₁₈ in formula (I-1).

L ₂ represents a phenylene group, a naphthylene group, an alkylene group or a heterocyclic group, and includes those having a substituent. Specific examples and preferred examples of the phenylene group and naphthylene group represented by L ₂ include those similar to the phenylene group and naphthylene group represented by L ₁ in formula (I-1).

The alkylene group represented by L ₂ may be a methylene group at both ends, and may have an oxy group, sulfide group, imino group, sulfonyl group or the like in the main chain.

The heterocycle represented by L ₂ is a linking group having two bonds extending from any substitutable position on the aromatic ring and non-aromatic ring containing a hetero atom. Specific examples of the heterocyclic ring that can be a divalent linking group represented by L ₂ include furan, thiophene, pyrrole, pyridine, pyrimidine, pyridazine, pyrazine, quinoline, isoquinoline, pyrazole, imidazole, triazole, oxazole, isoxazole, Examples include thiazole, benzoxazole, benzimidazole, benzothiazole, indazole, pyrrolidine, piperidine, morpholine, tetrahydropyran, dioxane and the like.

  Ra represents an alkyl group, an aryl group or a heterocyclic group, and includes those having a substituent. Rb represents a hydrogen atom, an alkyl group or an aryl group, and includes those having a substituent.

Specific examples of the alkyl group, aryl group, and heterocyclic group represented by Ra and Rb are the same as the alkyl group, aryl group, and heterocyclic group represented by R _{11 to} R ₁₈ in formula (I-1). Can be mentioned.

R ₂₁ and R ₂₂ , R ₂₃ and R ₂₄ , R ₂₅ and R ₂₆ , R ₂₇ and R ₂₈ may be bonded to each other to form a ring, and include those having a substituent. Examples of the ring formed by combining R ₂₁ and R ₂₂ , R ₂₃ and R ₂₄ , R ₂₅ and R ₂₆ , R ₂₇ and R ₂₈ are R ₁₁ and R ₁₂ , R _{13 in the} general formula (I-1). And R ₁₄ , R ₁₅ and R ₁₆ , and R ₁₇ and R ₁₈ may be the same as the ring formed by bonding to each other.

The compound represented by the general formula (I-2) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M is synonymous with M in General Formula (I-1). Furthermore, the compound represented by the general formula (I-2) does not contain a group represented by —N═N— or a diaminostilbene structure in the molecule.

  Although the specific example of a compound represented by general formula (I-2) based on this invention is given to the following, this invention is not limited to these.

  Next, the compound represented by formula (I-3) according to the present invention will be described.

In the general formula (I-3), R _{31 to} R ₃₄ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. L ₃ represents a phenylene group, a naphthylene group, an alkylene group or a heterocyclic group. A ₃₁ and A ₃₂ each independently represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group or a hydroxylamino group. R ₃₅ and R ₃₆ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

R ₃₁ and R ₃₂ , R ₃₃ and R ₃₄ may be bonded to each other to form a ring. However, the compound represented by the general formula (I-3) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by the general formula (I-3) does not contain a group represented by -N = N- or a diaminostilbene structure in the molecule.

  The compound represented by formula (I-3) will be described in detail.

In General Formula (I-3), R _{31 to} R ₃₄ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and include those having a substituent. L ₃ represents a phenylene group, a naphthylene group, an alkylene group, or a heterocyclic group, and includes those having a substituent. Specific examples and preferred examples of R _{31 to} R ₃₄ are the same as R _{11 to} R ₁₈ in formula (I-1).

A ₃₁ and A ₃₂ each independently represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, or a hydroxyamino group.

Examples of the alkyl group constituting the alkoxy group represented by A ₃₁ or A ₃₂ include the same alkyl groups represented by R _{11 to} R ₁₈ in formula (I-1).

Examples of the aryl group constituting the aryloxy group represented by A ₃₁ or A ₃₂ include the same aryl groups represented by R _{11 to} R ₁₈ in the general formula (I-1).

Examples of the heterocyclic group constituting the heterocyclic oxy group represented by A ₃₁ or A ₃₂ include the same heterocyclic groups as those represented by R _{11 to} R ₁₈ in formula (I-1).

As the alkylthio group, arylthio group, and alkyl group, aryl group, and heterocyclic group constituting the alkylthio group, arylthio group, and heterocyclic thio group represented by A31 and A32, the alkyl represented by R _{11 to} R ₁₈ in the general formula (I-1) Examples thereof include the same groups as those mentioned above, an aryl group and a heterocyclic group.

The alkyl group, aryl group, and heterocyclic group represented by R ₃₅ and R ₃₆ have the same meanings as Ra and Rb in formula (I-2).

However, General Formula (I-3) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M has the same meaning as M in formula (I-1).

  Furthermore, the compound represented by the general formula (I-3) does not contain a group represented by —N═N— or a diaminostilbene structure in the molecule.

  Specific examples of the compound represented by formula (I-3) according to the present invention are given below, but the present invention is not limited thereto.

  Next, the compound represented by formula (I-4) according to the present invention will be described.

In the general formula (I-4), L ₄ represents a phenylene group, a naphthylene group, or an alkylene group.

X ₁ represents an oxygen atom or a sulfur atom, and X ₂ represents an oxygen atom, a sulfur atom or —NH—. A ₄₁ , A ₄₂ , A ₄₃ and A ₄₄ are each independently an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a hydroxylamino group, or —NR ₄₁ R ₄₂ (R ₄₁ And R ₄₂ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₄₁ and R ₄₂ may be bonded to each other to form a ring).

The compound represented by the general formula (I-4) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by the general formula (I-4) does not contain a group represented by —N═N— or a diaminostilbene structure in the molecule.

  Next, the compound represented by formula (I-4) according to the present invention will be further described.

L ₄ in the general formula (I-4) represents a phenylene group, a naphthylene group, or an alkylene group, and includes those having a substituent. As the phenylene group, naphthylene group, and alkylene group, the same groups as those described above for L ₂ in formula (I-2) can be given.

The alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group and heterocyclic thio group in A _{41 to} A ₄₄ include those having a substituent, and A ₃₁ , A in the general formula (I-3) Similar to ₃₂ . When A _{41 to} A ₄₄ represent —NR ₄₁ R ₄₂ , R ₄₁ , R ₄₂ and the ring formed by combining R ₄₁ and R ₄₂ include those having a substituent, and are represented by the general formula (I-1) The same thing as R < ₁₁ > -R < ₁₈ > in can be mentioned.

In General Formula (I-4), X ₁ represents an oxygen atom or a sulfur atom, and X ₂ represents an oxygen atom, a sulfur atom, or —NH—.

However, the compound represented by the general formula (I-4) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M has the same meaning as M in formula (I-1).

  Furthermore, the compound represented by the general formula (I-4) does not contain a group represented by —N═N— or a diaminostilbene structure in the molecule.

  Specific examples of the compound represented by formula (I-4) according to the present invention are given below, but the present invention is not limited thereto.

  The compound represented by the general formula (I) exemplified above can be added in the form of any salt such as sodium salt and ammonium salt.

  When the compound represented by the general formula (I) according to the present invention has a plurality of asymmetric carbons in the molecule, there are a plurality of stereoisomers with respect to the same structure. These stereoisomers are shown, and only one of a plurality of stereoisomers can be used, or several of them can be used as a mixture.

  Further, in the present invention, only one type of the compound represented by the general formula (I) according to the present invention may be used, but two or more types may be mixed and used as necessary, such as improvement of solubility. preferable.

  From the viewpoint of the effect of the present invention, the amount of the compound represented by the general formula (I) according to the present invention added to the stabilizing liquid or the rinsing liquid is preferably 0.1 mmol or more and 20 mmol or less per liter of the used liquid. 0.5 mmol or more and 10 mmol or less are particularly preferable.

  The compound represented by formula (I) can be synthesized with reference to, for example, Koji Matsui, Journal of Synthetic Organic Chemistry, Vol. 17, 528 (1959) and Japanese Patent No. 2618748. That is, a method in which cyanuric chloride is first reacted with a phenylenediamine derivative or a naphthalenediamine derivative, and then amines are sequentially reacted is preferable. Alternatively, it is also preferable to react the phenylenediamine derivative or naphthalenediamine derivative in the second stage or at the end. 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. Bases used include organic bases such as triethylamine, pyridine, 1,8-diazabicyclo [5,4,0] -7-undecene, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, carbonate Inorganic bases such as potassium hydrogen can be mentioned. Of these, 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 150 ° C., and preferably in the range of −10 ° C. to 100 ° 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 40 ° C to 100 ° C.

  Next, development processing steps applicable in the method for processing a silver halide color photographic material of the present invention will be described.

  In the processing method of the silver halide color light-sensitive material of the present invention, the processing is carried out through a color development processing step, a desilvering processing step, a washing processing step or a stabilization processing step. The liquid, the fixing liquid, the washing water, the rinsing liquid or the stabilizing liquid, and the respective replenishers are used.

  First, the color developer used in the color development processing step will be described.

  A known aromatic primary amine developing agent can be used in the color developer according to the present invention. Examples of these compounds include the following compounds.

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4 : 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5: 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-6: 4 -Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7: N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8: N , N-dimethyl-p-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10: 4-amino-3-methyl-N Ethyl-N- (β-ethoxyethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline In the color developer used in the present invention, a color developing agent is used. In order to reduce disappearance due to oxidation, it is preferable to contain a preservative. Representative preservatives include hydroxylamine derivatives. Examples of the hydroxylamine derivatives that can be used in the present invention include hydroxylamine salts such as hydroxylamine sulfate and hydroxylamine hydrochloride, as well as JP-A-1-97953, 1-186939, 1-186940, Hydroxylamine derivatives described in, for example, 1-1875557 can be used.

  Other preservatives include hydroxamic acids, hydrazides, phenols, α-hydroxy ketones, α-amino ketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals. , Alcohols, oximes, diamide compounds, and condensed amines. These are disclosed in JP-A 63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63- 58346, 63-43138, 63-146041, 63-44657, 63-44656, US Pat. Nos. 3,615,503, 2,494,903, JP-A-52. -1433020, Japanese Patent Publication No. 4830696 and the like.

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

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

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

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

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

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

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

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

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

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

  In the present invention, the color developer can be used in any pH range, but is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0 from the viewpoint of rapid processing. It is done.

  Next, details of the bleach-fixing step according to the present invention will be described.

  In the present invention, any bleaching agent can be used as a bleaching agent used in the bleach-fixing solution, and in particular, an organic complex salt of iron (III) (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, cyclohexanediamine). Aminopolycarboxylic acids such as tetraacetic acid and ethylenediaminedisuccinic acid, complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; Hydrogen and the like are preferable.

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

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

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

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

  Bleach fixers may contain sulfites such as sodium sulfite, potassium sulfite, ammonium sulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite as preservatives. In general, ascorbic acid, a carbonyl bisulfite adduct, or a carbonyl compound may be added. Furthermore, you may add a buffering agent, a fluorescent whitening agent, a chelating agent, an antifoamer, an antifungal agent, etc. as needed.

  In the present invention, in order to increase the activity of the bleach-fixing solution, air or oxygen may be optionally blown in the processing bath and in the processing replenisher storage tank, or a suitable oxidizing agent such as peroxidation may be used. Hydrogen, bromate, persulfate, or the like may be added as appropriate.

  The pH of the bleach-fixing solution is preferably 5.0 to 9.0, more preferably 5.5 to 8.0. The pH of the bleach-fixing solution is the pH of the processing tank at the time of processing the photosensitive material, and not the pH of the replenishing solution.

  Next, the stabilizing solution will be described.

  It is particularly preferred for the purposes of the present invention that the stabilizer contains a chelating agent having a chelate stability constant for iron ions of 8 or more. Here, the chelate stability constant is L.I. G. Sillen, A.M. E. "Stability Constants of Metal-ion Complexes" by Martell, The Chemical Society, London (1964), S.M. Chaberek, A .; E. This means a constant generally known by Martell's “Organic Sequencing Agents” Wiley (1959).

Examples of the chelating agent having a chelate stability constant for iron ions of 8 or more include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. The iron ion means ferric ion (Fe ³⁺ ).

  Specific examples of the chelating agent having a chelate stability constant with ferric ion of 8 or more include the following compounds, but are not limited thereto. That is, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, Diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, Examples include techol-3,5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate, particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1. -Diphosphonic acid, etc. Among them, 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

  The amount of the chelating agent used is preferably 0.01 to 50 g per liter of the stabilizing solution, more preferably 0.05 to 20 g.

  Moreover, an ammonium compound is mentioned as a preferable compound added to a stabilizer. These are supplied by various inorganic and organic ammonium salts, specifically ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, fluoride. Ammonium fluoride, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, laurin Ammonium tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, malic acid water Ammonium, ammonium hydrogen oxalate, ammonium hydrogen phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ethylenediaminetetraacetic acid ammonium, ethylenediaminetetraacetic acid ferric ammonium, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, Ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4,6-trinitrophenol ammonium and the like. These may be used alone or in combination of two or more. The addition amount of the ammonium compound is preferably in the range of 0.001 mol to 1.0 mol, and more preferably in the range of 0.002 to 0.8 mol, per liter of the stabilizer.

Furthermore, it is preferable that the stabilizer contains sulfite. The sulfite may be any organic or inorganic substance as long as it releases sulfite ions, but is preferably an inorganic salt. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite. The sulfite is preferably added in an amount of at least 1 × 10 ⁻³ mol / liter, more preferably 5 × 10 ⁻³ mol / liter to 10 ⁻¹ mol / liter, in the stabilizer. Such an amount is added, and has an effect of preventing stains in particular. As an addition method, it may be added directly to the stabilizing solution, but it is preferably added to the stable replenishing solution.

  Other compounds that can be added to generally known stabilizers include polyvinylpyrrolidone (PVP K-15, K-30, K-90), organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid). Acid), pH adjusters (phosphate, borate, hydrochloric acid, sulfuric acid, etc.), fungicides (phenol derivatives, catechol derivatives, imidazole derivatives, triazole derivatives, siabendazole derivatives, organic halogen compounds, other papers) Antifungal agents known as pulp industry slime control agents) or optical brighteners, surfactants, preservatives, metal salts such as Bi, Mg, Zn, Ni, Al, Sn, Ti, Zr, etc. is there. One or more of these compounds can be selected and used as long as the effects of the present invention are not impaired.

  After the stabilization treatment, no water washing treatment is required, but rinsing by a small amount of water washing in a very short time, surface washing, etc. can be optionally performed.

The presence of a soluble iron salt in the stabilizing solution is preferable for achieving the effects of the present invention. The soluble iron salt is preferably used in the stabilizing solution at a concentration of at least 5 × 10 ⁻³ mol / liter, more preferably in the range of 8 × 10 ⁻³ to 15 × 10 ⁻² mol / liter, and still more preferably The range is 12 × 10 ⁻³ to 10 × 10 ⁻² mol / liter. These soluble iron salts may be added to the stabilizing solution (tank solution) by adding them to the stabilizing solution replenisher, or they may be added to the stabilizing solution (tank solution) by elution from the photosensitive material in the stabilizing solution. It may be added to the stabilizer (tank solution) by adhering it to the photosensitive material to be processed from the pre-bath and bringing it in.

  Further, in the present invention, a stabilizing solution in which calcium ion and magnesium ion are reduced to 5 ppm or less by performing an ion exchange resin treatment may be used, and a method of further containing the above-mentioned antibacterial agent or halogen ion releasing compound. It may be used.

  In the present invention, the pH of the stabilizing solution is preferably in the range of 5.5 to 10.0. The pH adjuster that can be contained in the stabilizing solution may be any of commonly known alkali agents or acid agents.

  In the present invention, the washing or stabilizing solution is also characterized in that it contains only additives such as scale inhibitor, antifungal agent, or preservative in addition to the sulfite. Examples of compounds having these effects include orthophenylphenol, benzoisothiazolin-3-one, 2,2-dibromo-2-nitroethanol, 2-bromo-2-nitro-1,3-propanediol, and 8-hydroxy. Examples include quinoline, hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, 2,4-dichloro-S-hydroxytriazine sodium. Particularly preferred are orthophenylphenol, 2-bromo-2-nitro-1,3-propanediol, 2,4-dichloro-S-hydroxytriazine sodium and the like.

  In the treatment process of the stabilization tank, when it is constituted by a plurality of processing tanks, it is preferable to replenish each tank individually and become waste liquid, but it is not effective in reducing the replenishment amount. . Therefore, it is preferable to use a so-called counter current method in which the replenisher enters the last tank, sequentially overflows to the previous tank, and overflows from the front tank as waste liquid.

  In the processing method of the silver halide color light-sensitive material of the present invention, the processing that constitutes each processing step described above with a compound that shifts the maximum spectral absorption wavelength (λmax) of the sensitizing dye aqueous solution according to the present invention by ± 5 nm or more. Although it is characterized by being added to the treatment liquid in at least one tank of the tank, it is preferably added to the stabilization tank from the viewpoint of further exerting the effects of the present invention, and moreover, the stabilization treatment step includes a plurality of treatment processes. In the case of a counter current system comprising a tank, it is preferable to add at least to the final stabilization tank.

In the method for processing a silver halide color light-sensitive material of the present invention, the replenishment amount of each processing solution is preferably 50 to 500 ml, more preferably 100 to 400 ml, per 1 m ^{2 of the} silver halide color light-sensitive material in the color development step. Particularly preferred is 150 to 350 ml. The replenishing amount in the bleach-fixing step is preferably 50 to 300 ml, more preferably 80 to 250 ml, and still more preferably 80 to 200 ml per 1 m ^{2 of the} silver halide color photographic material. The replenishment amount in the stabilization step is preferably 100 to 1000 ml, more preferably 150 to 800 ml, and particularly preferably 180 to 650 ml as a whole. Further, the processing time of each step is preferably 30 to 150 seconds, more preferably 40 to 150 seconds, and still more preferably 80 to 140 seconds, as the color development time (time for performing the color development step). The processing time of the bleach-fixing step is preferably set within 90 seconds, particularly preferably 30 to 80 seconds. The stabilization time (time for performing the stabilization step) is preferably 40 to 200 seconds, more preferably 60 to 170 seconds, and still more preferably 80 to 160 seconds.

  The color development time refers to the time from when the silver halide color photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks, and in the case of one tank, the color development is performed. It refers to the time from entering the tank to entering the bleaching or bleach-fixing tank of the next processing step, and includes the crossover time (out-of-liquid transport time). Similarly, the time required for the bleach-fixing process is the time from when the silver halide color photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks. For example, it refers to the time until the photosensitive material is immersed in the subsequent stabilization tank, and includes the crossover time therebetween.

  The stabilization time also refers to the time from when the photosensitive material is immersed in the first tank until it exits the final tank. In the case of one tank, the time that is in the liquid for the drying process after entering the stabilization liquid. Including the crossover time between them. The crossover time is preferably as short as possible from the viewpoint of stain and fog prevention, and is preferably 10 seconds or less, more preferably 5 seconds or less, and even more preferably 3 seconds or less.

  In the stabilization step, the crossover time is preferably 5 seconds or less and substantially 0 from the viewpoint of suppressing edge contamination. The edge contamination referred to here refers to the stain on the cut end surface (edge portion) of the paper support of the photosensitive material after processing. The means for making the crossover time substantially zero can be achieved by using a conveying system such as a submerged blade as described in FIGS. 2 to 5 of JP-A-5-66540.

  The processing solution temperature in the color development step, desilvering step, and stabilization step is generally 30 to 40 ° C, preferably 38 to 60 ° C, more preferably 38 to 50 ° C. The drying process accelerates drying by absorbing moisture with a squeeze roller or cloth immediately after the stabilization process from the viewpoint of reducing the amount of moisture carried into the image film of the silver halide color light-sensitive material. Is also possible. Naturally, drying can be accelerated by increasing the temperature or changing the shape of the spray nozzle to increase the drying air. Further, as described in JP-A-3-157650, drying can be accelerated by adjusting the blowing angle of the dry air to the photosensitive material or by the method of removing the exhaust air.

  Further, aeration may be performed in the bleaching step. Any means known in the art can be used for aeration. Regarding aeration, the items described in Eastman Kodak Co., Ltd., Z-121, Yuging Process C-41 3rd Edition (1982), BL-1 to BL-2 can be used. Further, in the bleaching step, it is preferable to enhance stirring, and the contents described in JP-A-3-33847, page 8, upper right column, line 6 to lower left column, line 2 are used as they are. it can. Among these, the jet stirring method in which the bleaching composition is sprayed on the emulsion surface of the light-sensitive material is preferable. Further, in the bleaching step and the bleach-fixing step, the overflow liquid after use can be recovered for processing, and the components can be added to correct the composition and then reused (regenerated).

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

  The silver halide light-sensitive material according to the present invention has a light-sensitive silver halide layer containing a silver halide emulsion spectrally sensitized with at least one sensitizing dye on a support, and is used for a proof having a width of 450 mm or more. It is a silver halide color photosensitive material.

  The photosensitive layer containing a silver halide emulsion spectrally sensitized with a sensitizing dye in the present invention is mainly a yellow dye when the silver halide color photosensitive material according to the present invention is used for color proofing. Cyan imaging with a yellow image forming layer containing a silver halide emulsion containing a forming coupler, a magenta image forming layer containing a silver halide emulsion containing a magenta dye forming coupler, and a silver halide emulsion containing a cyan dye forming coupler In addition, a non-photosensitive layer is provided as necessary. Examples of the non-photosensitive layer include an intermediate layer provided between the reflective support and the image forming layer, or between each image forming layer, and the image forming layer. In order to provide protection during operation and desired surface properties, a non-photosensitive colloid layer, i.e., a protective layer, located farthest from the reflective support according to the present invention is included. It is.

  In particular, when the printed matter based on the silver halide color light-sensitive material is a low-gloss printed matter, particularly a printed matter produced using matte paper, the colorimetric value of the printed matter and the observed image (texture, density) In order to improve the conformity of the light-sensitive material, each support has at least one silver halide emulsion layer and a non-photosensitive colloid layer located farthest from the reflective support. 60 degree specular gloss measured in accordance with JIS-Z 8741 on the side having a colloidal layer containing irregular porous fine particles and having a silver halide emulsion layer after development processing is 2.0 or more, 9 And a silver halide color light-sensitive material characterized by being 0.0 or less. By applying the processing method of the present invention to the development processing of a silver halide color photographic material having such a configuration, uneven white background in a wide proof material can be further suppressed.

  First, the non-photosensitive colloid layer contains irregular porous fine particles, and the 60-degree specular gloss measured in accordance with JIS-Z 8741 on the side having the silver halide emulsion layer after development processing is 2 A silver halide color light-sensitive material having a value of 0.0 or more and 9.0 or less will be described.

  The amorphous porous fine particles according to the present invention are preferably silica particles.

  The average primary particle diameter of the amorphous porous fine particles according to the present invention is preferably 1.5 μm or more and 6.5 μm or less. If the average primary particle size of the irregular porous fine particles is 1.5 μm or more, the gloss of the formed image surface will not be too high, and the colorimetric values and texture of the printed matter printed on the reference matte paper Thus, it is possible to obtain consistency in image characteristics. Further, when the average primary particle diameter of the amorphous porous fine particles is 6.5 μm or less, it is possible to obtain the excellent quality of the formed image without impairing the devitrification of the formed image.

The average particle size of the amorphous porous fine particles according to the present invention refers to the amorphous porous fine particles themselves or a dispersion thereof directly observed with an electron microscope, or a silver halide color photosensitive material containing the amorphous porous fine particles. The cross section and the surface of the above are observed with an electron microscope, and the particle size of a large number of, for example, 1,000 arbitrary inorganic amorphous porous matting agents is measured and measured as a simple average value (number average), It can be obtained by measuring by a laser diffraction / scattering method. The individual particle diameter referred to in the present invention is represented by a diameter assuming a circle equal to the projected area. The amount of the amorphous porous fine particles added to the non-photosensitive colloid layer (hereinafter also referred to as a protective layer) located farthest from the support is 300 mg / m ² or more and 600 mg / m ² or less. Is preferred. If the amount of the amorphous porous fine particles added is 300 mg / m ² or more, the gloss of the formed image surface does not become too high, and the colorimetric value and texture of the printed matter printed on the matte paper as a reference, Consistency of image characteristics can be obtained. Further, when the content of the amorphous porous fine particles in the protective layer is 600 mg / m ² or less, the formed image itself can be excellent in quality without impairing the devitrification of the formed image.

  The amorphous porous fine particles according to the present invention are preferably matting agents composed of an inorganic material having pores on the surface.

  Examples of amorphous porous fine particles used for the above purpose are light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc hydroxide, sulfide. Zinc, zinc carbonate, hydrotalcite, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, pseudoboehmite, aluminum hydroxide, lithopone, zeolite, magnesium hydroxide, Inorganic fine particles such as glass beads can be mentioned, among which porous silicas are preferable.

  Such amorphous porous fine particles may be used in a state of being uniformly dispersed in the binder as primary particles, or added in a state of being dispersed in the binder by forming secondary agglomerated particles. May be.

Examples of the porous silica preferably used as the amorphous porous fine particles in the present invention include synthetic amorphous silica described in JP-A-55-51583 and JP-A-56-148583, and JP-A-60- Synthetic amorphous silica containing fluorine described in 222282, synthetic amorphous silica surface-treated with a silane coupling agent described in JP-A-60-224580 and JP-A-62-178384, JP-A-63 Synthetic silica fine particles having a Na ₂ O content of 0.5% by mass or more described in JP-A-3173811, synthetic silica fine particles having a specific surface area of 100 m ² / g or more described in JP-A 1-115677, and JP Synthetic silica fine particles treated with alumina surface described in JP-A-62-2286787, Ca, Mg described in JP-A-1-259998. Is a synthetic silica fine particle surface-treated with Ba, a synthetic silica fine particle having an oil absorption of 180 ml / g or more, disclosed in JP-A-60-219084, JP-A-6-92011, JP-A-6-297830 and JP-A-7-81214. Examples thereof include the cationic colloidal silica described and colloidal silica linked or branched in the form of a bead described in JP-A-5-278324 and 7-81214.

  In the silver halide color light-sensitive material according to the present invention, a non-porous matting agent can be used in combination as long as the object and effects of the present invention are not impaired. For example, as an organic substance, Japanese Examined Patent Publication No. 44-3643. Polyvinyl alcohol described in the publication, etc., polystyrene or polymethacrylate described in Swiss Patent No. 330,158, etc., polyacrylonitrile described in US Pat. No. 3,079,257, etc., US Pat. An organic matting agent such as polycarbonate described in the specification of No. 022,169 can be exemplified.

  In the silver halide color light-sensitive material according to the present invention, the 60-degree specular gloss measured in accordance with JIS-Z 8741 after processing on the side coated with the silver halide emulsion layer is 2.0 or more. , 9.0 or less is preferable.

  The 60-degree specular gloss referred to in the present invention is a value measured according to the measurement method defined in JIS-Z-8741. Examples of the apparatus that can be used for the measurement of 60-degree specular gloss according to the present invention include HORIBA GLOSS CHECKER IG-310 (manufactured by HORIBA), precision gloss meter GM-26D, True Gross GM-26DPRO, and variable angle gloss meter. Examples thereof include GM-3D (manufactured by Murakami Color Research Laboratory), VG-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), and a digital variable angle gloss meter (Suga Test Instruments Co., Ltd.).

  If the 60-degree specular gloss measured in accordance with JIS-Z 8741 after processing is 9.0 or less, the gloss of the formed image surface will not be too high, and the matte paper used as a reference It is possible to obtain coincidence of colorimetric values, texture, and image characteristics with a printed product. Moreover, if it is 2.0 or more, the quality of the formed image itself can be obtained without impairing the devitrification of the formed image.

  In the present invention, as means for achieving the 60-degree specular gloss as defined above, the amorphous porous fine particles are added to the non-photosensitive colloid layer located farthest from the support, and the amorphous porous particles are added. This can be achieved by appropriately selecting or combining the addition amount of fine particles or the average particle size.

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

  As the support used in the present invention, any material may be used, including paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, or white pigment. Good polypropylene, polyethylene terephthalate support, baryta paper or the like can be used. Of these, a reflective support in which both sides of a paper substrate are coated with a resin layer such as a polyolefin resin is preferable.

  A reflective support (hereinafter also referred to as resin-coated paper or RC paper) in which both sides of a paper substrate are coated with a resin layer such as a polyolefin resin will be described.

  Paper base paper used for resin-coated paper is made from wood pulp as a main raw material and, if necessary, paper making using synthetic pulp such as polypropylene or synthetic fibers such as nylon or polyester in addition to wood pulp. As wood pulp, for example, any of LBKP, LBSP, NBKP, NBSP, LDP, NDP, LUKP, NUKP can be used, but more LBKP, NBSP, LBSP, NDP, LDP with more short fibers are used. Is preferred. However, the ratio of LBSP or LDP is preferably 10% by mass or more and 70% by mass or less.

  The pulp is preferably a chemical pulp (sulfate pulp or sulfite pulp) with few impurities, and a pulp having a whiteness improved by bleaching is also useful.

  In the base paper, sizing agents such as higher fatty acids and alkyl ketene dimers, white pigments such as calcium carbonate, talc and titanium oxide, paper strength enhancing agents such as starch, polyacrylamide and polyvinyl alcohol, fluorescent whitening agents, polyethylene glycols A water retaining agent such as a dispersant, a softening agent such as quaternary ammonium, and the like can be appropriately added.

  The freeness of the pulp used for papermaking is preferably 200 to 500 ml as defined by CSF, and the fiber length after beating is a 24 mesh residual mass% defined by JIS-P-8207, and 42 30-70 mass% of sum with the mass% of a mesh remainder is preferable. In addition, it is preferable that the mass% of 4 mesh remainder is 20 mass% or less.

The basis weight of the base paper is preferably 30 to 250 g, particularly preferably 50 to 200 g. The thickness of the base paper is preferably 40 to 250 μm. The base paper can be given a high smoothness by subjecting it to a calendar process at the paper making stage or after paper making. The density of the base paper is generally 0.7 to 1.2 g / cm ³ (according to the method defined in JIS-P-8118). Furthermore, the base paper stiffness is preferably 20 to 200 g under the conditions specified in JIS-P-8143. A surface sizing agent may be applied to the surface of the base paper. As the surface sizing agent, the same sizing agents that can be added to the base paper can be used. The pH of the base paper is preferably 5 to 9 when measured by a hot water extraction method defined in JIS-P-8113.

  The polyethylene covering the front and back surfaces of the base paper is mainly low-density polyethylene (LDPE) or high-density polyethylene (HDPE), but some other LLDPE, polypropylene, etc. can also be used.

  Moreover, a white pigment can be added to the polyethylene layer on the photosensitive layer coating surface side. As the white pigment, inorganic and / or organic white pigments can be used. Preferably, inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate and alkaline earths such as calcium carbonate are used. Examples thereof include silicas such as metal carbonates, finely divided silicic acid, and synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide, more preferably rutile or anatase type titanium oxide, and these are added to polyethylene to improve opacity and whiteness. The titanium oxide content is 1 to 20% by mass, preferably 2 to 15% by mass, based on polyethylene.

  The resin layer of the paper support having water-resistant resin layers on both sides used in the present invention may be a single layer or a plurality of layers. When the resin layer is made into a plurality of layers and a white pigment is contained at a high concentration on the surface side in contact with the silver halide emulsion layer, the sharpness improving effect is great, which is one of the preferred forms for forming a proof image.

  The amount of polyethylene used on the front and back of the base paper is selected so as to optimize the film thickness of the coating composition and the curl at low humidity and high humidity after providing the back layer, but the coating composition according to the present invention It is preferable that the polyethylene layer on the side to be coated is 20 to 40 μm, and the back layer side is 10 to 30 μm.

  Further, the RC paper coated with polyethylene preferably has the following characteristics.

1) Tensile strength: strength specified by JIS-P-8113, preferably 20-300N in the vertical direction and 10-200N in the horizontal direction 2) Tear strength: as defined by JIS-P-8116 The longitudinal direction is preferably 0.1 to 2N and the lateral direction is preferably 0.2 to 2N. 3) Compression elastic modulus: ≧ 10 ³⁰ N / cm ²
4) Back surface Beck smoothness: 100 to 800 seconds are preferable under the conditions specified in JIS-P-8119. 5) Opacity: Transmission with light in the visible range under measurement conditions of linear light incidence / diffuse light transmission conditions. The rate is preferably 20% or less, particularly preferably 15% or less. 6) Whiteness: Hunter whiteness as defined in JIS-P-8123, preferably 90% or more. Further, when measured by JIS-Z-8722 (non-fluorescent) and JIS-Z-8717 (containing fluorescent agent) and displayed by the color display method defined in JIS-Z-8730, L ^* = 90 to 98, a ^* = − 5 to +5, b ^* = − 10 to +5 are preferable.

  In the reflective support according to the present invention mainly composed as described above, the center line surface roughness SRa of the resin layer surface on the surface side on which the photosensitive layer is applied is preferably 0.6 μm or more. More preferably, it is 0.75 μm or more, and particularly preferably 0.75 μm or more and 5.0 μm or less. If the center line surface roughness SRa on the surface of the resin layer is 0.6 μm or more, for example, it is possible to further improve the consistency of the observed image quality such as glossiness and image density of the resulting image with respect to printed matter using high-quality paper. Can be made.

  Next, other components of the silver halide photosensitive material of the present invention will be described.

  The silver halide emulsion used in the silver halide light-sensitive material of the present invention is preferably a silver halide emulsion comprising 95 mol% or more of silver chloride from the viewpoint of exhibiting the object effects of the present invention. Silver chlorobromide, silver chloroiodobromide, silver chloroiodide and the like having any halogen composition are used. Among them, a silver chlorobromide containing 95 mol% or more of silver chloride, a silver halide emulsion having a portion containing a high concentration of silver bromide is particularly preferably used, and 0.05% of silver iodide is present in the vicinity of the surface. Silver chloroiodide containing ˜0.5 mol% is also preferably used. In a silver halide emulsion having a portion containing a high concentration of silver bromide, the portion containing a high concentration of silver bromide may be a so-called core-shell type silver halide emulsion, or a complete layer A so-called epitaxy-bonded region may be formed in which only regions having different compositions are present without being formed. The portion where silver bromide is present at a high concentration is particularly preferably formed at the apex of the crystal grain on the surface of the silver halide grain. Further, the composition may change continuously or discontinuously.

  The negative silver halide emulsion used in the silver halide light-sensitive material of the present invention preferably contains heavy metal ions. This is expected to improve so-called reciprocity failure and prevent desensitization in high-illuminance exposure and prevent softening in the shadow region.

  Heavy metal ions that can be used for such purposes include Group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt, and twelfth metals such as cadmium, zinc, and mercury. Group transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium can be given. Of these, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. When the heavy metal ion forms a complex, as its ligand, cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, ammonia, water, pyridine, Pyrrol, pyrazole, imidazole, thiazole, 1,2,4-triazole, 2,2′-biimidazole, 2,2′-bipyridine or 2,2 ′: 6 ′, 2 ″ -terpyridine compound is preferably used. , Cyanide ion, chloride ion, bromide ion, water, nitrosyl, 5-methylthiazole, 1,2,4-triazole, etc. These ligands may be used alone or in combination with a plurality of ligands. May be.

  As a method of containing heavy metal ions in the silver halide emulsion, the heavy metal compound is added to each step before the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. What is necessary is just to add in arbitrary places.

The heavy metal compound can be dissolved together with the halide salt and added continuously throughout the grain formation process. It can also be prepared by forming silver halide fine particles containing these heavy metal compounds in advance and adding them. The amount of heavy metal ions added to the silver halide emulsion is preferably 1 × 10 ⁻⁹ mol or more and 1 × 10 ⁻² mol or less, particularly 1 × 10 ⁻⁸ mol or more, 5 mol or more per mol of silver halide. × 10 ⁻⁵ mol or less is preferable.

  Any silver halide grains can be used in the present invention. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737, The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973), etc., particles having an octahedron, tetrahedron, dodecahedron, etc. can be produced and used. Furthermore, particles having twin planes may be used.

  The grains used in the present invention are preferably grains having a single shape, but it is particularly preferred to add two or more monodispersed silver halide emulsions to the same image forming layer.

  The particle size of the silver halide grains used in the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably in consideration of suitability for rapid processability and reaching sensitivity, and other photographic performance. Is in the range of 0.2 to 1.0 μm.

  This grain size can be determined by measuring the projected area of the silver halide grains or using an approximate diameter. If the silver halide grains are substantially uniform in shape, the particle size distribution can be expressed fairly accurately as a diameter or projected area.

  The grain size distribution of the silver halide grains used in the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably a coefficient of variation of 0. .2 or more monodispersed emulsions of 15 or less are added to the same image forming layer. The variation coefficient here is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R
Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.

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

  The silver halide emulsion used in the present invention may be obtained by any of the acidic method, neutral method and ammonia method. The silver halide grains may be grown at a time, or may be grown after preparing seed grains. The method for preparing the seed particles and the method for growing them may be the same or different.

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

  Further, an apparatus for supplying a water-soluble silver salt and a water-soluble halide salt aqueous solution from an adding apparatus disposed in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524, German Patent No. 2 , 921,164, etc., an apparatus for continuously adding an aqueous solution of a water-soluble silver salt and a water-soluble halide salt, the reaction mother liquor outside the reactor described in JP-B-56-501776, etc. An apparatus for forming grains while keeping the distance between the silver halide grains constant by taking out and concentrating by ultrafiltration may be used.

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

  The negative silver halide emulsion used in the present invention can be appropriately combined with a sensitizing method using a gold compound, a sensitizing method using a chalcogen sensitizer, and the like. As the chalcogen sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, triethylthiourea, allylthiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like.

The addition amount of the sulfur sensitizer is preferably appropriately changed depending on the type of silver halide emulsion to be applied and the expected effect, but is generally 5 × 10 ^{−10 to} 5 per mol of silver halide. The range is × 10 ⁻⁵ mol, preferably 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol.

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but is usually 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ per mole of silver halide. Mole is preferred. More preferably, it is 1 * 10 < ^-5 > -1 * 10 <^-8> mol. These compounds can also be added for various purposes not as a sensitizer but at the stage of preparing a coating solution.

  As a chemical sensitization method for the negative silver halide emulsion used in the present invention, a reduction sensitization method may be used.

  The silver halide light-sensitive material of the present invention can also have a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength region of 400 to 900 nm. The silver halide emulsion contains one or a combination of two or more sensitizing dyes.

  As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compound can be used. As the blue-sensitive sensitizing dye, the general formula [I] according to the present invention can be used. In addition to the sensitizing dyes represented, a known sensitizing dye, for example, BS-1 to 8 described in JP-A-3-251840, page 28, may be used in combination as long as the object effects of the present invention are not impaired. Can do. As the green photosensitive sensitizing dye, GS-1 to 5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to 8 described in page 29 of the same publication are preferably used.

  These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization. In addition, these dyes may be added as a solution by dissolving in water or an organic solvent miscible with water such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide, or a sensitizing dye. May be added as a water miscible solvent solution, emulsion or suspension having a density greater than 1.0 g / ml.

As a method for dispersing the sensitizing dye, in addition to a method of mechanically pulverizing and dispersing fine particles having a size of 1 μm or less in an aqueous system using a high-speed stirring type disperser, a pH of 6 to 5 as described in JP-A No. how mechanically pulverized and dispersed to 1μm or less of the fine particles in the water-based under the conditions of ^{8,60~80 ℃, 3.8 × 10 -2 N} / m or less surface tension described in JP-B-60-6496 A method of dispersing in the presence of a surfactant that suppresses to a minimum, dissolved in an acid that does not substantially contain water and that does not exceed pKa as described in JP-A-50-80826, and adds the solution to an aqueous solution A method of dispersing and adding this dispersion to a silver halide emulsion can be used.

  The dispersion medium used for dispersion is preferably water, but a small amount of an organic solvent can be added to adjust the solubility, or a hydrophilic colloid such as gelatin can be added to improve the stability of the dispersion.

  Examples of the dispersion apparatus that can be used to prepare the dispersion include, for example, a ball mill, a sand mill, an ultrasonic disperser, and the like, in addition to the high-speed stirring disperser described in FIG. 1 of JP-A-4-125561. Can be mentioned.

  Further, when using these dispersing devices, as described in JP-A-4-125632, a pre-treatment such as dry pulverization may be performed in advance, followed by wet dispersion.

  The silver halide emulsion used in the present invention may contain one or a combination of two or more sensitizing dyes.

In the silver halide emulsion used in the present invention, for the purpose of preventing fogging that occurs during the preparation process of the silver halide color light-sensitive material, reducing performance fluctuation during storage, and preventing fogging during development, Known antifoggants and stabilizers can be used. Examples of preferable compounds that can be used for such purposes include nitrogen-containing heterocyclic mercapto compounds represented by the general formula (II) described in the lower column on page 7 of JP-A-2-14636. Specific examples of preferred compounds are (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and JP-A 2000- No. 267235, page 8, right column, lines 32 to 36, can be mentioned. Depending on the purpose, these compounds are added at any step such as a silver halide emulsion grain preparation step, a chemical sensitization step, a chemical sensitization step, or a coating solution preparation step. When chemical sensitization is performed in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol. . In the coating solution preparation step, when added to the silver halide emulsion layer, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver halide, and 1 × 10 ⁻⁵ to 1 ×. 10 ⁻² mol is more preferred. When added to a layer other than the silver halide emulsion layer, the content in the coating film is preferably about 1 × 10 ⁻⁹ to 1 × 10 ⁻³ mol per 1 m ² .

  Other additives can be added to the silver halide emulsion used in the present invention for various purposes. For example, disulfides and polysulfide compounds such as A-20, C-1, C-9, C-14, C-15, C-16, C-40 and the like specifically described in JP-A-2-146036 It is preferable to use thiosulfonic acid compounds such as D-1, D-3, D-6 and D-8, inorganic sulfur and the like.

  As the coupler used in the silver halide light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent. In addition to the yellow dye-forming coupler according to the present invention having a spectral absorption maximum wavelength in the wavelength range of 350 to 500 nm, a particularly representative product has a spectral absorption maximum wavelength in the wavelength range of 500 to 600 nm. A magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm is representative of those known as cyan dye-forming couplers.

  As the magenta coupler used in the silver halide light-sensitive material of the present invention, a compound represented by the general formula MI or M-II described on page 2 of JP-A-8-328210 is preferable. Specific examples of preferred compounds include MCP-1 to MCP-41 described on pages 6 to 16 of the same. Furthermore, as other specific examples, compounds M-1 to M-61 described on pages 6 to 21 of European Patent 0,273,712 and 36 to 92 of 0,235,913 are disclosed. Among the compounds 1-223 described on the page are those other than the representative examples described above.

The magenta coupler can be used in combination with other types of magenta couplers. Generally, the total amount of magenta coupler is 1 × 10 ⁻³ mol to 1 mol, preferably 1 × 10 ⁻² per mol of silver halide. It can be used in the range of mol to 8 × 10 ⁻¹ mol.

In the silver halide photographic material of the present invention, the λ _max of the spectral absorption of the magenta image to be formed is preferably 530 to 560 nm, and λ L _0.2 is preferably 580 to 635 nm. λL _0.2 means a wavelength at which the absorbance is 0.2 longer than the wavelength indicating the maximum absorbance when the maximum absorbance is 1.0 in the spectral absorbance curve of the image dye. This amount is a reference amount indicating the magnitude of unnecessary absorption on the long wave side of the image dye, and indicates that the closer to λ _max is, the smaller unnecessary absorption is preferable.

  The magenta image forming layer of the silver halide light-sensitive material of the present invention preferably contains a yellow coupler in addition to a magenta coupler. Preferred yellow couplers to be contained in the magenta image-forming layer of the silver halide light-sensitive material of the present invention include known pivaloyl acetanilide type or benzoyl acetanilide type couplers. Specific examples of preferable yellow couplers to be contained in the magenta image-forming layer of the silver halide light-sensitive material of the present invention include, for example, YCP-1 to YCP described on the right column on pages 6 to 15 of JP-A-8-314079. Although the coupler represented by -39 is mentioned, of course, it is not limited to these.

  In the silver halide light-sensitive material of the present invention, a known phenol-based, naphthol-based, imidazole-based, or azole-based coupler can be used as the cyan coupler contained in the cyan image forming layer. For example, phenol couplers substituted with alkyl groups, acylamino groups, or ureido groups, naphthol couplers formed from a 5-aminonaphthol skeleton, and 2-equivalent naphthol couplers introduced with an oxygen atom as a leaving group are representative. The Among these, preferred compounds include compounds represented by general formulas [CI] and [C-II] described on page 13 of JP-A-6-95283.

  As the azole coupler, a pyrazoloazole coupler represented by the general formula [I] or [II] described on page 2 of JP-A-8-171185, or described in JP-A-11-282138 Examples thereof include pyrroloazole couplers represented by the general formula (I).

The cyan coupler can be used usually in the range of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol per mol of silver halide in the silver halide emulsion layer.

  In the silver halide light-sensitive material of the present invention, a known yellow coupler, preferably an acylacetanilide type coupler can be used.

  Specific examples of yellow couplers that can be used in the present invention include, for example, compounds described on pages 5 to 9 of JP-A-3-241345, compounds represented by Y-I-1 to Y-I-55, Alternatively, compounds described on pages 11 to 14 of JP-A-3-209466 and compounds represented by Y-1 to Y-30 can also be preferably used. Furthermore, couplers represented by the general formula [Y-I] described on page 21 of JP-A-6-95283, compounds of general formulas (I) and (II) described in JP-A-2002-352023, and the like can also be mentioned. .

  Further, from the viewpoint of obtaining good color reproducibility, high color developability and good light resistance, an alkoxy group is located at the 2-position of the anilide moiety as described in JP-A-63-123047 at the 5-position. Yellow coupler having acylamino group, acetanilide type coupler having pyrimidin-4-one bonded with a nitrogen atom substituted with an alkyl group having 1 to 6 carbon atoms as described in US Pat. No. 5,455,149 An acetanilide type coupler to which a pyrimidin-4-one substituted with a substituted alkyl group described in JP-A No. 2002-296740 is bonded; and an pyrimidine-substituted with an aryl group or heterocyclic group described in JP-A No. 2002-296671 4-one-bonded acetanilide type couplers, divalent atoms such as heteroatoms described in JP-A No. 2002-318442 An acetanilide type coupler to which a pyrimidin-4-one introduced with a linking group is bonded, an acetanilide type coupler to which a pyrimidin-4-one substituted with an alkyl group having 7 or more carbon atoms described in JP-A-2002-318443 is bonded; Examples include acetanilide type couplers to which [1,2,4] thiadiazine-1,1-dioxide is bonded, as described in JP-A Nos. 2002-352023 and 2003-173007.

In the silver halide light-sensitive material of the present invention, the λ _max of the spectral absorption of the formed yellow image is preferably 425 nm or more, and λ L _0.2 is preferably 515 nm or less.

The spectral absorption λL _0.2 of the yellow color image is a value defined by the content described in JP-A-6-95283, page 21, right column, lines 1 to 24. It represents the magnitude of unnecessary absorption.

  In order to adjust the spectral absorption characteristics of the magenta color image, cyan color image, and yellow color image, a compound having a known color tone adjusting action together with the compound represented by the general formula (HBS-1) according to the present invention Can be added. Examples of the compound for this purpose include a phosphate ester compound represented by the general formula [HBS-I] and a phosphine oxide compound represented by [HBS-II] described on page 22 of JP-A-6-95283. It is done.

  Each of the magenta, cyan, and yellow couplers can be used in combination with an anti-fading agent for preventing fading of the formed dye image due to light, heat, humidity, and the like. Preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541, and phenolic compounds represented by general formula IIIB described in JP-A-3-174150. An amine compound represented by the general formula A described in JP-A No. 64-90445, and a metal complex represented by the general formulas XII, XIII, XIV, XV described in JP-A No. 62-182741 are particularly preferable. Preferred for magenta dyes. Further, compounds represented by the general formula I ′ described in JP-A-1-196049 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

  When an oil-in-water emulsion dispersion method is used when adding an anti-stain agent or other organic compound used in the silver halide photosensitive material of the present invention, it is usually added to a water-insoluble high boiling organic solvent having a boiling point of 150 ° C. or higher. If necessary, it is dissolved in combination with a low boiling point and / or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low boiling organic solvent after the dispersion or simultaneously with the dispersion may be incorporated. Examples of the high-boiling organic solvent that can be used for dissolving and dispersing the stain inhibitor include phosphate esters such as tricresyl phosphate and trioctyl phosphate, phosphine oxides such as trioctyl phosphine oxide, Higher alcohol compounds represented by (ai) to (ax) described on page 5 of JP-A 4-265975 are preferably used. The dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high-boiling organic solvents can be used in combination.

  In the silver halide light-sensitive material of the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used. In particular, as dyes having absorption in the visible region, the dyes of AI-1 to 11 described in JP-A-3-251840, page 308, and special dyes can be used. The dyes described in Kaihei 6-3770 are preferably used.

  It is preferable in that the white background can be further improved by adding a fluorescent brightening agent to the silver halide light-sensitive material of the present invention. The fluorescent whitening agent is not particularly limited as long as it is a compound that can absorb ultraviolet rays and emit visible light fluorescence, but is a diaminostilbene compound having at least one sulfonic acid group in the molecule, These compounds are preferable because they have an effect of promoting the elution of the sensitizing dye out of the silver halide color light-sensitive material. Another preferred form is a solid particulate compound having a fluorescent whitening effect.

  In the silver halide light-sensitive material of the present invention, various known surfactants can be used in combination. As a preferable compound as a surfactant used for dispersing a photographic additive used in a light-sensitive material or adjusting the surface tension during coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or its The thing containing a salt is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. A dispersion of an oil-soluble additive emulsified with these surfactants is usually added to a coating solution containing a silver halide emulsion. The time from application to application to application is preferably short, preferably within 10 hours, and more preferably within 3 hours and within 20 minutes.

  In the silver halide light-sensitive material of the present invention, a compound that reacts with an oxidizing agent of a developing agent is added to an intermediate layer provided between silver halide emulsion layers to prevent color turbidity, or directly to the silver halide emulsion layer. It is preferable to improve fog and the like by adding. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Particularly preferred compounds are compounds represented by the general formula II described in JP-A-4-133056, and examples thereof include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17. .

  In the silver halide light-sensitive material of the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of a dye image. Preferred ultraviolet absorbers include benzotriazoles, and particularly preferred compounds are compounds represented by general formula III-3 described in JP-A-1-250944, and general formulas described in JP-A-64-66646. Compounds represented by III, UV-1L to UV-27L described in JP-A-63-187240, compounds represented by general formula I described in JP-A-4-1633, and compounds described in JP-A-5-165144 Examples include compounds represented by general formulas (I) and (II).

  The silver halide light-sensitive material of the present invention preferably contains an oil-soluble dye or pigment because the white background is improved. Typical examples of oil-soluble dyes include compounds 1-27 described in JP-A-2-842, pages 8-9.

  In the silver halide light-sensitive material of the present invention, it is advantageous to use gelatin as a binder. However, if necessary, other gelatins such as gelatin derivatives, gelatin and other polymer graft polymers, proteins other than gelatin are used. Hydrophilic colloids such as sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer materials such as mono- or copolymers can also be used.

  As a hardener for these binders, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination. It is preferable to use the compounds described in JP-A-61-249054 and JP-A-61-245153. In order to prevent the growth of mold and bacteria that adversely affect photographic performance and image storage stability, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer.

  In coating a silver halide color light-sensitive material using a silver halide emulsion, a thickener may be used for the purpose of improving the coating property. As the application method, extrusion coating or curtain coating capable of simultaneously applying two or more layers is particularly useful.

  In general, the width of the silver halide light-sensitive material can be any width depending on the application, but in the present invention, a silver halide color light-sensitive material having a width of 450 mm or more is used for proofing. Preferably, it is 800 mm or more and 2000 mm or less.

In the silver halide color light-sensitive material according to the present invention, the white background after development processing, L ^* is 91 to 96 in CIE1976Lab colorimetric space, a ^* is 0 to 2.0, b ^* is -2.0 + 2 0.0 is preferred.

In the silver halide color light-sensitive material according to the present invention, the chromaticity of the white background (unexposed portion) after color development processing is CIE1976Lab color space (hereinafter referred to as CIELAB color space), and L ^* is 91 to 91. 96, a ^* is preferably 0 to 0.2, and b ^* is preferably −2.0 to +2.0.

  Here, the details of the CIELAB color space are described in detail in “Fine Imaging and Color Hardcopy” on page 354 (1999, published by Corona) edited by the Japanese Society of Photography and Imaging Society of Japan. Further, the trichromatic stimulus value when using this color space is a value obtained according to the method described in JIS Z8717 that defines the tristimulus value measurement method of the X, Y, and Z coordinates of the fluorescent reflecting object. The chromaticity in the CIELAB color space is measured by placing the standard white chromaticity on CIE 65 (6504K), which is an international standard for standard daylight. Therefore, a chromaticity measuring device capable of measuring the chromaticity in the CIELAB color space can be used for the measurement for verifying that the above condition A is satisfied. For example, it can be measured using a high-speed spectrophotometric color difference meter CMS-1200 (manufactured by Murakami Color Research Laboratory Co., Ltd.).

  Next, an image recording method on the silver halide color photographic material according to the present invention will be described.

  As the exposure light source of the exposure apparatus used in the present invention, any known light source can be preferably used, but a laser or a light emitting diode (hereinafter referred to as LED) is more preferably used.

  As the laser, a semiconductor laser (hereinafter referred to as LD) is preferably used because it is compact and has a long light source life.

  LDs are used for applications such as optical pickups for DVDs, CDs for music CDs, barcode scanners for POS systems, and optical communications, and have the advantage of being inexpensive and capable of providing relatively high output. is doing. Specific examples of the LD include aluminum, gallium, indium, arsenic (650 nm), indium, gallium, phosphorus (up to 700 nm), gallium, arsenic, phosphorus (610-900 nm), gallium, aluminum, arsenic (760-850 nm). And the like. Recently, a laser that oscillates blue light has been developed. However, at present, it is advantageous to use an LD as a light source having a wavelength longer than 610 nm.

  As a laser light source having an SHG element, light emitted from an LD or YAG laser is converted to a half-wavelength light by an SHG element and emitted, and since visible light is obtained, there is no green light source. ~ Used as a light source in the blue region. An example of this type of light source is a YAG laser combined with an SHG element (532 nm). Examples of the gas laser include a helium / cadmium laser (about 442 nm), an argon ion laser (about 514 nm), a helium neon laser (about 544 nm and 633 nm), and the like. In particular, a helium neon laser is preferably used as the G light source.

  LEDs having the same composition as LD are known, but various LEDs from blue to infrared have been put into practical use.

  As the exposure light source used in the present invention, each laser may be used alone, or may be used in combination as a multi-beam. In the case of an LD, for example, a beam composed of 10 luminous fluxes can be obtained by arranging 10 LDs. On the other hand, in the case of a helium neon laser, light emitted from the laser is divided into, for example, 10 light beams by a beam separator. In the case of a helium neon laser, a relatively well-shaped light beam can be easily obtained.

  In the case of LD, the intensity change of the exposure light source used in the present invention may be directly modulated to change the current value flowing through each LD, or an element such as an AOM (acousto-optic element). It may be used to change the intensity. In the case of a gas laser, devices such as AOM and EOM (electro-optic element) are generally used.

  One feature of the present invention is that it is a color proof that can output an area gradation image, but the area gradation image referred to in the present invention is the gradation of the color of individual pixels. It is not expressed, but is expressed by the size of the area of the portion colored at a specific density, and may be considered synonymous with a halftone dot.

  In general, in the case of area gradation exposure, the purpose can be achieved by developing colors of Y, M, and C. More preferably, it is preferable to perform exposure using different exposure amounts of two or more so as to make black at a density higher than the color density of a single color. In order to identify that a single color such as M or C has further developed on the black ink, it is preferable to perform exposure using different exposure values of three or more values. In printing, a specially colored plate may be used, but in order to reproduce this, it is preferable to use an exposure amount of 4 or more for different exposures.

  In the case of a laser light source, the beam diameter is preferably 25 μm or less, more preferably 6 to 22 μm. If it is smaller than 6 μm, it is preferable in terms of image quality, but adjustment is difficult or the processing speed decreases. On the other hand, if it is larger than 25 μm, unevenness increases and the sharpness of the image also deteriorates. By optimizing the beam diameter, high-definition images without unevenness can be written at high speed.

  In order to draw an image with such light, it is necessary to scan the light flux on the silver halide photosensitive material. The photosensitive material is wound around a cylindrical drum and rotated at a high speed in a direction perpendicular to the rotational direction. A cylindrical outer surface scanning method for moving a light beam may be used, and a cylindrical inner surface scanning method in which a silver halide photosensitive material is brought into close contact with a cylindrical depression for exposure can also be preferably used. A planar scanning method may be employed in which the polyhedron mirror is rotated at a high speed to expose the silver halide photosensitive material conveyed by moving the light beam at right angles to the conveying direction. In order to obtain a high image quality and a large image, the cylindrical outer surface scanning method is more preferably used.

  In order to perform exposure by the cylindrical outer surface scanning method, the silver halide photosensitive material must be brought into close contact with the cylindrical drum accurately. For this to be done accurately, it needs to be accurately aligned and transported. The silver halide photographic material used in the present invention can be preferably used because the surface on the side to be exposed is wound outward so that it can be aligned more accurately. From the same viewpoint, the support used for the silver halide photosensitive material used in the present invention has an appropriate rigidity, and the Taber rigidity is preferably 0.8 to 4.0.

  The drum diameter can be arbitrarily set according to the size of the silver halide photosensitive material to be exposed. The number of revolutions of the drum can also be set arbitrarily, but an appropriate number of revolutions can be selected according to the beam diameter of the laser beam, the energy intensity, the writing pattern and the sensitivity of the photosensitive material. From the viewpoint of productivity, it is preferable that scanning exposure can be performed at a higher rotation speed. Specifically, 200 to 3000 rotations per minute is preferably used.

  The silver halide photosensitive material can be fixed to the drum by mechanical means, or a large number of fine holes that can be sucked on the drum surface are provided according to the size of the photosensitive material. It can also be adhered by suction. In order to prevent troubles such as image unevenness, it is important to make the photosensitive material as close as possible to the drum.

  As the exposure light source of the exposure apparatus used in the present invention, any known light source can be preferably used, but a laser or a light emitting diode (hereinafter referred to as LED) is more preferably used.

  As the laser, a semiconductor laser (hereinafter referred to as LD) is preferably used because it is compact and has a long light source life. LDs are used for applications such as DVDs, optical pickups for music CDs, barcode scanners for POS systems, optical communications, etc., and they are inexpensive and can provide relatively high output. have. Specific examples of the LD include aluminum, gallium, indium, arsenic (650 nm), indium, gallium, phosphorus (up to 700 nm), gallium, arsenic, phosphorus (610-900 nm), gallium, aluminum, arsenic (760-850 nm). And the like. Recently, a laser that oscillates blue light has been developed. However, at present, it is advantageous to use an LD as a light source having a wavelength longer than 610 nm.

  As a laser light source having an SHG element, light emitted from an LD or YAG laser is converted to a half-wavelength light by an SHG element and emitted, and since visible light is obtained, there is no green light source. ~ Used as a light source in the blue region. An example of this type of light source is a YAG laser combined with an SHG element (532 nm).

  Examples of the gas laser include a helium / cadmium laser (about 442 nm), an argon ion laser (about 514 nm), a helium neon laser (about 544 nm and 633 nm), and the like.

  LEDs having the same composition as LD are known, but various LEDs from blue to infrared have been put into practical use.

  As the exposure light source used in the present invention, each laser may be used alone, or may be used in combination as a multi-beam. In the case of an LD, for example, a beam composed of 10 luminous fluxes can be obtained by arranging 10 LDs. On the other hand, in the case of a helium neon laser, light emitted from the laser is divided into, for example, 10 light beams by a beam separator.

  The intensity change of the exposure light source can be directly modulated to change the value of the current flowing through each element in the case of an LD or LED. In the case of an LD, the intensity may be changed using an element such as an AOM (acousto-optic modulator). In the case of a gas laser, devices such as AOM and EOM (electro-optic modulator) are generally used.

  When an LED is used as the light source, a method of exposing the same pixel with a plurality of elements may be used if the amount of light is weak.

  Moreover, you may use an organic light emitting element as a light source which replaces these, These are described in Unexamined-Japanese-Patent No. 2000-258846 etc., for example.

  In the present invention, the term area gradation image is used, but this is not expressed by the shade of the color of each pixel, but by the size of the area of the color developed at a specific density. And may be considered synonymous with halftone dots.

  In general, in the case of area gradation exposure, the purpose can be achieved by developing colors of Y, M, C, and black. More preferably, in order to identify that a single color such as M or C has developed in addition to black, it is preferable to perform exposure using different exposure amounts of three or more values. In printing, a special color plate may be used, but in order to reproduce this, it is preferable to perform exposure using different exposure values of four or more values.

  In the case of a laser light source, the beam diameter is preferably 25 μm or less, more preferably 6 to 22 μm. If it is smaller than 6 μm, it is preferable in terms of image quality, but adjustment is difficult or the processing speed decreases. On the other hand, if it is larger than 25 μm, unevenness increases and the sharpness of the image also deteriorates. By optimizing the beam diameter, high-definition images without unevenness can be written at high speed.

  In order to draw an image with such light, it is necessary to scan the silver halide color photosensitive material with a light beam. The silver halide color photosensitive material is wound around a cylindrical drum and rotated in a rotating direction while rotating at high speed. A cylindrical outer surface scanning method in which a light beam is moved in a direction perpendicular to the cylindrical surface may be employed, and a cylindrical inner surface scanning method in which a silver halide photosensitive material is brought into close contact with a cylindrical depression for exposure can also be preferably used. A planar scanning method may be employed in which the silver halide color photosensitive material conveyed by rotating the polyhedral mirror at high speed is exposed by moving the light beam at right angles to the conveying direction. In order to obtain a high image quality and a large image, the cylindrical outer surface scanning method is more preferably used.

  In order to perform exposure by the cylindrical outer surface scanning method, the silver halide color photosensitive material must be brought into close contact with the cylindrical drum accurately. For this to be done accurately, it needs to be accurately aligned and transported. The silver halide color light-sensitive material according to the present invention can be preferably used because the surface to be exposed is wound outwardly more accurately. From the same viewpoint, the support used in the silver halide color photographic material according to the present invention has an appropriate rigidity, and preferably has a Taber rigidity of 0.8 to 4.0.

  The drum diameter can be arbitrarily set according to the size of the silver halide color photosensitive material to be exposed. The number of revolutions of the drum can be arbitrarily set, but an appropriate number of revolutions can be selected depending on the beam diameter of the laser beam, the energy intensity, the writing pattern, the sensitivity of the silver halide color photosensitive material, and the like. From the viewpoint of productivity, it is preferable that scanning exposure can be performed at a higher rotation speed. Specifically, 200 to 3000 rotations per minute is preferably used.

  The silver halide color photosensitive material may be fixed to the drum by mechanical means, or a number of fine holes that can be sucked on the drum surface are provided according to the size of the silver halide color photosensitive material. Alternatively, the silver halide color light-sensitive material can be attracted and adhered. Adhering the silver halide color light-sensitive material to the drum as much as possible is important to prevent troubles such as image unevenness.

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

Example 1
<< Preparation of aqueous sensitizing dye >>
Sensitizing dyes BS-1, GS-1, GS-3, and RS-2 were each weighed in 5 mg, added to 1000 ml of pure water, and dissolved at room temperature with stirring. Among the sensitizing dyes, only GS-1 was not completely dissolved in pure water, but was a dispersed suspension.

<Measurement of spectral absorption characteristics>
Using the above-prepared 0.1% dye solution, a spectral absorption curve was created using a Hitachi type 330 Hitachi spectrophotometer manufactured by Hitachi, Ltd., and the wavelength indicating the maximum absorbance: the maximum absorption wavelength λmax1 was determined. Next, after adding and dissolving Compound-1, Exemplified Compound I-82, and Exemplified Compound I-83 at a concentration of 0.1% in the dye solution, the spectral absorption curve is again obtained in the same manner as described above. And the wavelength showing the maximum absorbance: the maximum absorption wavelength λmax2 was determined.

  Next, the fluctuation range (Δλmax) of λmax depending on whether or not a compound was added was determined by the following formula, and the obtained results are shown in Table 1.

      Δλmax (nm) = maximum absorption wavelength λmax2-maximum absorption wavelength λmax1

  As is clear from the results shown in Table 1, by adding Exemplified Compound I-82 and Exemplified Compound I-83 to the dye solution, the maximum absorption wavelength of each sensitizing dye solution is shifted to the longer wave side by 5 nm or more. You can see that

Example 2
<Preparation of silver halide color photosensitive material>
[Preparation of Sample 101]
Pulp made of 50% by weight of sulfate-method bleached hardwood pulp (LBKP) and 50% by weight of sulfate-method bleached softwood pulp (NBSP) for photographic grade paper is beaten so that the freeness (CSF) is 350 ml. 100 parts by mass, 3 parts by mass of cationized starch, 0.2 parts by mass of anionized polyacrylamide, 0.4 parts by mass of alkyl ketene dimer emulsion (as ketene dimer), 0.4 parts by mass of polyamide epichlorohydrin resin and Appropriate amounts of optical brightener and colorant were added to prepare a paper slurry. After that, the paper stock is formed on the long net paper machine running the paper slurry at 200 m / min while giving an appropriate turbulence, and the linear pressure is adjusted in the range of 150 N / cm to 1000 N / cm in the wet part. After performing the three-stage wet press, it was treated with a smoothing roll, followed by a two-stage tightness press in which the linear pressure was adjusted in the range of 300 N / cm to 700 N / cm in the subsequent drying part, followed by drying. did. Then, during drying, a size press solution consisting of 4 parts by weight of carboxy-modified polyvinyl alcohol, 0.05 parts by weight of optical brightener, 0.002 parts by weight of coloring dye, 4 parts by weight of sodium chloride, and 92 parts by weight of water was 25 g / Size press at m ² , dried so that the final base paper moisture is 8% by mass with absolutely dry moisture, machine calender treatment under the condition of linear pressure 500 N / cm, basis weight 98 g / m ² , A white base paper having a thickness of 100 μm was prepared.

  Next, as a resin layer on the back side of the white base paper, polyethylene was melt-extruded at 300 ° C. to coat a back laminate layer having a thickness of 15 μm.

Next, after kneading polyethylene and anatase-type titanium dioxide as a surface side resin layer (photosensitive layer coating surface side), the mixture is melt extruded at 300 ° C. to obtain 2.0 g / m ^{2 of} titanium dioxide and a thickness of 15 μm. A reflective support 1 having a resin coating layer on both sides was prepared without coating a water-resistant resin layer and performing a molding treatment with a molding roller.

Next, on the reflective support 1 (Taber stiffness = 3.5, PY value = 2.7 μm, centerline surface roughness SRa = 0.2 μm), each layer having the structure described in Table 2 below is formed of titanium oxide. A multilayer silver halide color light-sensitive material coated on the polyethylene layer-containing polyethylene layer side and further coated with a layer containing gelatin 6.00 g / m ² and silica matting agent 0.65 g / m ² on the back side 101 was produced. This sample 101 had a 60-degree specular gloss of 62.

The coupler was dissolved in a high boiling point solvent, ultrasonically dispersed, and added as a dispersion. At this time, (SU-1) was used as a surfactant. Moreover, (H-1) and (H-2) were added as a hardening agent. Further, (F-1) was added to each layer so that the total amount was 0.04 g / m ² .

  As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension.

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Sulfosuccinic acid di (2-ethylhexyl) sodium salt SU-3: Sulfosuccinic acid di (2,2,3,3,4,4,4) 5,5-octafluoropentyl) sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di -T-octylhydroquinone HQ-2: 2,5-di ((1,1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone and 2,5- A mixture of di-sec tetradecyl hydroquinone and 2-sec-dodecyl-5-sec-tetradecyl hydroquinone in a mass ratio of 1: 1: 2. Q-4: 2,5-di -t- butyl hydroquinone PVP: Polyvinylpyrrolidone

  Each photosensitive silver halide emulsion used in the preparation of Sample 101, which is the silver halide color photosensitive material, was prepared according to the following method.

(Preparation of blue-sensitive silver halide emulsion)
In 1 liter of 2% gelatin aqueous solution kept at 40 ° C., the following (A solution) and (B solution) were simultaneously added while controlling pAg = 7.3 and pH = 3.0, and the following (C solution) And (Liquid D) were simultaneously added while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled according to the method described in JP-A-59-45437, and pH was controlled using sulfuric acid or a sodium hydroxide aqueous solution.

<Liquid A>
Sodium chloride 3.42g
Potassium bromide 0.03g
Water added to finish 200ml <Liquid B>
Silver nitrate 10g
Water added to finish 200ml <C solution>
Sodium chloride 102.7g
Potassium hexachloroiridium (IV) 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium bromide 1.0 g
Water added to finish 600ml <Liquid D>
300 g of silver nitrate
Finished by adding water to 600 ml. After completion of addition, desalting was performed using a 5% aqueous solution of demole N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas, and then mixed with an aqueous gelatin solution to obtain an average particle size. A monodispersed cubic emulsion EMP-101 having 0.71 μm, a coefficient of variation of grain size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained.

  The emulsion EMP-101 was optimally chemically sensitized at 60 ° C. using the following compounds to obtain a blue-sensitive silver halide emulsion Em-B101.

Sodium thiosulfate 0.8mg / mol AgX
Chloroauric acid 0.5mg / mol AgX
Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-1 4 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-2 1 × 10 ⁻⁴ mol / mol AgX
Potassium bromide 0.2g / mol AgX
Next, in the preparation of the emulsion EMP-101, the average grain size was changed in the same manner except that the addition times of (A liquid) and (B liquid) and (C liquid) and (D liquid) were changed. A monodispersed cubic emulsion EMP-102 having a diameter of 0.64 μm, a coefficient of variation of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained.

  A blue-sensitive silver halide emulsion Em-B102 was prepared in the same manner as in the preparation of the blue-sensitive silver halide emulsion Em-B101, except that the emulsion EMP-102 was used instead of the emulsion EMP-101. A blue-sensitive silver halide emulsion using a 1: 1 mixture of -B101 and Em-B102 in the seventh layer was prepared.

(Preparation of green sensitive silver halide emulsion)
In the preparation of the emulsion EMP-101, the average particle size of 0 was similarly obtained except that the addition times of (A liquid) and (B liquid) and (C liquid) and (D liquid) were changed. A monodisperse cubic emulsion EMP-103 having a thickness of .40 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.

  The emulsion EMP-102 was optimally chemically sensitized at 55 ° C. using the following compound to obtain a green photosensitive silver halide emulsion Em-G101.

Sodium thiosulfate 1.5mg / mol AgX
Chloroauric acid 1.0mg / mol AgX
Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: GS-1 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: GS-2 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: GS-3 2 × 10 ⁻⁴ mol / mol AgX
Sodium chloride 0.5g / mol AgX
Subsequently, in the preparation of the emulsion EMP-103, the average particle size was changed in the same manner except that the addition time of (Liquid A) and (Liquid B) and the addition time of (Liquid C) and (Liquid D) were changed. A monodispersed cubic emulsion EMP-104 having a 0.50 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

  A green-sensitive silver halide emulsion Em-G102 was prepared in the same manner as in the preparation of the green-sensitive silver halide emulsion Em-G101, except that EMP-104 was used instead of EMP-103. Em-G101 and Em -A green-sensitive silver halide emulsion using a 1: 1 mixture of G102 in the fifth layer.

(Preparation of red-sensitive silver halide emulsion)
The prepared emulsion EMP-103 was optimally chemically sensitized at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion Em-R101.

Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer: STAB-1 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-4 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-1 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-2 1 × 10 ⁻⁴ mol / mol AgX
Supersensitizer: SS-1 2 × 10 ⁻⁴ mol / mol AgX
Next, the prepared emulsion EMP-103 was optimally chemically sensitized at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion Em-R102.

Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer: STAB-1 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-4 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-1 2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-2 2 × 10 ⁻⁴ mol / mol AgX
Supersensitizer: SS-1 2 × 10 ⁻⁴ mol / mol AgX
A 1: 1 mixture of the red-sensitive silver halide emulsion Em-R101 and the red-sensitive silver halide emulsion Em-R102 prepared above was used as the red-sensitive silver halide emulsion for the third layer.

  Details of the additives used in the preparation of each of the above photosensitive silver halide emulsions are as follows.

STAB-1: 1-phenyl-5-mercaptotetrazole STAB-2: 1- (4-Ethoxyphenyl) -5-mercaptotetrazole STAB-3: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-4: p-Toluenethiosulfonic acid

<Development processing conditions>
(Development processing condition 1)
Processing process Processing temperature Processing time Replenishment amount (ml / m ² )
Color development 40.0 ± 0.3 ℃ 120 seconds 250ml
Bleach fixing 40.0 ± 0.5 ℃ 60 seconds 150ml
Stabilization-1 40.0 ± 0.5 ℃ 35 seconds −
Stabilization-2 40.0 ± 0.5 ℃ 35 seconds −
Stabilization-3 40.0 ± 0.5 ℃ 35 seconds 400ml
Drying 55-75 ° C. 20 seconds Note that the capacity of the color developer tank is 21 L, the capacity of the bleach-fixing tank is 8 L, the stabilization of the three-stage multi-stage countercurrent system, and the capacity of the stabilization tanks of 1 to 3 is respectively 6L.

  The treatment liquids used in the above treatment steps are as follows.

<Color developer tank solution and replenisher>
Tank liquid Replenisher Pure water 800ml 800ml
Diethylene glycol 10g 10g
Potassium bromide 0.25g 0.25g
Potassium chloride 0.5g 3.0g
N-ethyl-N- (β-hydroxyethyl) -4-aminoaniline sulfate
2.6g 3.5g
N, N-disulfoethylhydroxylamine sodium salt
20.0g 20.0g
Diethylenetriaminepentaacetic acid sodium salt 2.0 g 2.0 g
Potassium carbonate 30g 30g
Potassium bicarbonate 6.0g 6.0g
Water was added to a total volume of 1 liter, and the tank solution was adjusted to pH = 10.1 and the replenisher solution was adjusted to pH = 10.5 with sulfuric acid or potassium hydroxide.

<Bleach fixer tank solution and replenisher>
Tank liquid Replenisher Diethylenetriaminepentaacetic acid ferric complex salt 0.15 mol 0.20 mol Diethylenetriaminepentaacetic acid 0.01 mol 0.01 mol Ammonium thiosulfate (75% aqueous solution) 120 g 150 g
2-Amino-5-mercapto-1,3,4-thiadiazole
1.6g 2.0g
Sodium metabisulfite 20g 30g
Imidazole 7.0 g 10 g
Potassium bromide 16g 20g
Water was added to a total volume of 1 liter, and the tank solution was adjusted to pH = 6.5 and the replenisher solution was adjusted to pH = 5.5 with aqueous ammonia or sulfuric acid.

<Stabilizing liquid tank liquid 1 and replenishing liquid 1>
Tank liquid = replenisher o-phenylphenol 1.0g
1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g
Ammonium sulfite (40% aqueous solution) 10g
Ethylenediaminetetraacetic acid 3.0 g
Potassium hydroxide (50% aqueous solution) 5.0 g
Water was added to bring the total volume to 1 liter, and the pH was adjusted to 7.0 with sulfuric acid or potassium hydroxide (50% aqueous solution).

(Development processing condition 2)
In the above development processing condition 1, this was designated as development processing condition 2 except that 1 g / L of compound-1 (above) was added to the stabilization liquid tank solution and the replenisher used in the stabilization step. .

(Development processing condition 3)
In the above-mentioned development processing condition 1, this was designated as development processing condition 3 except that 1 g / L of Exemplified Compound I-82 was added to the stabilization liquid tank solution and the replenisher used in the stabilization step.

(Development processing condition 4)
In the above development processing condition 1, this was designated as development processing condition 4 except that 1 g / L of Exemplified Compound I-83 was added to the stabilization liquid tank solution and the replenisher used in the stabilization step.

《Image formation》
[Cutting the sample]
The prepared sample 101 was cut into three sheet sizes of 350 mm wide × 970 mm long, 492 mm wide × 970 mm long, and 670 mm wide × 970 mm long.

[Exposure equipment]
A drum exposure type exposure apparatus having the following light source was used.

  As a light source, five blue LEDs were arranged in the main scanning direction, and the exposure timing was gradually delayed so that the same place could be exposed with five LEDs. In addition, an exposure head was prepared in which 20 LEDs were arranged in the sub-scanning direction and the exposure for 20 adjacent pixels could be performed at once. Similarly for green and red, exposure heads were prepared by combining LEDs in the same manner as described above.

  A sheet sample of each size is wound around a cylindrical drum of a 670 mm wide cylindrical outer surface scanning system, and sucked from a punch hole provided on the surface and brought into intimate contact, and each beam diameter is about 10 μm while rotating at high speed. The sub-scanning pitch was about 100 μm, and the exposure time per pixel was about 100 nanoseconds.

  The exposure images are 3, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, yellow (Y), magenta (M), cyan (C), and black (K). A 100% halftone image was exposed.

[Development processing]
The sample of each size subjected to the above exposure and the sample of each size not exposed were subjected to continuous processing up to two rounds using the development processing conditions 1 to 4. The term “two rounds” as used herein means that the continuous processing is performed until the color developer replenisher in an amount twice (42 L) of the color developer tank volume (21 L) is replenished.

<Evaluation>
[Evaluation of stability on white background]
The color difference ΔE1 was measured for each unexposed sample at the start of continuous processing and at the end of two rounds of continuous processing according to the following method.

For color difference measurement, a white background portion (unexposed portion) is measured using a spectrocolorimeter CM-2022 manufactured by Konica Minolta Sensing Co., Ltd., using a geometric condition d-0 for illumination and light reception, a xenon pulse light source, and a 2 ° field of view. Then, 10 values of L ^* , a ^* , and b ^{* in} the auxiliary standard light D50 were measured to determine the average value, and the color difference of each sample at the start of continuous processing and at the end of continuous processing was determined. The color difference ΔE1 was obtained from the following equation.

ΔE1 = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2
Here, ΔL ^* , Δa ^* , and Δb ^* represent differences between the samples at the start of continuous processing and at the end of continuous processing, respectively.

[Evaluation of width tolerance on white background]
For each unexposed sample at the end of two rounds of continuous processing, the color difference ΔE2 was measured according to the following method.

In the color difference measurement, the values of L ^* , a ^* , and b ^* are measured at equal intervals of 20 points in the width direction in the same manner as the above method, and the color difference between the measured values that are most distant in the color space is measured. Asked. The color difference ΔE2 was obtained from the following equation.

ΔE2 = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2
Here, ΔL ^* , Δa ^* , and Δb ^* each represent a difference between measured values that are most deviated in the color space.

[Evaluation of uniformity of white background]
The state of the white background was visually observed on the entire surface of each unexposed sample at the end of two rounds of continuous processing, and the uniformity of the white background was evaluated according to the following criteria.

○: Uniform white background characteristics, no unevenness is observed. Δ: White background unevenness is slightly recognized, but whiteness is within the practically acceptable limit. ×: Clear white background unevenness is recognized, which is a practical problem. [Evaluation of wearability during exposure]
100 samples of each size are wound around a cylindrical drum of a cylindrical outer surface scanning method with a width of 670 mm of the exposure apparatus, and are exposed while being rotated at a high speed while being sucked and brought into close contact with a punch hole provided on the surface. The number of defective mounting at this time was measured, and the mounting property during exposure was evaluated according to the following criteria.

○: Number of defective mounting was 3 or less △: Number of defective mounting was 4 or more, 8 or less ×: Number of mounting failure was 9 or more Table 3 shows the results obtained.

  As is clear from the results shown in Table 3, a silver halide color light-sensitive material having a width of 450 mm or more was continuously used by using a stabilization process in which a compound having an effect of shifting the maximum absorption wavelength of the sensitizing dye aqueous solution by 5 nm or more was added. The level of the processed present invention is superior to the comparative example in white background stability in continuous processing, white width unevenness resistance and white background uniformity, and also excellent in the ability to be mounted on a cylindrical drum during exposure. It can be seen that both white background stability, which is important for proofing, and production suitability (wearability during exposure) are achieved.

Example 2
<< Preparation of silver halide color photosensitive material >>
Sample 102 was prepared in the same manner as in the preparation of Sample 101, which was the silver halide color photosensitive material described in Example 1, except that the configurations of the reflective support and the eighth layer were changed as follows. Note that the 60-degree specular gloss of the sample 102 was 5.

[Change of reflective support]
In the production of the reflective support 1 (SRa = 0.2) used for the production of the sample 101 described in Example 1, after the surface-side resin layer was melt-extrusion laminated, various kinds of rugged structures with different sizes and densities were formed on the surface. A reflective support 2 was prepared and used in the same manner except that a fine uneven pattern was appropriately formed by pressure contact with a molding roller, and the centerline surface roughness SRa was changed to 1.5.

[Change of the 8th layer (UV absorbing layer)]
In the same manner as in the eighth layer (ultraviolet absorption layer) of Sample 101 described in Example 1, except that the addition amount of the silica matting agent was changed from 0.01 g / m ² to 0.50 g / m ² , A layer was formed.

<< Image formation and evaluation >>
In the image formation and each evaluation described in Example 1, exposure, development processing, and each evaluation were performed in the same manner except that the above-prepared sample 102 was used instead of the sample 101, and the obtained results are shown in Table 4. Shown in

  As is clear from the results shown in Table 4, a large amount of silica matting agent was added to the outermost layer (eighth layer), and the silver halide color light-sensitive material having a low glossiness was the same as the result of Example 1. Compared with the comparative example, the level of the present invention is excellent in white background stability in continuous processing, white width unevenness resistance and white background uniformity, and also in excellent wearability to a cylindrical drum during exposure. It can be seen that both white background stability and production suitability (wearability at the time of exposure), which are important in (1), are achieved. Further, when a large amount of silica matting agent is not added and ΔE2 in the case of treatment conditions 1 and 2 is added, ΔE2 expands, and thus a greater effect is exhibited. I understand that

Example 3
<< Preparation of silver halide color photosensitive material >>
The sample 101 described in Example 1 has a white background characteristic (measured by the spectrocolorimeter CM-2022) when developed under the development processing condition 1 described in Example 1, and L ^* = 92.5, a ^* = 0.80 and b ^* = 1.00.

In the preparation of the sample 101, the amount of fluorescent whitening agent used in the preparation of the reflective support 1 was adjusted as appropriate, and the white background characteristics after the development treatment were L ^* = 92.5, a ^* = 0.80, Sample 103 was prepared in the same manner except that b ^* = − 4.00.

<< Image formation and evaluation >>
In the image formation and each evaluation described in Example 1, exposure and development processing (development processing conditions) were performed in the same manner as in the method described in Example 1 using the sample 101 described in Example 1 and the sample 103 prepared above. 1 and 3) and each evaluation (evaluation of width variation of white background and evaluation of uniformity of white background) are performed, and the obtained results are shown in Table 5.

  As is clear from the results shown in Table 5, in the comparative example in which the fluorescent whitening agent was used and the center of the white background was shifted in the bluish direction as in the sample 103, the chromaticity fluctuation in the width was reduced. Although the measured value (ΔE1) is large, the white background uniformity when visually observed is different in the degree of recognition of unevenness. In the sample 101 having a more natural white background characteristic, it is apparent that, in the comparative example, the fluctuation of the white background by visual observation becomes obvious, and the effect of the present invention is particularly exhibited under such conditions. .

Claims (6)

A proof silver halide color photosensitive material having a width of 450 mm or more having a photosensitive silver halide layer containing a silver halide emulsion spectrally sensitized with at least one sensitizing dye on a support is developed at least for color development. In a method for processing a silver halide color light-sensitive material that undergoes development processing through each processing step of a processing step, a desilvering processing step, a water washing processing step, or a stabilization processing step, at least one processing tank constituting each processing step A processing solution for silver halide color light-sensitive material, wherein the processing solution comprises a compound that shifts the maximum spectral absorption wavelength (λmax) of the aqueous solution of the sensitizing dye by ± 5 nm or more. The silver halide color according to claim 1, wherein the compound that shifts the maximum spectral absorption wavelength (λmax) of the aqueous solution of the sensitizing dye by ± 5 nm or more is a compound represented by the following general formula (I): Processing method of photosensitive material.

[Wherein, X ₁ , X ₂ , Y ₁ and Y ₂ are each independently —N (R ₁ ) R ₂ , —OR ₃ , —SR ₃ , a heterocyclic group, a hydroxyl group, a hydroxylamino group or a halogen atom. Z ₁ and Z ₂ each represent —NR ₄ —, —O— or —S—, L represents an arylene group, an alkylene group, an alkenylene group or a heterocyclic group, and R ₁ and R ₂ each represent hydrogen. An atom, an alkyl group, an aryl group or a heterocyclic group; R ₃ represents an alkyl group, an aryl group or a heterocyclic group; and R ₄ represents a hydrogen atom, an aryl group, a heterocyclic group or an alkyl group. R ₁ and R ₂ may combine to form a nitrogen-containing heterocycle. However, the molecule represented by the general formula (I) does not have an azo group or a diaminostilbene structure. ] The compound represented by the general formula (I) is at least one selected from the compounds represented by the following general formulas (I-1) to (I-4). Processing method of silver halide color photosensitive material.

[Wherein, R _{11 to} R ₁₈ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. L ₁ represents a phenylene group or a naphthylene group. Three or more of R _{11 to} R ₁₈ are aryl groups. R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , R ₁₇ and R ₁₈ may be bonded to each other to form a ring. However, the molecule represented by the general formula (I-1) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by the general formula (I-1) does not contain a group represented by -N = N- or a diaminostilbene structure in the molecule. ]

[Wherein, R _{21 to} R ₂₈ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. L ₂ represents a phenylene group, a naphthylene group, an alkylene group or a heterocyclic group. Ra represents an alkyl group, an aryl group or a heterocyclic group, and Rb represents a hydrogen atom, an alkyl group or an aryl group. R ₂₁ and R ₂₂ , R ₂₃ and R ₂₄ , R ₂₅ and R ₂₆ , R ₂₇ and R ₂₈ may be bonded to each other to form a ring. However, the compound represented by the general formula (I-2) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by general formula (I-2) does not contain -N = N- or a diaminostilbene structure in the molecule. ]

[Wherein, R _{31 to} R ₃₄ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. L ₃ represents a phenylene group, a naphthylene group, an alkylene group or a heterocyclic group. A ₃₁ and A ₃₂ each independently represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group or a hydroxylamino group. R ₃₅ and R ₃₆ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ₃₁ and R ₃₂ , R ₃₃ and R ₃₄ may be bonded to each other to form a ring. However, the compound represented by the general formula (I-3) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by general formula (I-3) does not contain the group represented by -N = N- in the molecule. ]

[Wherein L ₄ represents a phenylene group, a naphthylene group or an alkylene group. X ₁ represents an oxygen atom or a sulfur atom, and X ₂ represents an oxygen atom, a sulfur atom or —NH—. A ₄₁ , A ₄₂ , A ₄₃ and A ₄₄ are each independently an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a hydroxylamino group, or —NR ₄₁ R ₄₂ (R ₄₁ And R ₄₂ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₄₁ and R ₄₂ may be bonded to each other to form a ring). However, the compound represented by the general formula (I-4) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by the general formula (I-4) does not contain a group represented by —N═N— or a diaminostilbene structure in the molecule. ] The silver halide color light-sensitive material has at least one silver halide emulsion layer on the support and a non-photosensitive colloid layer farthest from the support, and the non-photosensitive colloid layer Has a 60-degree specular gloss measured in accordance with JIS-Z 8741 on the surface side containing the amorphous porous fine particles and having the silver halide emulsion layer after the development processing, and 9. 4. The method for processing a silver halide color light-sensitive material according to claim 1, wherein the processing method is 0 or less. The white background after the development processing of the silver halide color light-sensitive material has an L ^* in the CIE 1976 Lab color space of 91 to 96, a ^* of 0 to 2.0, and b ^* of −2.0 to +2.0. The processing method of the silver halide color photosensitive material of any one of Claims 1-4 characterized by these. The treatment liquid containing a compound that shifts the maximum spectral absorption wavelength (λmax) of the aqueous solution of the sensitizing dye by ± 5 nm or more is a washing water or a stabilizing liquid used in the washing treatment process or the stabilization treatment process. The processing method of the silver halide color photosensitive material of any one of Claims 1-5.