JP2001281822A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material less liable to a gradation change due to the entering of a bleach-fixing solution into a color developing solution, in particular the enhancement of contrast (and/or the increase of sensitivity) and less liable to the increase of fog due to a change of color development time. SOLUTION: The silver halide color photographic sensitive material contains at least one compound selected from dimercaptopyrimidine compounds, dimercapto-1,3,5-triazine compounds and dimercapto-1,2,4-triazine compounds, silver halide grains in at least one silver halide emulsion layer of the sensitive material have >=95 mol% silver chloride content and 1) >=50% of the total projected area is occupied by flat platy grains having 111} or 100} faces as principal planes and an average aspect ratio of >=2.0 or 2) the silver halide grains are cubic grains.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide color photographic material. In particular, a tough silver halide color photographic light-sensitive material has a small change in gradation even when a subsequent bleach-fixing solution is mixed in the color developing solution, and a small increase in fog even when the color developing time is extended. It is about.

[0002]

2. Description of the Related Art In the field of photographic processing services, when a silver halide color photographic light-sensitive material using a high silver chloride emulsion, particularly a color photographic paper, is rapidly developed, there are some potential processes involved in the development process. The problem is involved. One of them is gradation variation due to the incorporation of a bleach-fix solution in a color developing solution, in particular, high contrast (and / or increased sensitivity).
Generally, color development processing is performed, for example, on color photographic paper.
The developing process is performed by passing through each bath in the order of a color developing bath, a bleach-fix bath (or a bleach bath and a fixing bath), and a washing bath.
It is rare that a bleach-fixing solution that subsequently passes into the color developing solution, but it occurs at a certain frequency. When the bleach-fixing solution is mixed into the color developing solution, the composition of the color developing solution changes. Or the sensitivity increases. Moreover, the silver halide emulsions in the yellow, magenta, and cyan emulsion layers are individually susceptible to this effect, and the color balance of the three colors is greatly disrupted. This causes remarkable loss of image quality for silver halide color photographic light-sensitive materials, especially for color photographic paper directly observed by a user. For this reason, a tough photosensitive material that does not cause a gradation change (particularly a high contrast and / or an increase in sensitivity) due to the incorporation of a bleach-fix solution into a color developing solution has been keenly desired.

As a second potential problem, it is known that the developer activity of the color developer varies due to the difference in the frequency of the running process. There is a problem that the characteristics fluctuate. On the other hand, when the developing activity of the color developing solution is reduced, it can be dealt with by increasing the color developing time, but this is counter to the current rapid processing and is not realistic. Accordingly, a photosensitive material whose photographic properties are hardly fluctuated in response to fluctuations in the development activity of the color developing solution, that is, fluctuations in the color development time, is also eagerly desired. These problems are remarkable in a silver halide color photographic light-sensitive material using a high silver chloride emulsion having a silver chloride content of 95 mol% or more, especially in a color photographic paper.顕 著 な This is a remarkable problem in color photographic paper using a flat high silver chloride emulsion.

[0004] The addition of a mercaptopyrimidine compound to a light-sensitive material is disclosed in JP-A-52-58532.
No. 1,462,211. However, the former is used for improving the bleach-fixing ability, and the latter is used for improving the humidity dependency during exposure and stabilizing the latent image.
Many of these compounds are insufficient for the above problems, and adversely affect photographic sensitivity and gradation. The addition of a mercaptotriazine compound to a light-sensitive material is known from JP-A-8-304950. However, this is added to a printing photosensitive material which is a black-and-white photosensitive material, and is used for dissolving at high temperature and high pH or for preventing two-color fog and brown silver contamination. It is not a solution. In addition, many mercaptotriazine compounds, like the mercaptopyrimidine compounds, have many adverse effects on photographic sensitivity and gradation.

[0005]

The first problem to be solved by the present invention is that gradation fluctuation, particularly high contrast (and / or increased sensitivity) due to the incorporation of a bleach-fix solution into a color developing solution.
To provide a silver halide photographic light-sensitive material having a small amount of silver halide. A second object is to provide a silver halide photographic light-sensitive material in which an increase in fog is small with respect to a change in color development time. Thirdly, there is no adverse effect on basic photographic performance such as photographic sensitivity, fog, and gradation while solving the first and second problems.
An object of the present invention is to provide a silver halide photographic light-sensitive material. 4th
Another object of the present invention is to provide a silver halide photographic material which solves the first, second, and third problems similarly when performing rapid processing.

[0006]

As a result of intensive studies by the present inventors, the above object has been achieved by the following [1] to [3]. [1] Dimercaptopyrimidine compound, dimercapto-
1,3,5-triazine compound, dimercapto-1,
A silver halide grain of at least one silver halide emulsion layer containing at least one compound selected from 2,4-triazine compounds and having a silver chloride content of 95 mol% or more, and a projected area Silver halide color photographic light-sensitive material, wherein 50% or more of the silver halide grains are tabular grains having a {111} plane or {100} plane as a main plane and an average aspect ratio of 2.0 or more. [2] At least one compound selected from a dimercaptopyrimidine compound, a dimercapto-1,3,5-triazine compound and a dimercapto-1,2,4-triazine compound represented by the following general formula (1) A silver halide color photographic light-sensitive material, wherein the silver halide grains in at least one silver halide emulsion layer are cubic grains having a silver chloride content of 95 mol% or more. General formula (1)

[0007]

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[0008] In the formula, R ₁ represents -SM group, a hydrogen atom, a substituted alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carboxy group, a sulfo group, R ₂ and R ₃ each independently represents a hydrogen atom or a substituent. However, R ₁ to R ₃
At least one of is -SM group, also, is not R ₁ and R ₂ are hydrogen atoms at the same time. M represents a hydrogen atom or a cation. Note that a plurality of Ms may be the same or different from each other. [3] The pyrimidine or triazine compound is at least one compound selected from a pyrimidine compound represented by the following general formula (1A) or a triazine compound represented by the following general formula (2). The silver halide color photographic light-sensitive material according to the item [1] or [2], which is characterized by the above-mentioned. General formula (1A)

[0009]

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Wherein R ₁ and R ₃ are each independently —SM
Represents a group, a hydrogen atom, a substituted alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group or a carboxy group. However, at least one of R ₁ and R ₃ is -SM
And R ₁ and R ₂ are not hydrogen atoms at the same time. R ₂ represents a hydrogen atom, an alkyl group, an amino group, or a halogen atom. Here, at least one of R ₁ to R ₃
One is a water-soluble group or a group having a water-soluble group. M represents a hydrogen atom or a cation. Note that a plurality of Ms may be the same or different from each other. General formula (2)

[0011]

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In the formula, R ₄ represents a -SM group, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group or a carboxy group. Here, R ₄ is a water-soluble group or a group having a water-soluble group. M represents a hydrogen atom or a cation. Note that a plurality of Ms may be the same or different from each other.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First, the dimercaptopyrimidine compound, dimercapto-1,3,5-triazine compound and dimercapto-1,2,4-triazine compound used in the present invention will be described.

In the present invention, "mercapto" refers to -S
Represents an M group. That is, it is defined to mean not only the -SH group but also the -SM group. Here, M represents a hydrogen atom or a cation. Note that a cation is an ion having a positive charge and has a charge of 1
It may be monovalent, divalent or trivalent. For example, alkali metal ions, alkaline earth metal ions, ammonium ions, onium ions, and more specifically,
Na, K, Li, Ca, Mg, Al, ammonium and the like. Preferred are monovalent cations, such as alkali metal ions and ammonium ions. The -SM group in the general formulas (1), (1A) and (2) described below has the same meaning as the above-described -SM group. Dimercaptopyrimidine compound as defined in the present invention,
The dimercapto-1,3,5-triazine compound and the dimercapto-1,2,4-triazine compound are at least two mercapto groups, that is,-in the present invention,-
A group of compounds having at least two SM groups, which may have a substituent on these heterocycles;
It also includes an SM group. Thus, tri- or tetramercaptopyrimidine, trimercapto-1,2,4-
It also includes triazine and trimercapto-1,3,5-triazine.

In the present invention, the pyrimidine compound is a monocyclic pyrimidine compound, which does not include a benzo-fused quinazoline or a purine condensed with an imidazole ring. is there. The water-soluble group defined in the present invention is a carboxyl group,
Sulfo group, sulfino group, phosphono group, ammonium group,
It is a highly water-soluble hydrophilic group, such as an amino group, a phosphonio group, or a group in which the acid portion of the group becomes a salt, which has high water solubility by protonation in water having a pH of 6 to 8, and a water-soluble group. Is a group having the group as a substituent. Therefore, the water-soluble group defined in the present invention does not include a group having a weak interaction with a water molecule, such as a mercapto group and a hydroxyl group. In the present invention,
Dimercaptopyrimidine compound, dimercapto-1,
3,5-triazine compound, dimercapto-1,2,4
-Triazine compounds are collectively referred to as "dimercaptoheterocyclic compounds".

In the present invention, the "dimercaptoheterocyclic compound" may have various substituents, and the substituents include the following. Halogen atom (for example, fluorine atom, chlorine atom, bromine atom), alkyl group (for example, methyl, ethyl, i-propyl, t-butyl, n-octyl, cyclopropyl, cyclohexyl), alkenyl group (for example, allyl, -Butenyl,
3-pentenyl), alkynyl group (eg, propargyl, 3-pentynyl), aralkyl group (eg, benzyl, phenethyl), aryl group (eg, phenyl, naphthyl, 4-methylphenyl), heterocyclic group (eg,
Pyridyl, furyl, imidazolyl, piperidyl, morpholino), alkoxy groups (eg, methoxy, ethoxy,
Butoxy), an aryloxy group (for example, phenoxy,
2-naphthyloxy), amino group (for example, unsubstituted amino, dimethylamino, ethylamino, anilino), ureido group (for example, unsubstituted ureide, N-methylureide, N-phenylureido), urethane group (for example, methoxy) Carbonylamino, phenoxycarbonylamino), sulfonyl group (eg, mesyl, tosyl), sulfinyl group (eg, methylsulfinyl, phenylsulfinyl), sulfonamide group (eg, methanesulfonamide), sulfamoyl group (eg, N-methylsulfa) Moyl), an alkyloxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl), an acyl group (eg, formyl, acetyl, benzoyl, pivaloyl), Aryloxy group (e.g., acetoxy, benzoyloxy), an alkylthio group (e.g.,
Methylthio, ethylthio), arylthio group (for example,
Phenylthio), cyano, hydroxy, mercapto, carboxy, phosphono, nitro, sulfo,
Examples thereof include a sulfino group, an ammonium group (for example, trimethylammonio), and a silyl group (for example, trimethylsilyl). These groups may be further substituted. Also,
When there are two or more substituents, they may be the same or different.

As the dimercaptopyrimidine compound, a 2,4-dimercaptopyrimidine compound or a 2,6-dimercaptopyrimidine compound is preferably used. The hydrogen atom of the mercapto group is, , Li atom or ammonium cation. In the present invention, a dimercaptopyrimidine compound or a dimercapto-1,3,5-triazine compound is preferable, a dimercaptopyrimidine compound is more preferable, and a -SM group having 2 to 3 groups is more preferable.
Pyrimidines having only two, particularly preferably two. Among them, the dimercaptopyrimidine compound and the dimercapto-1,3,5-triazine compound preferably used in the present invention are compounds represented by the aforementioned general formula (1) or (2).

Next, the compound represented by formula (1) will be described in detail. In the general formula (1), M represents a hydrogen atom or a cation, and examples of the cation include an alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and an ammonium ion (eg, unsubstituted ammonium ion, triethylammonium ion) ) Represents a quaternary ammonium ion (for example, tetramethylammonium ion). Preferably it is a monovalent cation.

In the general formula (1), R ₁ represents -SM, a hydrogen atom, a substituted alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carboxy group or a sulfo group; R ₂ and R ₃ each independently represent a hydrogen atom or a substituent. However, at least one of R ₁ to R ₃ is a —SM group, and R ₁ and R ₂ are not simultaneously hydrogen atoms. M represents a hydrogen atom or a cation. Note that a plurality of Ms may be the same or different from each other. The substituted alkyl group for R ₁ preferably has 1 to 20 carbon atoms, and particularly is a linear, branched or cyclic substituted alkyl group having 1 to 10 carbon atoms, and the substituent is the aforementioned “dimercapto” Substituents which the "heterocyclic compound" may have. Among the substituents, preferred groups are hydrophilic groups including a water-soluble group, and among them, an ammonio group, an amino group capable of being protonated in water having a pH of 6 to 8, a carboxyl group, and a sulfo group are preferable. A carboxyl group and a sulfo group are preferred, and a sulfo group is particularly preferred. Examples of these are hydroxymethyl, 2-hydroxyethyl, carboxymethyl, 2-carboxyethyl, 2-sulfoethyl, 3-sulfopropyl and the like. The aryl group preferably has 6 to 20 carbon atoms, particularly a monocyclic or condensed aryl group having 6 to 10 carbon atoms,
For example, phenyl, naphthyl and the like. Of these, a phenyl group which may have a substituent is preferable. The amino group is
A substituted or unsubstituted amino group, wherein the substituted amino group is an alkylamino group (preferably an alkylamino group having 1 to 20 carbon atoms, particularly preferably an alkylamino group having 1 to 10 carbon atoms, for example, methylamino, ethylamino, propyl Amino), dialkylamino group (preferably having 1 to 2 carbon atoms)
0, particularly preferably a dialkylamino group having 1 to 10 carbon atoms, for example, dimethylamino, diethylamino), an arylamino group (preferably an arylamino group having 6 to 20 carbon atoms, particularly preferably 6 to 10 carbon atoms) For example,
Phenylamino, p-methylphenylamino).
The alkoxy group is preferably an alkoxy group having 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy and n-propyloxy.
The aryloxy group preferably has 6 to 2 carbon atoms.
0, particularly preferably an aryloxy group having 6 to 10 carbon atoms, for example, phenoxy. The alkylthio group is preferably an alkylthio group having 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methylthio, butylthio and octylthio. The arylthio group is preferably an arylthio group having 6 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, for example, phenylthio,
And naphthylthio.

As the substituents for R ₂ and R _3, the substituents which the aforementioned “dimercaptoheterocyclic compound” may have and the groups R _{1 to} R ₃ described below may be further substituted. Good groups are mentioned. These substituents include-
SM group, amino group, hydroxyl group, carboxyl group,
A halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and a sulfo group are preferable, and a -SM group is more preferable.
An amino group, a carboxyl group, a halogen atom, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group. In addition, each group of R _{1 to} R ₃ may be further substituted with a substituent, and examples of the substituent include the following.

A halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, a nitro group, an ammonium group (for example, trimethylammonio), a phosphonio group, a sulfo group (including salts), a sulfino group (including salts), Carboxy group (including salt), phosphono group (including salt), hydroxy group, mercapto group, hydrazino group, alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, cyclopentyl, Cyclohexyl), alkenyl group (for example, allyl, 2-butenyl,
3-pentenyl), alkynyl group (eg, propargyl, 3-pentynyl), aralkyl group (eg, benzyl, phenethyl), aryl group (eg, phenyl, naphthyl, 4-methylphenyl), heterocyclic group (eg,
Pyridyl, furyl, imidazolyl, piperidyl, morpholino), alkoxy groups (eg, methoxy, ethoxy,
Butyloxy), an aryloxy group (for example, phenoxy, 2-naphthyloxy), an alkylthio group (for example,
Methylthio, ethylthio), arylthio group (for example,
Phenylthio), an amino group (eg, unsubstituted amino,
Methylamino, dimethylamino, ethylamino, alinino), acyl group (eg, acetyl, benzoyl, formyl, pivaloyl), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), Carbamoyl group (eg, unsubstituted carbamoyl, N, N-dimethylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl), acyloxy group (eg, acetoxy, benzoyloxy), acylamino group (eg, acetylamino, benzoylamino) , An alkoxycarbonylamino group (eg, methoxycarbonylamino), an aryloxycarbonylamino group (eg, phenoxycarbonylamino), a ureido group (eg, unsubstituted , N-methylureido, N-phenylureido), alkylsulfonylamino group (eg, methylsulfonylamino), arylsulfonylamino group (eg, phenylsulfonylamino), alkylsulfonyloxy group (eg, methylsulfonyloxy), aryl A sulfonyloxy group (eg, phenylsulfonyloxy), an alkylsulfonyl group (eg, mesyl), an arylsulfonyl group (eg, tosyl), an alkoxysulfonyl group (eg, methoxysulfonyl), an aryloxysulfonyl group (eg, phenoxysulfonyl), A sulfamoyl group (eg, unsubstituted sulfamoyl, N-methylsulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl), an alkylsulfinyl group (eg, Methylsulfinyl), arylsulfinyl group (e.g., phenylsulfinyl), alkoxysulfinyl sulfinyl group (e.g., methoxysulfinyl), an aryloxy sulfinyl group (e.g., phenoxy cis sulfinyl)
And a phosphoric acid amide group (for example, N, N-diethylphosphoric acid amide). These groups may be further substituted. When there are two or more substituents, they may be the same or different.

In the compound represented by the general formula (1),
Preferably, at least one of R _{1 to} R ₃ is a water-soluble group or a group having a water-soluble group, and more preferably the water-soluble group (a water-soluble group of a group having a water-containing group). Is a carboxy group (including a salt), a sulfo group (including a salt), an ammonium group (for example, trimethylammonio,
Dimethylammonio), an amino group (for example, dimethylamino) which can be protonated in water having a pH of 6 to 8, and a group selected from a phosphonio group, and more preferably a carboxyl group (including a salt) and a sulfo group (including a salt). ), An ammonio group, a phosphonio group, more preferably a carboxy group (including a salt), a sulfo group (including a salt),
Particularly preferred is a sulfo group (including a salt).

Among the compounds represented by the general formula (1), more preferred are the compounds represented by the aforementioned general formula (1A). Hereinafter, the compound represented by Formula (1A) will be described in detail. In the general formula (1A), M has the same meaning as M in the general formula (1). R ₁ and R ₃ independently represents -SM, hydrogen atom, a substituted alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group or a carboxy group. Where R ₁ and R ₃
At least one represents a -SM group, and R ₁ and R ₂ are not simultaneously hydrogen atoms. R ₂ is a hydrogen atom,
Represents an alkyl group, an amino group or a halogen atom. Here, at least one of R ₁ to R ₃ is a water-soluble group or a group having a water-soluble group. M represents a hydrogen atom or a cation. Note that a plurality of Ms may be the same or different from each other. The substituted alkyl group, aryl group, amino group, alkoxy group, and aryloxy group for R ₁ have the same meaning as described in the general formula (1), and preferred ones are also the same. R
_The alkyl group represented by ₂ preferably has 1 to 20 carbon atoms.
And especially a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl,
Propyl, isopropyl, cyclopropyl and the like. The amino group represented by R ₂ has the same meaning as the amino group represented by R ₁ . Examples of the halogen atom represented by R ₂ include a chlorine atom, a bromine atom, and a fluorine atom.

In the general formula (1A), at least one group represented by R _{1 to} R ₃ is a water-soluble group or a group having a water-soluble group. Examples of the water-soluble group include a carboxy group (including a salt), Sulfo groups (including salts), ammonium groups (eg,
Trimethylammonio, dimethylammonio, etc.), p
H6-8 water-protonizable amino groups (e.g.,
Dimethylamino) and a phosphonio group are preferable, and a carboxyl group (including a salt), a sulfo group (including a salt), an ammonio group, and a phosphonio group are more preferable, and a carboxy group (including a salt) and a sulfo group (including a salt) are more preferable. And a sulfo group (including a salt). Further, a preferable group having a water-soluble group is a group substituted by the above-mentioned preferable water-soluble group. Each of the groups R _{1 to} R ₃ may be further substituted with a substituent, and the substituent may be a group which may be substituted by each of the groups R _{1 to} R ₃ in the aforementioned general formula (1). And the substituents mentioned above.

The compound represented by formula (1) (preferably (1A)) preferably used in the present invention is
Is a monovalent cation, R ₁ is an alkylamino group, an arylamino group or an alkoxy group, R ₂ is a hydrogen atom, and R ₃ is a —SM group.

In the compound represented by formula (1) (preferably (1A)), more preferably, M is a monovalent cation, R ₁ is an alkylamino group or an arylamino group, and R _{2 is} Is a hydrogen atom, and R ₃ is-
It is an SM group.

In the compound represented by formula (1) (preferably (1A)), M is preferably a monovalent cation, and R ₁ has an alkylamino group having a sulfo group or a sulfo group. An arylamino group, R
₂ is a hydrogen atom and R ₃ is a —SM group.

Next, the compound represented by formula (2) will be described in detail. In the general formula (2), M has the same meaning as M in the general formula (1).

In the general formula (2), R ₄ is -SM
Represents a group, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, and a carboxy group. Among them, -SM group, aryl group, amino group, alkoxy group,
The aryloxy group and the carboxy group have the same meanings as R ₁ in formula (1), and preferred ones are also the same. The alkyl group is preferably one having 1 to 20 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, cyclopropyl and the like. is there.

The compound represented by formula (2) preferably used in the present invention is a compound wherein M is a monovalent cation and R ₄ is an alkylamino group, an arylamino group or an alkoxy group. In the general formula (2), more preferably, M is a monovalent cation, and R ₄
Is an alkylamino group or an arylamino group.

In the general formula (2), most preferably,
M is a monovalent cation, and R ₄ is an alkylamino group having a sulfo group or an arylamino group having a sulfo group.

Next, specific examples of the dimercaptopyrimidine compound, the dimercapto-1,3,5-triazine compound and the dimercapto-1,2,4-triazine compound (general formulas (1), (1A) and Specific examples of the compound represented by the general formula (2) are shown below, but the compounds defined in the present invention are not limited thereto.
(Note that (1) and (2) added to the exemplified compound No. correspond to the general formula (1) and the general formula (2), respectively, provided that the general formula (1A) ), But it is clear from each chemical structural formula.)

[0033]

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[0034]

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[0035]

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The dimercaptopyrimidine compound and the dimercaptotriazine compound defined in the present invention can be easily synthesized according to a synthesis method described in the following literature. The dimercaptopyrimidine compound used in the present invention can be synthesized based on the method described in JP-A-9-274289 and the literature cited in the specification. Further, dimercaptotriazine compounds are disclosed in
No. -21806, No. 8-6215, No. 3-2824
Compounds can be synthesized based on the methods described in JP-A Nos. 57 and 9-212810 and the references cited therein.

In the dimercaptopyrimidine compound and the dimercaptotriazine compound defined in the present invention, those having a water-soluble group or a group having water-solubility as a substituent are preferable. Fluctuations in sensitivity when the bleach-fixing solution is mixed into the developing solution are further suppressed, which more advantageously acts to suppress fog when the developing time fluctuates (extends). In addition, it also suppresses the occurrence of uneven color density as a problem related to the processing steps of the photosensitive material. Note that the color density unevenness is a color density that is originally uniform when exposed to light and then developed, but the color density is not uniform when actually run using an automatic developing device. That there is. In the present invention, suppression of the occurrence of the unevenness in color density can be cited as the third problem to be solved in the present invention.

In the present invention, only one kind of the dimercaptopyrimidine compound or the dimercaptotriazine compound may be added, or two or more kinds thereof may be added.
These compounds are used in at least one of the silver halide photosensitive materials.
It is preferable to use it by adding it to the hydrophilic colloid layer of the layer, and it may be added to the silver halide emulsion layer or may be added to a layer other than the silver halide emulsion layer. Preferably,
It is added to a hydrophilic colloid layer other than the silver halide emulsion layer. In the present invention, a preferable addition amount of the dimercaptopyrimidine compound or the dimercaptotriazine compound is 1 × 10 ⁻⁷ to 1 × 10 ⁻² mol per mol of silver halide when added to the silver halide emulsion layer. And more preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol. Also, when added to a layer other than a silver halide emulsion layer, the per coating area 1m ^2, 1 × 10 ^-7 ~
It is in the range of 1 × 10 ⁻³ mol, more preferably 1 × 10 ⁻³ mol.
^-7 to 1 × 10 ^-4 mol.

Next, the silver halide grains used in the present invention will be described. In the present invention, the silver halide grains used in combination with the dimercaptopyrimidine compound and the dimercaptotriazine compound have a silver chloride content of 95 mol% or more, and 1) 50% or more of the projected area is {111} face or Tabular grains having a main plane of 100 ° and an average aspect ratio of 2.0 or more, or 2) cubic grains.
In the present invention, these silver halide grains may be used alone or in combination, or may be used in combination with other silver halide grains (preferably having a silver chloride content of 95 mol% or more). (Silver particles).

In the present invention, the silver halide grains include silver chloride, silver chlorobromide, silver chloroiodobromide, and silver chloroiodide grains in which 95 mol% or more is silver chloride in order to speed up the processing time. It is necessary to use Preferably, the silver chloride content is 95 to 99.99 mol%, more preferably 97%.
To 99.9 mol%, more preferably 98 to 99.9 mol%. Japanese Patent Application Laid-Open No. 3-8 / 1993 for the purpose of enhancing high illuminance sensitivity or spectral sensitization sensitivity, or enhancing the temporal stability of a photosensitive material.
0.015 on the emulsion surface as described in
High silver chloride grains containing up to 3 mol% of silver iodide may be preferably used. The halogen composition of the emulsion may be different or equal between grains, but it is preferable to use an emulsion having the same halogen composition between grains, since it is easy to make the properties of each grain uniform. Regarding the distribution of the halogen composition inside the silver halide emulsion grains, there is a so-called uniform type grain having the same composition in any part of the silver halide grains, or the core inside the silver halide grains.
Particles having a so-called laminated structure in which the halogen composition differs between the shell and the shell (core) [single or multiple layers] surrounding the shell,
Alternatively, a particle having a structure having a different halogen composition in a non-layered manner inside or on the surface of the particle (in the case of being on the particle surface, a structure in which a different composition is bonded to the edge, corner or plane of the particle) is appropriately selected. Can be used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, which is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, the boundary between different portions in the halogen composition may be a clear boundary or an unclear boundary due to the formation of a mixed crystal due to a composition difference. It may also be one that has a continuous and positive structural change.

The high silver chloride emulsion used in the present invention preferably has a structure having a silver bromide localized phase in the form of a layer or a non-layer as described above inside and / or on the surface of silver halide grains. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%.
More than 20 mol% is more preferred. The silver bromide content of the silver bromide localized phase is analyzed using an X-ray diffraction method (for example, described in “The Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis” Maruzen) or the like. be able to. These localized phases can be inside the grains, at the edges, corners or planes of the grain surfaces. One preferred example is one grown epitaxially at the corners of the grains. It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, a substantially pure silver chloride emulsion having a silver chloride content of 98% to 100% by mole is preferably used.

The silver halide grains contained in the photographic emulsion may have a regular crystal form such as cubic, tetradecahedral or octahedral, or irregular shapes such as spherical or tabular. A compound having an (irregular) crystal form or a compound having these compound forms can be used. Further, it may be composed of a mixture having various crystal forms. In the present invention, among them, 1) 50% or more of the projected area has a {111} plane or {100} plane as a main plane and an average aspect ratio of 2.0
The above tabular grains or 2) cubic grains. The silver halide grains specified in the present invention can be used in combination with the silver halide grains having shapes other than those specified in the present invention. In the present invention, JP-A-8-234345,
JP-A-9-166636 and JP-A-10-123658
A silver chloroiodide emulsion having a silver iodide layer in the vicinity of the surface as described in No. 1 is also preferably used.

The silver halide cubic grains used in the present invention preferably contain 50% or more, preferably 70% or more, more preferably 90 to 100% of grains having a cubic crystal form. The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the equivalent spherical diameter, and the number average is calculated) is 0.1.
μm to 1 μm is preferred, more preferably 0.1 μm
m to 0.5 μm, most preferably 0.1 μm to
0.4 μm. Further, the particle size distribution is preferably a monodispersion having a coefficient of variation (the standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less, more preferably 10% or less. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The other silver halide emulsion used in the present invention has a total projected area of all silver halide grains of 50.
% Or more has a {100} plane or {111} plane as a main plane, preferably 60 to 100%, more preferably 80 to 100%, and still more preferably 90 to 100%.
%, Particularly preferably 95 to 100%, of which the surface is the main plane, and the aspect ratio is 2.0 or more, preferably 2.0 to 100, more preferably 2.0 to 50, and still more preferably 4 to 100%. 0.0 to 50, particularly preferably 6.0 to 50
Silver halide tabular grains. The tabular grains have a thickness of 0.01 to 0.30 μm, preferably 0.02 to 0.30 μm.
0.20 μm, more preferably 0.05-0.15 μm
And the projected diameter is 0.1 to 10 μm, preferably 0.1 to 10 μm.
These are tabular grains of 2 to 5.0 μm. The coefficient of variation of projected diameter and thickness (standard deviation of distribution / average projected diameter or average thickness) is preferably 0-0.4, more preferably 0-0.
3, more preferably 0.01 to 0.2. Here, the aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of a particle. The larger the aspect ratio, the thinner and flatter the particles. In the present invention, the tabular grains have an aspect ratio of 1.2 or more,
The average aspect ratio means an average value of aspect ratios of all tabular grains in the emulsion. The projected diameter refers to the diameter of a circle having an area equal to the projected area of the grains, and the thickness refers to the distance between two main planes of the tabular grains. The projected diameter of a tabular grain refers to the diameter of a circle having an area equal to the projected area when the principal plane is placed parallel to the substrate surface and observed from the perpendicular direction.

As a method for forming tabular silver halide emulsion grains having {100} major planes, a silver salt aqueous solution and a halide salt aqueous solution are added to a dispersion medium such as an aqueous gelatin solution with stirring and mixed. At this time, for example, JP-A-6-301129 and JP-A-6-3479
No. 29 discloses silver iodide and, for example, JP-A-9-34.
No. 045 discloses a method in which silver bromide is present, a nucleus is distorted due to a difference in crystal lattice size from silver chloride, and screw dislocations are introduced. When a screw dislocation is introduced,
Since the formation of the two-dimensional nucleus on the plane is no longer rate-limiting, crystallization proceeds on this plane, and two ２1
Tabular grains are formed by introduction into the 00 ° plane. JP-A-6-347928 uses imidazoles and 3,5-diaminotriazoles, and JP-A-8-339044 uses polyvinyl alcohols to add a {100} plane formation promoter. A method for forming {100} tabular grains is disclosed.

As a method for forming tabular silver halide emulsion grains having {111} major planes, for example, US Pat. Nos. 4,400,463 and 5,185,239.
No. 5,176,991 and JP-A-63-2138.
No. 36, US Pat. No. 5,176,992, Japanese Patent Application No. 10
In the -123789, aminoazaindene,
A method for forming particles in the presence of a crystal habit controlling agent of triaminopyrimidine, hydroxyaminoazine, thiourea, xanthonoid, or pyridinium salt is disclosed.

The silver halide grains used in the present invention have a {100} plane having a silver chloride content of 95 mol% or more as a main plane or a {111} plane as a main plane. Tabular grains are preferred, and the tabular grains are preferably silver halide tabular grains containing at least silver iodide.
The silver iodide content is preferably 0.01 to 1 mol%, more preferably 0.05 to 0.7 mol%, and still more preferably 0.1 to 0.5 mol%. Silver chloride content 95 mol%
If the above conditions are satisfied, silver bromide may be contained, but the preferred silver bromide content is 0.01 to 5 mol%, more preferably 0.1 to 2 mol%, and still more preferably. 0.3 to 1 mol%. The silver halide tabular grains used in the present invention are preferably tabular grains having a {111} plane as a main plane.

The silver halide tabular grains used in the present invention are a silver halide emulsion layer containing a yellow dye-forming coupler,
Any of the silver halide emulsion layers containing a magenta dye-forming coupler and the silver halide emulsion layers containing a cyan dye-forming coupler can be used, but a silver halide emulsion layer containing a yellow dye-forming coupler and a halogen containing a magenta dye-forming coupler can be used. It is preferably used in at least one of the silver halide emulsion layers, and most preferably used in a silver halide emulsion layer containing a yellow dye-forming coupler.

The silver halide grains which are cubic grains or tabular grains used in the present invention will be further described below.

The emulsion used in the present invention preferably contains a thiocyanate, and typically includes a sodium salt, a potassium salt and the like. The addition position is not limited to any one of the steps, but it is preferable to add it after the formation of the grains and before the end of the chemical sensitization. The addition amount of the thiocyanate, per mol of silver halide 1 × 10 ^{- 6}
Mol to 3 × 10 ⁻³ mol, more preferably 2 × 10 ⁻³ mol
It is 10 ^-4 to 1 × 10 ^-3 mol.

The silver halide emulsion used in the present invention is:
Various polyvalent metal ion impurities can be introduced during the process of emulsion grain formation or physical ripening. Examples of compounds used include iron, iridium, ruthenium,
Osmium, rhenium, rhodium, cadmium, zinc,
Salts or complex salts of metals of Group VIII of the periodic table such as lead, copper and thallium can be used in combination. In the present invention, a metal compound having at least four cyano ligands, such as iron, ruthenium, osmium, and rhenium, is particularly preferred in that it further enhances high illuminance sensitivity and suppresses latent image sensitization. In addition, the iridium compound also has a great effect on imparting high illuminance exposure suitability. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol per mol of silver halide. These metal ions will be described in more detail, but are not limited thereto.

The iridium ion-containing compound is a trivalent or tetravalent salt or complex salt, preferably a complex salt. For example, first iridium chloride (III), first iridium bromide (II
I), iridium chloride (IV), sodium hexachloroiridium (III), hexachloroiridium (I
V) potassium acid, hexaammine iridium (IV) salt,
Halogens such as trioxalatoiridium (III) salts and trioxalatoiridium (IV) salts, amines, and oxalato complex salts are preferred. The platinum ion-containing compound is a divalent or tetravalent salt or complex salt, preferably a complex salt. For example, platinum (IV) chloride, potassium hexachloroplatinum (IV), tetrachloroplatinum (II) acid, tetrabromoplatinum (II) acid, tetrakis (thiocyanato)
Sodium platinum (IV), hexaammine platinum (IV) chloride and the like are used.

The palladium ion-containing compound is usually a divalent or tetravalent salt or complex salt, and a complex salt is particularly preferred. For example, sodium tetrachloropalladium (II), sodium tetrachloropalladium (IV), potassium hexachloropalladium (IV), tetraamminepalladium (II) chloride, tetracyanopalladium (II)
Potassium acid or the like is used. As the nickel ion-containing compound, for example, nickel chloride, nickel bromide, potassium tetrachloronickel (II), hexaamminenickel (II) chloride, sodium tetracyanonickelate (II) and the like are used.

Rhodium ion-containing compounds are usually preferably trivalent salts or complex salts. For example, potassium hexachlororhodate, sodium hexabromorhodate, ammonium hexachlororhodate and the like are used. The iron ion-containing compound is a divalent or trivalent iron ion-containing compound, and is preferably an iron salt or an iron complex salt having water solubility in the concentration range used. Particularly preferred is an iron complex salt which can be easily contained in silver halide grains. For example, ferrous chloride,
Ferric chloride, ferrous hydroxide, ferric hydroxide, ferrous thiocyanate, ferric thiocyanate, iron hexacyano (II)
Complex salts, hexacyanoiron (III) complex salts, ferrous thiocyanate complex salts, and ferric thiocyanate complex salts. Further, a six-coordinate metal complex having at least four cyan ligands as described in European Patent EP 0,336,426A is also preferably used.

The above-mentioned metal ion-providing compound is prepared by dispersing a metal ion in a gelatin aqueous solution, a halide aqueous solution, a silver salt aqueous solution, or another aqueous solution when forming silver halide grains, or in advance. The silver halide grains used in the present invention can be contained in the silver halide grains by adding silver halide grains and dissolving the grains. The metal ions used in the present invention can be contained in the particles either before, during or immediately after the formation of the particles. This can be changed depending on where the metal ions are contained in the particles.

The silver halide emulsion used in the present invention is:
Subjected to chemical sensitization. Regarding the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used.

The silver halide emulsion used in the present invention is
It is preferably subjected to gold sensitization known in the art. This is because, by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed using a laser beam or the like can be further reduced. For gold sensitization, compounds such as chloroauric acid or a salt thereof, gold thiocyanates or gold thiosulfates can be used. The addition amount of these compounds may vary widely depending on the case, but is from 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably from 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol per mol of silver halide. is there.

In the present invention, gold sensitization is carried out by other sensitization methods,
For example, it may be combined with sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using a compound other than a gold compound.

The emulsion used in the present invention preferably contains a thiosulfonic acid compound and a sulfinic acid compound. In particular, it is preferable to contain a thiosulfonic acid compound and a sulfinic acid compound represented by formulas (X) and (Y), respectively.

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In the general formulas (X) and (Y), R ²¹ and R ²² independently represent an aliphatic group, an aromatic group or a heterocyclic group, and M ²¹ and M ²² independently represent a cation. Represents The aliphatic groups represented by R ²¹ and R ²² in the general formulas (X) and (Y) include linear, branched, and cyclic alkyl groups, alkenyl groups, and alkynyl groups. However, the carbon number is preferably such that it is soluble in water; a lower alcohol such as methanol or ethanol; an organic solvent such as ethyl acetate; or a mixed solvent thereof. Examples of the aromatic group represented by R ²¹ and R ²² include a phenyl group and a naphthyl group, and examples of the heterocyclic group include 5 to 7 containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom as a hetero atom. Member rings are preferred, and the rings may be saturated or unsaturated. Further, a ring obtained by condensing another ring such as a benzene ring may be used. The substituents which can be substituted on these aliphatic groups, aromatic groups and heterocyclic groups are not particularly limited in the number or type, but may be dissolved in water or an organic solvent as described above or a mixed solvent thereof. Are preferred, or at least do not hinder.

Specific examples of the substituent include an alkoxy group,
Examples include an aryl group, an alkyl group, a halogen atom, an amino group, a carboxyl group, a hydroxyl group, and a heterocyclic group. The cations represented by M ²¹ and M ²² include alkali metals (eg, Li ⁺ , Na ⁺ , K ⁺ ), ammonium ions (NH ₄ ⁺ , tetraethylammonium ion)
And the like. Representative specific examples of the thiosulfonic acid compound and the sulfinic acid compound are described below.

[0063]

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The addition amount of the thiosulfonic acid compound is preferably from 1 × 10 ^{−6 to} 5 × 10 ⁻³ per mol of silver halide.
Mole, more preferably 3 × 10 ^{-6 to} 5 × 10 ^-4 mole.

[0066]

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[0067]

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The addition amount of the sulfinic acid compound is preferably from 1 × 10 ⁻⁶ mol to 1 × 1 per mol of silver halide.
The amount is 0 ^-3 mol, more preferably 3 × 10 ^-6 to 4 × 10 ^-4 mol. It is preferable to add the thiosulfonic acid compound and the sulfinic acid compound in a state where the amounts to be added are mixed in advance and to add them at the same time. The position at which the mixture is added is not limited to any one of the steps, but is preferably added during grain formation and during the chemical sensitization step. Particle formation 5
It is more preferable to add it by the end of 0% and to add it at the beginning of chemical sensitization.

Various silver halide emulsions for use in the present invention may be used for the purpose of preventing fogging of the emulsion or the photographic material during the production process, storage or photographic processing, or stabilizing photographic performance. Compounds can be included. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles,
Mercaptothiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (particularly 1-phenyl-
5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines and the like; thioketo compounds such as oxazolinethione; azaindenes;
For example, triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindene) pentaazaindenes; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide and the like. Many compounds known as antifoggants or stabilizers can be added. Particularly preferred are mercaptotetrazoles. This is preferable because it has a function of further increasing the high illuminance sensitivity in addition to preventing fog and stabilizing.

In the silver halide color photographic light-sensitive material according to the present invention, gelatin is used as a hydrophilic binder.
If necessary, other gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, and hydrophilic colloids such as synthetic hydrophilic polymer substances such as mono- or copolymers may also be used. It can be used in combination with gelatin.

The gelatin used in the silver halide color photographic light-sensitive material according to the present invention may be any of lime-processed gelatin and acid-processed gelatin, and gelatin produced from any of bovine bone, cowhide and pigskin. However, lime-processed gelatin obtained from cow bone and pig skin is preferred.

In the present invention, the silver halide
Hydrophilicity farthest from the support on the side coated with the emulsion layer
Photosensitive silver halide emulsion layer up to colloid layer and insensitive
Hydrophilic binder contained in light hydrophilic colloid layer
Is 6.5 g / m2 from the viewpoint of rapid processing.^TwoLess than,
Most preferably 5.5 g / m^TwoLess than and 4.0 g / m ^Two
That is all. If the amount of hydrophilic binder is small, especially color development
It is effective for speeding up the development and washing steps.

In the present invention, [amount of hydrophilic binder / thickness of silver halide] in all silver halide emulsion layers
The ratio is preferably 1.5 or more. Hereinafter, this ratio is referred to as [B / AgX] ratio in the present invention. Here, the amount of hydrophilic binder means the amount of hydrophilic binder (g / m ² ) per 1 m ^{2 of the} silver halide emulsion layer. The amount of the hydrophilic binder is divided by the specific gravity to represent the thickness, and it is understood that the amount of the hydrophilic binder in the present invention is an amount proportional to the thickness.
On the other hand, the term "silver halide emulsion thickness" means a thickness (μm) occupied by silver halide emulsion grains in the silver halide emulsion layer in a direction perpendicular to the support. In the present invention, assuming that the silver halide emulsion layer is ideally coated, the side length (μm) of the cube in the case of cubic grains and the thickness (in the direction perpendicular to the main plane in the case of tabular grains) μm) is the thickness of the silver halide emulsion. When silver halide emulsion grains of different sizes are used in combination, the mass average of each grain is defined as the silver halide emulsion thickness.

As is clear from the above definition, the [B / AgX] ratio in the present invention indicates that the larger the ratio, the smaller the emulsion thickness in the emulsion layer.
In the present invention, the [B / AgX] ratio is 1.50 or more from the viewpoint of suppression of pressure fogging and reduction of color mixture during processing.
It is preferably at least 1.70, more preferably at least 1.90, most preferably at least 6.0.

In the present invention, the silver halide emulsion layer containing the yellow coupler may be arranged at any position on the support, but the silver halide emulsion layer containing the magenta coupler or the silver halide emulsion containing the cyan coupler may be used. It is preferable that the coating is provided at a position farther from the support than at least one of the layers. Further, from the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color by the sensitizing dye, the yellow-coupler-containing silver halide emulsion layer is located farthest from the support than the other silver halide emulsion layers. Preferably, it is coated. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably a layer at the center of the other silver halide emulsion layers, and from the viewpoint of reducing photo-fading, the cyan coupler-containing silver halide emulsion layer is preferably The lowermost layer is preferred. Further, each of the color forming layers of yellow, magenta and cyan may be composed of two or three layers. For example, JP-A-4-75055 and JP-A-9-114
No. 035, 10-246940, U.S. Pat.
As described in JP-A-76-159 and the like, it is also preferable to provide a coupler layer containing no silver halide emulsion adjacent to the silver halide emulsion layer to form a color-forming layer.

The silver halide emulsion layer containing the yellow coupler is preferably coated farthest from the support than the silver halide emulsion layer, but the silver halide emulsion layer containing the yellow coupler contains a hydrophilic binder. The amount is preferably not more than 1.35 g / m ^2, more preferably 1.25 g / m ^2.
g / m ² or less, most preferably 1.20 g / m ² or less 0.
It is 60 g / m ² or more. The silver halide emulsion preferably has a side length of 0.80 when cubic grains are used.
μm or less, more preferably 0.75 μm or less, most preferably 0.70 μm or less and 0.30 μm or more. When tabular grains are used, the side length is preferably 0.40 μm.
The thickness is preferably 0.02 μm or more, more preferably 0.30 μm or less, further preferably 0.20 μm or less, and most preferably 0.15 μm or less and 0.05 μm or more.
The aspect ratio of the tabular grains is preferably from 2 to 10, more preferably from 3 to 8. Further, in order to control sensitivity, gradation and other photographic performance, it is preferable to use a mixture of silver halide emulsions having different sizes and shapes.

In the present invention, the coating amount of the silver halide emulsion is preferably not more than 0.60 g / m ^{2 and not} less than 0.10 g / m ^2, more preferably not more than 0.55 g / m ^{2 and not} more than 0.20 g / m ^2.
m ² or more, most preferably 0.50 g / m ² 0.25
g / m ² or more.

When cubic silver halide emulsion grains are used for the cyan coloring layer and the magenta coloring layer, the side length is preferably 0.50 μm or less, more preferably 0.40 μm or less and 0.10 μm or more. .

In the present invention, the film thickness of the photographic layer constitution means
It represents the thickness before processing of the photographic layer configuration above the support.
Specifically, it can be determined by any of the following methods. First, it can be determined by cutting a silver halide color photographic light-sensitive material perpendicularly to a support and observing the cut surface with a microscope. The second method is to calculate the film thickness from the coating amount (g / m ² ) and specific gravity of each component in the photographic layer constitution. For example, the specific gravity of typical gelatin used for photography is 1.34 g / ml, the specific gravity of silver chloride is 5.59 g / ml, and other lipophilic additives are measured before coating. Thus, the film thickness can be calculated by the second method.

In the present invention, the preferred thickness of the photographic layer structure is 9.0 μm or less, more preferably 8.0 μm.
m, most preferably 7.0 μm or less and 3.5 μm or more.

In the present invention, the hydrophobic photographic material is
An oil-soluble component excluding the dye-forming coupler, wherein the oil-soluble component is a lipophilic component remaining in the photosensitive material after processing. Specifically, a dye-forming coupler, a high-boiling organic solvent, a color mixing inhibitor,
UV absorbers, lipophilic additives, lipophilic polymers or polymer latexes, matting agents, slipping agents, etc., which are usually added to photographic constituent layers as lipophilic fine particles. Therefore, water-soluble dyes, hardeners, water-soluble additives, silver halide emulsions and the like do not fall under oil-soluble components. Usually, a surfactant is used when preparing the lipophilic fine particles, but the surfactant is not treated as an oil-soluble component in the present invention.

In the present invention, the total amount of the oil-soluble components is preferably 4.5 g / m ² or less, more preferably 4.0 g / m ^2.
m ² or less, most preferably 3.8 g / m ² or less 3.0 g /
m ² or more. In the present invention, the value obtained by dividing the mass (g / m ² ) of the hydrophobic photographic material contained in the layer containing the dye-forming coupler by the mass (g / m ² ) of the dye-forming coupler is 4.5 or less. And more preferably 3.
5 or less, and most preferably 3.0 or less.

In the present invention, the ratio of the oil-soluble component to the hydrophilic binder in the constitution of the photographic layer can be arbitrarily set. The preferred ratio in the photographic layer constitution other than the protective layer is 0.05 to 1.50 by mass, more preferably 0.10 to 1.4.
0, most preferably 0.20 to 1.30. By optimizing the ratio of each layer, the film strength, scratch resistance, and curl characteristics can be adjusted.

The silver halide emulsion used in the color photographic light-sensitive material of the present invention contains at least one of the silver halide emulsion layers containing the silver halide emulsion defined in the present invention. Of these, it is preferable to use the silver halide emulsion specified in the present invention in the blue-sensitive emulsion layer. As other silver halide used in the color light-sensitive material of the present invention, silver chloride, silver bromide, silver (iodo) chlorobromide, silver iodobromide, silver iodochloride and the like can be used. For the purpose of processing, the silver chloride content is 90 mol% or more, further 95 mol% or more,
In particular, it is preferable to use a high silver chloride emulsion of 98 mol% or more.
Further, it preferably has a silver bromide localized phase. When tabular grains having a {100} plane or a {111} plane are used, the [B / AgX] ratio can be increased, and the color development can be accelerated, and the color mixture during processing can be reduced. preferable.

The light-sensitive material according to the present invention has a dye capable of being decolorized by a treatment described in EP-A-337,490 A2, pp. 27-76, in a hydrophilic colloid layer for the purpose of improving sharpness and the like in an image. (An oxonol-based dye) so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more, or a divalent or tetravalent alcohol (for example, trimethylolethane) ) Is preferably contained in an amount of 12% by mass or more (more preferably 14% by mass or more).

The silver halide photographic light-sensitive material of the present invention includes:
In addition, conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the transmission type support include transmission films such as cellulose nitrate film and polyethylene terephthalate, as well as 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG).
And a polyester of NDCA, terephthalic acid and EG, etc., provided with an information recording layer such as a magnetic layer is preferably used. The reflective support is particularly laminated with a plurality of polyethylene layers and polyester layers,
A reflective support containing a white pigment such as titanium oxide in at least one such water-resistant resin layer (laminate layer) is preferred.

It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, benzoxazole type, coumarin type,
A pyrazoline-based fluorescent whitening agent can be used, and a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by mass, more preferably 0.001 to 0.5% by mass, based on the resin. The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

The above-mentioned reflection type support comprises a silver halide emulsion,
Further, different metal ion species doped in silver halide grains, storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization (sensitizer), spectral sensitization (spectral sensitizer), Cyan, magenta, yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (anti-stain and anti-fading agents), dyes (colored layers), gelatin species, layer composition of photosensitive material, coating pH of photosensitive material, etc. As described above, those described in the patents of Tables 1 and 2 can be preferably applied to the present invention.

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[Table 1]

[0090]

[Table 2]

The cyan, magenta and yellow couplers used in combination in the present invention are described in
No. 2-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6, JP-A-2-33144, page 3, upper right column, line 14 to page 18, upper left column, last line and page 30, upper right Column 6th line to page 35, lower right column, line 11 or EP 355,660A
No. 2, page 4, lines 15-27, page 5, lines 30-28
Couplers described in the last line of the page, the 29th to 31st lines of the 45th page, the 23rd line of the 47th page to the 50th line of the 63rd page, JP-A-8-122984 and JP-A-9-222704 are also useful.
As the cyan coupler, a pyrrolotriazole coupler is preferably used.
Particularly preferred are couplers represented by the general formula (I) or (II) of the above-mentioned No. 3, couplers represented by the general formula (I) of JP-A-6-347960, and exemplified couplers described in these patents.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, a polymer redox compound described in JP-A-5-333501, WO98 / 3376
0, U.S. Pat. No. 4,923,787, etc .; phenidone and hydrazine compounds;
No. 10-282615, German Patent No. 196291
For example, a white coupler described in No. 42A1 can be used. In particular, when increasing the pH of the developer to speed up the development, German Patent No. 1918186786A1
No. 19806846A1, European Patent No. 839,
No. 623A1, No. 842,975A1, French Patent No. 2
It is also preferable to use a redox compound described in, for example, 760460A1.

In the present invention, as an ultraviolet absorber,
It is preferable to use an ultraviolet absorber having a high molar extinction coefficient. Examples of such a compound include compounds having a triazine skeleton.
No. 55-152776, JP-A-5-1970074
Nos. 5-232630, 5-307232, 6-211813, 8-53427, and 8-23
No. 4364, No. 8-239368, No. 9-31067
No., No. 10-115598, No. 10-147577
No. 10-182621, Tokuyohei 8-501291
No. 711,804A and German Patent No. 19
Preferred are those described in U.S. Pat.

As the antibacterial and antifungal agents that can be used in the present invention, those described in JP-A-63-271247 are useful.
Gelatin is preferred as the hydrophilic colloid used in the photographic layer constituting the photosensitive material, and particularly, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably at most 5 ppm, more preferably at most 3 ppm. .
The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a normal negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. For the cathode ray tube used for image exposure, various luminous bodies that emit light in a spectral region are used as necessary. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

In the case where the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode ray tube also has a phosphor which emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, the cathode ray tube is exposed. The image signal of a plurality of colors may be input to the display unit to emit light from the display screen. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
In general, plane-sequential exposure is preferable for high image quality because a cathode ray tube with high resolution can be used.

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

When such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the photosensitive material of the present invention depends on the scanning used.
It can be set arbitrarily according to the wavelength of the exposure light source.
Solid-state laser using semiconductor laser as excitation light source or
Is obtained by combining a semiconductor laser and a nonlinear optical crystal.
SHG light source can halve laser oscillation wavelength
Therefore, blue light and green light can be obtained. Therefore, photosensitive material
The spectral sensitivity maximum is held in the normal three wavelength ranges of blue, green and red.
It is possible to add. In such scanning exposure
The exposure time is based on the pixel when the pixel density is 400 dpi.
If the size is defined as the exposure time, the preferred exposure
10 for time ^-FourSeconds or less, more preferably 10^-6Seconds
Below.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table. Further, for processing the light-sensitive material of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5 upper left column The processing materials and processing methods described in the 17th line to the 20th line on the lower right column on page 18 can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

The method of developing the light-sensitive material of the present invention after exposure is a method in which development processing is performed in at least a step including color development and bleaching (bleaching or fixing), and is preferably color development, bleach-fixing (bleaching and bleaching). Fixing) followed by washing in the order of water washing, but the conventional method of developing with a developer containing an alkali agent and a developing agent, an activator solution such as an alkali solution containing a developing agent in a photosensitive material and containing no developing agent In addition to a wet method such as a method of developing with a developing method, a thermal developing method without using a processing liquid can be used. In particular,
Since the activator method does not contain a developing agent in the processing solution, it is easy to manage and handle the processing solution, and the load is small when processing the waste solution, and is a preferable method from the viewpoint of environmental protection. In the activator method, examples of a developing agent or a precursor thereof incorporated in a photosensitive material include, for example, JP-A-8-234388, JP-A-9-152686, and JP-A-9-152686.
-152693, 9-211814, 9-16
The hydrazine type compounds described in No. 0193 are preferred.

A developing method in which the amount of silver applied to the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, Japanese Patent Application Laid-Open
An image forming method using an activator solution containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152699 is preferably used. In the activator method, after processing with an activator solution, usually a desilvering process is performed, but in an image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted, and a simple method such as washing with water or stabilizing process can be performed. Further, in a method in which image information is read from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photography is used.

As the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention, known materials and processing methods can be used. Preferably, Research Disclosure Item 36
544 (September 1994), pages 536 to 541, and JP-A-8-234388 can be used.

In the present invention, the term "color development time" means the time from when the photosensitive material enters the color developing solution to when it enters the bleach-fixing solution in the next processing step. For example, when processing is performed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developing solution (so-called submerged time) and the time when the photosensitive material leaves the color developing solution and is bleach-fixed in the next processing step The sum of the time during which it is transported in the air toward the bath (so-called air time) is referred to as the color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution to when it enters the next washing or stabilizing bath. The term “washing or stabilizing time” refers to the time during which the photosensitive material is in the washing or stabilizing solution and is in the solution for the drying step (so-called submerged time).
Say. In the rapid processing aimed at by the present invention, the color development time is preferably 30 seconds or less, more preferably 20 seconds or less.
Seconds or less, most preferably 15 seconds or less and 6 seconds or more. Similarly, the bleach-fix time is preferably 30 seconds or less, more preferably 20 seconds or less, and most preferably 15 seconds or less and 6 seconds or more. The washing or stabilization time is preferably 40 minutes.
Seconds or less, more preferably 30 seconds or less, and most preferably 2 seconds or less.
It is less than 0 seconds and more than 6 seconds.

The drying method according to the present invention may be any method known in the art for rapid drying of a color photographic light-sensitive material. It is preferable that drying can be performed within seconds, most preferably 5 seconds to 10 seconds.
As a drying method, either a contact heating method or a hot air blowing method may be used, but the combination of the contact heating method and the hot air blowing method enables quick drying compared to the case of using either method Is preferable. A further preferred embodiment of the present invention relating to the drying method is a method in which the photosensitive material is contact-heated by a heat roller and then blown and dried by warm air blown from the perforated plate or the nozzle group toward the photosensitive material. In the drying section, it is preferable that the mass velocity of the warm air blown per unit area of the heat receiving area of the photosensitive material is 1000 kg / m ² · hr or more. Further, it is preferable that the shape of the blowing outlet is a shape having a small pressure loss, and examples thereof include FIGS. 7 to 15 described in JP-A-9-33998. The light-sensitive material of the present invention has rapid processing properties and high sensitivity,
Since the pressure fogging is small and suitable not only for surface exposure but also especially for high illuminance scanning exposure, a good image can be obtained in the above color development time.

[0105]

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

Example 1 (Preparation of emulsion BLA) (Preparation of silver chloroiodobromide {111} tabular grain emulsion containing 91% of silver chloride) Sodium chloride was dissolved in 1.2 liters of water.
0 g and 2.8 g of inert gelatin were added, and 60 ml of an aqueous silver nitrate solution was stirred into a container kept at 33 ° C.
(9 g of silver nitrate) and 60 ml of an aqueous sodium chloride solution (3.2 g of sodium chloride) were added in one minute by a double jet method. One minute after the completion of the addition, 1 mmol of the crystal habit controlling agent 1 was added. One minute later, 3.0 g of sodium chloride was added. During the next 25 minutes, the temperature of the reaction vessel was raised to 60 ° C. After aging at 60 ° C. for 16 minutes, 290 g of a 10% aqueous solution of phthalated gelatin and 0.8 mmol of crystal habit control agent 1 were added. Thereafter, 754 ml of an aqueous silver nitrate solution (113
g) and 768 ml of an aqueous sodium chloride solution (41.3 g of sodium chloride) were added at an accelerated flow rate over 28 minutes. During this time, 30 ml of a 0.25 M aqueous sodium chloride solution containing 0.48 g of potassium iodide and 11 mg of yellow blood salt was added over 21 to 28 minutes. Then 75 ° C
, And 8 mol% of an aqueous solution of silver nitrate and 8 mol% of potassium bromide having a concentration of 2% were simultaneously added slowly. At this time, an aqueous solution of potassium iridium (IV) hexachloride was added in an amount of 3 × 10 ⁻⁷ mol per mol of the total silver. Further, the blue-sensitive spectral sensitizing dyes A, B, and C were used in a total amount of 8 per mole of silver.
× 10 ^-4 mol, and 12 g of sodium dodecylbenzenesulfonate (DBS) was added.
Left for 0 minutes.

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The precipitate was washed by settling at 40 ° C. and desalted. Further, 100 g of lime-processed gelatin was added, and pH6.
2, adjusted to pAg 7.0. Thereafter, a mixed solution of sodium thiosulfonate and sodium sulfinate (4 × 10 ⁻⁴ and 1 × 10 ⁻⁴ moles per mole of silver, respectively)
Was optimally chemically sensitized using chloroauric acid and 1- (3-methylureidophenyl) -5-mercaptotetrazole. From the electron micrograph, the particle shape is a tabular grain having a principal plane of {111} plane, a projected area equivalent diameter of 0.82 μm, a thickness of 0.13 μm, an aspect ratio of 6, a sphere equivalent diameter of 0.5 μm, and a cube. When converted to a considerable side length, it is 0.
40 μm and coefficient of variation 0.25. (0.4 mol% iodine content)

(Preparation of emulsion BLB) (Preparation of silver chloroiodide {111} tabular grain emulsion having a silver chloride content of 97%) In emulsion BLA, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were added at 75 ° C. Each 8 mol% was reduced to 1 mol%, and after the completion of 75%, 3 × 10 ⁻⁷ mol of an aqueous solution of potassium iridium (IV) hexachloride was added to 1 mol of the total silver. Other than that, it carried out similarly to emulsion BLA and obtained emulsion BLB. From the electron micrograph,
The emulsion BLB is a tabular grain having a principal plane of {111} plane, a projected area equivalent diameter, a thickness, an aspect ratio, a sphere equivalent diameter, a value converted into a cubic equivalent side length, and a variation coefficient. Was similar to emulsion BLA.

After a corona discharge treatment was applied to the surface of the support having both sides of the paper coated with a polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. Were sequentially coated to prepare a sample (101) of a silver halide color photographic light-sensitive material having the following layer structure. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Coating Solution for First Layer 57 g of yellow coupler (ExY), color image stabilizer (Cp
d-1) 7 g, color image stabilizer (Cpd-2) 4 g, color image stabilizer (Cpd-3) 7 g, color image stabilizer (Cpd-8) 2
g of solvent (Solv-1) 21 g and ethyl acetate 80 m
1 g of a 23.5% by weight aqueous gelatin solution containing 4 g of sodium dodecylbenzenesulfonate.
In 0 g, the mixture was emulsified and dispersed by a high-speed stirring emulsifier (dissolver), and water was added to prepare 900 g of emulsified dispersion A. On the other hand, the emulsified dispersion A and the emulsion BLA were mixed and dissolved to prepare a coating solution for the first layer so as to have the following composition. The emulsion coating amount indicates a coating amount in terms of silver amount.

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

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The silver and chlorobromide emulsions of the green and red-sensitive emulsion layers include:
The following spectral sensitizing dyes were used respectively. Green-sensitive emulsion layer

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(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 for large emulsions ^-FourMol, small size
3.6 × 10 for emulsion^-FourMol and sensitizing dye E
Per mole of silver halide and for large emulsions
4.0 × 10^-Five7.0 × for mole, small size emulsions
10^-FiveMole of sensitizing dye F per mole of silver halide.
2.0 × 10^-FourMol, small sa
2.8 × 10^-FourMole was added. ) Red-sensitive emulsion layer

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(The sensitizing dyes G and H were used in an amount of 8.0 × 1 for the large size emulsion per mol of silver halide, respectively)
0 ^-5 mol, it was added 10.7 × 10 ^-5 mol to the small size emulsion. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10 ⁻³ mol per mol of silver halide. )

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In addition, the green-sensitive emulsion layer and the red-sensitive emulsion layer
On the other hand, 1- (3-methylureidophenyl) -5-mer
Captotetrazole was added in an amount of 1 mol
3.3 × 10^-FourMol, 1.0 × 10^-3Moles and 5.
9 × 10^-FourMole was added. In addition, the second layer, fourth layer,
0.2 mg / m for each of the sixth and seventh layers ^Two,
0.2mg / m^Two, 0.6 mg / m^Two0.1 mg / m^Two
Was added so that In addition, a blue-sensitive emulsion layer and a green-sensitive emulsion layer
4-hydroxy-6-methyl-1,
3,3a, 7-tetrazaindene is replaced by halogen
1 × 10 per mole of silver halide^-FourMole, 2 × 10^-FourMoles
Added. Also, methacrylic acid and acrylic were used in the red-sensitive emulsion layer.
Butyl acid copolymer latex (mass ratio 1: 1, average
(200,000 to 400,000)) at 0.05 g / m^Two
Was added. The second, fourth and sixth layers have catechols
-3,5-disulfonate disodium each in 6
mg / m^Two, 6mg / m^Two, 18mg / m^TwoSo that
Was added. Also, to prevent irradiation,
(The number in parentheses indicates the coating amount).

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(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ;
Content 16% by mass, ZnO; content 4% by mass], a fluorescent whitening agent (4,4'-bis (5-methylbenzooxazolyl) stilbene, content 0.03% by mass), bluish dye ( Ultramarine blue)] First layer (blue-sensitive emulsion layer) Emulsion BLA (Sample 101) 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stability Agent (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21

Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B ′ having an average grain size of 0.45 μm and small-size emulsion B ″ having an average grain size of 0.35 μm ( The variation coefficients of the grain size distribution are 0.10 and 0.08, respectively. 0.4 mol% of silver bromide is locally applied to a part of the grain surface based on silver chloride in each size emulsion. 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-A) 0.14 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd- 4) 0.002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.11 Solvent (Solv-4) 0.22 Solvent (Solv-5) 0.20

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention layer (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 5: 5 mixture of large-size emulsion C ′ having an average grain size of 0.40 μm and small-size emulsion C ″ having an average grain size of 0.30 μm ( The variation coefficients of the grain size distributions are 0.09 and 0.11, respectively. For each size emulsion, 0.8 mol% of silver bromide is localized on a part of the surface of the silver chloride-based grain. 0.12 Gelatin 1.11 Cyan coupler (ExC-2) 0.13 Cyan coupler (ExC-3) 0.03 Color image stabilizer (Cpd-1) 0.05 Color image stabilizer (Cpd) -6) 0.06 Color image stabilizer (Cpd-7) 0.02 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-14) ) 0.01 Color image stabilizer (Cpd-15) 0.12 Color image stabilizer (Cpd -16) 0.03 Color image stabilizer (Cpd-17) 0.09 Color image stabilizer (Cpd-18) 0.07 Solvent (Solv-5) 0.15 Solvent (Solv-8) 0.05

Sixth layer (ultraviolet absorbing layer) Gelatin 0.46 Ultraviolet absorbing agent (UV-B) 0.45 Compound (S1-4) 0.0015 Solvent (Solv-7) 0.25 Seventh layer (protective layer) ) Gelatin 1.00 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

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Similarly, a sample (201) was prepared in which the emulsion BLA of the sample (101) was changed to the emulsion BLB. In addition, 4 × 10 ⁻⁶ mol / m ^{2 of the} exemplified compounds shown in Table 3 was added to the second layer of Samples (101) and (201) to prepare Samples shown in Table 3.

The following tests were conducted to examine the photographic characteristics of these samples. Test 1 Evaluation of sensitometry and resistance to long-term development of each sample To each coated sample, a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.) was used to give gradation exposure for sensitometry. Was. Exposure was performed for 10 seconds at low illuminance with an SP-1 filter attached. After the exposure, the following color development processing A1 and processing A2 were performed.

The processing steps will be described below. [Processing A1] The photosensitive material 101 was processed into a roll having a width of 127 mm, imagewise exposed using a minilab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., and then replenished twice in the color developing tank in the following processing steps. Until this was done, continuous processing (running test) was performed.
This treatment using the running liquid was designated as treatment A1. Further, the same processing as processing A1 was performed except that the color development processing was performed for 120 seconds. This was designated as process A2. Processing process Temperature Time Replenishment amount ^* Color development 38.5 ° C 45 seconds 45 ml Bleaching and fixing 38.0 ° C 45 seconds 35 ml Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds - rinse (3) ** 38.0 ℃ 20 seconds - rinse (4) ** 38.0 ℃ 30 seconds 121 ml * phosphorus replenishment rate ** Fuji Photo Film Co., Ltd. rinse cleaning system RC50D per photosensitive material 1 m ² The rinsing liquid is taken out of the rinse (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethylpolysiloxane-based surfactant 0.1 g 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8 g 8 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0 g 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g-odor Potassium iodide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescence 2.5 g 5.0 g Brightener (Hakor FWA-SF / Showa Chemical Co., Ltd.) Sodium sulfite 0.1 g 0.1 g Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 8.5 g 11.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 15.7 g potassium carbonate 3g 26.3g Add water 1000ml 1000ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 700 ml 600 ml iron (III) ammonium ethylenediaminetetraacetate 47.0 g 94.0 g 1.4 g 2.8 g m-carboxybenzenesulfinic acid 8.3 g 16.5 g nitric acid (67%) 16.5 g 33.0 g imidazole 14.6 g 29.2 g ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml ammonium sulfite 16.0 g 32.0 g ammonium bisulfite 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C./acetic acid and ammonia) 6.0 6.0

[Rinse solution] [Tank solution] [Replenisher] 0.02 g 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity of 5 μS / cm or less) 1000 ml 1000 ml pH 6.5 6.5

The yellow color density of each of the processed samples was measured, and the sensitivity of the emulsions BLA and BLB in each sample to 10-second exposure and low illuminance was determined. The sensitivity is 1.0 from the lowest color density.
It was defined as the reciprocal of the exposure amount that gives a high color density, and was expressed as a relative value when the developed sensitivity of the sample (101) was taken as 100. Further, the gradation was obtained from the slope of the straight line between the sensitivity point and the sensitivity point at the density of 1.5. Further, the yellow color density of the unexposed portion was measured, and the fogging was evaluated.

Test 2 Evaluation of Resistance of Each Sample to Bleaching-Fixing Solution The processing was performed in the same manner as in the processing A1, except that the bleach-fixing solution was added to the developing solution in an amount of 0.5 ml per liter of the developing solution. . This is referred to as process A3. Processing A1 and processing A3
Was determined. In this case, the sensitivity is defined as the reciprocal of the exposure amount that gives a color density 1.5 higher than the minimum color density, and the sensitivity obtained by subjecting the sample (101) to A1 processing to 100 is used.
And expressed as a relative value. The results are summarized in Table 3.

[0146]

[Table 3]

From Table 3, it can be seen that # 11 having a silver chloride content of 91% was # 11.
It can be seen that in the emulsion BLA having the 1｝ plane as the main plane, the addition of the exemplified compound does not function to suppress the increase in fogging due to long-term development (Test 1). It is also found that there is no function to suppress the increase in sensitivity due to the mixing of the bleach-fix solution (Test 2).
On the other hand, in the emulsion BLB having a {111} plane as the main plane having a silver chloride content of 97%, the increase in fogging due to long-term development was significantly suppressed by the addition of the exemplified compound (Test 1), and bleach-fixing was also performed. The increase in sensitivity due to mixing with the liquid is also remarkably suppressed, and the hardening tends to be small (Test 2). That is, in a high silver chloride {111} tabular emulsion having a silver chloride content of 97%, unlike the case of a silver chloride content of 91%, the resistance to long-term development is improved by the addition of the exemplified compound, and bleach-fixing. It has been clarified that the resistance to liquid mixing is also improved. When the silver chloride content is 91%, silver chloride is 97%.
%, It is preferable that the silver chloride content is high as defined in the present invention.

Example 2 The following BLC was used instead of the emulsion BLA used in Example 1, and the following BLD was used instead of BLB. Samples were prepared, and tests 1 and 2 were performed in the same manner as in Example 1. In this example and in Examples 3 and 4 described below, the same symbols as those in Example 1 represent the same emulsion, compound and treatment as used in Example 1 unless otherwise specified.

(Preparation of emulsion BLC) (Preparation of silver chlorobromide cubic grain emulsion having a silver chloride content of 92%) A silver chlorobromide cubic emulsion containing 92 mol% of silver chloride was prepared by a control double jet method. Average particle size 0.72μ
m was obtained. Thereafter, desalting and washing were performed by a usual flocculation method, and a gelatin aqueous solution was newly added and dissolved. Sensitizing dyes A and B were added to the emulsion as in the case of emulsion BLA of Example 1, and sodium benzenethiosulfonate and sodium benzenesulfinate, chloroauric acid, 1- (3-methylureidophenyl) -5 were added. Post-ripening with mercaptotetrazole. (Preparation of emulsion BLD) (Preparation of silver chlorobromide cubic grain emulsion having a silver chloride content of 98%) A silver chlorobromide cubic emulsion containing 98 mol% of silver chloride was prepared by a control double jet method, and the average grain size was prepared. 0.72μ
m was obtained. Thereafter, desalting and washing were performed by a usual flocculation method, and a gelatin aqueous solution was newly added and dissolved. Sensitizing dyes A and B were added to the emulsion as in the case of emulsion BLA of Example 1, and sodium benzenethiosulfonate and sodium benzenesulfinate, chloroauric acid, 1- (3-methylureidophenyl) -5 were added. Post-ripening with mercaptotetrazole.

Table 4 summarizes the results of tests 1 and 2 performed in the same manner as in Example 1. As shown in Table 4, in the cubic emulsion BLC having a silver chloride content of 92%, the addition of the exemplified compound does not suppress the increase in fogging due to long-term development (Test 1), but suppresses the increase in sensitivity due to the mixing of the bleach-fix solution. (Test 2). In contrast, a silver chloride content of 98
% Of the cubic emulsion BLD, the addition of the exemplified compound suppresses the increase in fogging due to long-term development (Test 1), and also suppresses the increase in sensitivity due to mixing with the bleach-fix solution (Test 2). That is, in the high silver chloride cubic emulsion having a silver chloride content of 98%, unlike the case of the silver chloride content of 92%, it was clarified that the exemplified compounds particularly improved the resistance to long-term development.

Here, Example 1 ({111} tabular emulsion)
In comparison with Example 2 (cubic emulsion), the cubic emulsion has the effect of improving the long-term development resistance by the addition of the compound defined in the present invention, whereas the {111} tabular emulsion has the effect defined in the present invention. It was found that the addition of the compound having both the bleach-fixing solution and the effect of improving the resistance to long-term development.

[0152]

[Table 4]

Example 3 A thinned sample was prepared by changing the layer constitution as follows.
Tests 1 and 2 of Example 1 were carried out in the same manner as described above except that the samples were subjected to color development by the following processes B1, B2 and B3 instead of the processes A1, A2 and A3. The layer configuration is shown in Sample (501). The sample (60
1) is a sample (501) in which emulsion BLA is changed to emulsion BLB. In addition, as in Example 1, 4 × 10 ⁻⁶ mol / m ^{2 of} the exemplified compound was added to the second layer of each of the samples (501) and (601) to prepare samples. As a result, similarly to the result of Example 1, in each of the samples of the present invention, the resistance to long-term development and the resistance to mixing with the bleach-fix solution were improved. From these results, the effect of the present invention was confirmed even in ultra-rapid processing of a thinned sample.

Preparation of Sample 501 First layer (blue-sensitive emulsion layer) Emulsion BLA 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer ( Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21

Second layer (color mixture prevention layer) Gelatin 0.60 Color mixture prevention agent (Cpd-19) 0.09 Color image stabilizer (Cpd-5) 0.007 Color image stabilizer (Cpd-7) 0.007 UV absorber (UV-C) 0.05 Solvent (Solv-5) 0.11

Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion B (the same emulsion as in sample 201) 0.14 gelatin 0.73 magenta coupler (ExM) 0.15 ultraviolet absorber (UV-A) 05 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-7) 0.008 Color image stabilizer (Cpd-8) 0.07 Color image stabilizer (Cpd-9) 0.03 colors Image stabilizer (Cpd-10) 0.009 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-4) 0.06 Solvent (Solv-4) 0.11 Solvent (Solv-5) 0.06

Fourth layer (color mixture prevention layer) Gelatin 0.48 Color mixture prevention layer (Cpd-4) 0.07 Color image stabilizer (Cpd-5) 0.006 Color image stabilizer (Cpd-7) 0.006 UV absorber (UV-C) 0.04 Solvent (Solv-5) 0.09

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C (the same emulsion as in sample 201) 0.12 gelatin 0.59 cyan coupler (ExC-2) 0.13 cyan coupler (ExC-3) 0 0.03 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-15) 0.19 Color image stabilizer (Cpd-18) 0.04 UV absorber (UV-7) 0.02 Solvent (Solv-5) 0.09

Sixth layer (ultraviolet absorbing layer) Gelatin 0.32 Ultraviolet absorbing agent (UV-C) 0.42 Solvent (Solv-7) 0.08 Seventh layer (protecting layer) Gelatin 0.70 Acrylic of polyvinyl alcohol Modified copolymer (degree of modification 17%) 0.04 Liquid paraffin 0.01 Surfactant (Cpd-13) 0.01 Polydimethylsiloxane 0.01 Silicon dioxide 0.003

Each of the produced samples was exposed in the same manner as in Tests 1 and 2 of Example 1, and the color development was performed by ultra-rapid processing in accordance with the following development processing B1. In addition, the same processing as the processing B1 was performed except that the color development processing was performed for 30 seconds. This was designated as process B2. The processing was performed in the same manner as the processing B1, except that the bleach-fixing solution was added to the developing solution in an amount of 0.5 ml per liter of the developing solution. This is processed B3
And

[Processing B1] The photosensitive material 501 was converted to 127
After processing into a roll having a width of mm and imagewise exposure, continuous processing (running test) was performed until the color developing tank capacity was replenished twice in the following processing step. The processing liquid using this running liquid was referred to as processing B1. Processing is mini-lab printer processor PP manufactured by Fuji Photo Film Co., Ltd.
1258AR was used.

Processing step Temperature Time Replenishment amount * Color development 45.0 ° C. 12 seconds 45 ml Bleach-fix 40.0 ° C. 12 seconds 35 ml Rinse (1) 40.0 ° C. 4 seconds-Rinse (2) 40.0 ° C. 4 sec - rinse (3) ** 40.0 ℃ 4 seconds - rinsing (4) ** 40.0 ℃ 4 seconds 121 ml * photosensitive material 1 m ² per replenishment amount ** Fuji Photo Film Co., Ltd. rinse cleaning system RC50D Install in rinse (3), take out rinse liquid from rinse (3), and send to reverse osmosis membrane module (RC50D) by pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethylpolysiloxane-based surfactant 0.1 g 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8 g 8 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0 g 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g-odor Potassium iodide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescence 2.5 g 5.0 g Brightener (Hakor FWA-SF / Showa Chemical Co., Ltd.) Sodium sulfite 0.1 g 0.1 g Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 8.5 g 11.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 10.0 g 22.0 g potassium carbonate 26. 3g 26.3g Add water 1000ml 1000ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 700 ml 600 ml iron (III) ammonium ethylenediaminetetraacetate 75.0 g 150.0 g 1.4 g 2.8 g ethylenediaminetetraacetic acid m-carboxybenzenesulfinic acid 8.3 g 16.5 g nitric acid (67%) 16.5 g 33.0 g imidazole 14.6 g 29.2 g ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml ammonium sulfite 16.0 g 32.0 g metabisulfite Potassium 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C / acetic acid and ammonia) 5.5 5.2

[Rinse liquid] [Tank liquid] [Replenisher] Dechlorinated sodium isocyanurate 0.02 g 0.02 g Deionized water (conductivity of 5 μS / cm or less) 1000 ml 1000 ml pH 6.0

Example 4 Using the sample used in Example 1, an image was formed by laser scanning exposure. As a laser light source, a YAG solid-state laser (oscillation wavelength 946) using a semiconductor laser GaAlAs (oscillation wavelength 808.5 nm) as an excitation light source is used.
nm) of SH of LiNbO ₃ having inversion domain structure
A wavelength of 473 nm converted by a G crystal and taken out, and a semiconductor laser GaAlAs (oscillation wavelength of 808.7 n)
m) as an excitation light source using a YVO ₄ solid-state laser (oscillation wavelength 1064 nm) as LiNb having an inversion domain structure.
532 wavelength-converted and extracted by O ₃ SHG crystal
nm and AlGaInP (oscillation wavelength: about 680 nm: type No. LN9R20 manufactured by Matsushita Electric Industrial Co., Ltd.). The laser light of each of the three colors was moved in a direction perpendicular to the scanning direction by a polygon mirror, so that the sample could be sequentially scanned and exposed. Fluctuations in light intensity due to the temperature of the semiconductor laser are suppressed by using a Peltier element to keep the temperature constant. Effective beam diameter is 80 μm
The scanning pitch was 42.3 μm (600 dpi), and the average exposure time per pixel was 1.7 × 10 ⁻⁷ seconds. After exposure, the samples were processed by the same color developing process B1 as used in Example 3, and all the samples were
It showed high sensitivity and was also suitable for image formation using laser scanning exposure.

[0167]

The light-sensitive material of the present invention is excellent in that there is little change in gradation due to mixing of a bleach-fixing solution into a color developing solution, and there is little increase in fog when the developing time fluctuates and the developing time is extended. It works. At the same time, the addition of the compound specified in the present invention does not adversely affect basic photographic performance such as photographic sensitivity, fog and gradation. Furthermore, it is excellent in the above-mentioned points even when performing rapid processing, and has suitability for high-illuminance exposure.

Claims (3)

[Claims] 1. A composition comprising at least one compound selected from the group consisting of a dimercaptopyrimidine compound, a dimercapto-1,3,5-triazine compound and a dimercapto-1,2,4-triazine compound. The silver halide grains of the silver halide emulsion layer have a silver chloride content of 95 mol% or more, and 50% or more of the projected area is # 11.
A silver halide color photographic light-sensitive material comprising tabular grains having a main plane of 1 or 100 and a mean aspect ratio of 2.0 or more. 2. A dimercaptopyrimidine compound, a dimercapto-1,3,5-triazine compound or a dimercapto-1,2,4-triazine compound represented by the following general formula (1): A silver halide color photographic light-sensitive material containing a compound, wherein the silver halide grains in at least one silver halide emulsion layer are cubic grains having a silver chloride content of 95 mol% or more. General formula (1) In the formula, R ₁ represents a —SM group, a hydrogen atom, a substituted alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carboxy group,
Represents a sulfo group, and R ₂ and R ₃ each independently represent a hydrogen atom or a substituent. However, at least one of R ₁ to R ₃ is a —SM group, and R ₁ and R ₂ are not simultaneously hydrogen atoms. M represents a hydrogen atom or a cation. Note that a plurality of Ms may be the same or different from each other. 3. The pyrimidine or triazine compound is at least one compound selected from a pyrimidine compound represented by the following general formula (1A) and a triazine compound represented by the following general formula (2). The silver halide color photographic light-sensitive material according to claim 1 or 2, wherein General formula (1A) In the formula, R ₁ and R ₃ each independently represent a —SM group, a hydrogen atom, a substituted alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group or a carboxy group. However, at least one of R ₁ and R ₃ represents a —SM group, and R ₁ and R ₂ are not simultaneously hydrogen atoms. R ₂
Represents a hydrogen atom, an alkyl group, an amino group, or a halogen atom. Here, at least one of R ₁ to R ₃ is a water-soluble group or a group having a water-soluble group. M represents a hydrogen atom or a cation. Note that a plurality of Ms may be the same or different from each other. General formula (2) In the formula, R ₄ represents a —SM group, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group or a carboxy group. Here, R ₄ is a water-soluble group or a group having a water-soluble group. M represents a hydrogen atom or a cation. Note that a plurality of Ms may be the same or different from each other.