JP2005121744A - Silver halide color photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photosensitive material easy to handle and superior in safelight safety, without lowering the originally required sensitivity for a wavelength band. <P>SOLUTION: The silver halide color photosensitive material has on a transparent support at least one each of yellow, cyan and magenta developing photosensitive silver halide emulsion layers and at least one non-photosensitive hydrophilic colloidal layer, and contains at least two dyes selected from an oxonol water-soluble dye, an indigo water-soluble dye and a phthalocyanine water-soluble dye in one of the silver halide emulsion layers or in the non-photosensitive hydrophilic colloidal layer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a silver halide color photographic light-sensitive material having improved workability and processing stability, and more particularly to a silver halide color photographic light-sensitive material for movies.

  Movie, which is an application of silver halide photography, is a method of obtaining a moving image by sequentially projecting 24 dense still images per second, and has an overwhelming image quality compared to other methods of reproducing moving images. Have. However, the recent rapid development of electronic technology and information processing technology suggests simpler video playback means with image quality close to that of movies such as projectors using DMD devices from Texas Instruments and ILA projectors from Hughes-JVC. It came to be able to do it. Accordingly, there is a need for movies to be provided with simplicity while maintaining the original high image quality, in particular, to simplify and shorten the time required for work at a developing station such as exposure and development.

  One of the factors that make handling of silver halide photographic light-sensitive materials difficult is that the material before development processing must be handled in a dark place. In the case of a photographic silver halide photographic material that must have the same characteristics as human vision, it must be handled in the dark in principle, but the information recorded on the photographic silver halide photographic material is Originally, in the case of a silver halide photographic light-sensitive material for printing for producing an ornamental image, it is not always necessary to handle it in a dark place. Many of the commercially available silver halide photographic light-sensitive materials for printing are capable of working under light in the wavelength region (hereinafter referred to as safe light) by reducing the sensitivity in a specific wavelength region. . For example, in the case of a silver halide photographic light-sensitive material for movie projection (Fuji Color Positive Film F-CP (trade name) manufactured by Fuji Photo Film Co., Ltd.), the photosensitive wavelength between the green light-sensitive emulsion layer and the red light-sensitive emulsion layer. The sensitivity to light in the vicinity of a wavelength of 590 nm is reduced, and a light source (for example, a low-pressure sodium lamp) that emits light in the vicinity can be used as a safe light. However, the red-sensitive emulsion layer has a small sensitivity in this wavelength region. Therefore, when the brightness of the safelight is too bright, or when exposed to the safelight for a long time, cyan fogging occurs due to the exposure of the red photosensitive emulsion layer, and an unfavorable image can be obtained. Therefore, from the viewpoint of workability, a material that hardly causes cyan fogging even when exposed to a brighter light source or exposed to a safelight for a longer time, that is, a silver halide photographic light-sensitive material having a lower sensitivity in the safelight wavelength range. It has been demanded.

As means for improving the workability in the dark (hereinafter referred to as safelight safety), a colorant having absorption near the target wavelength may be introduced into the photosensitive material. The colorant used for such purpose is required to satisfy the following performance. That is, there are the following three points.
(1) Have appropriate spectral absorption according to the purpose of use. That is, it has absorption in a target wavelength range, and the photosensitive material does not have absorption in a wavelength range that is originally required (no sensitivity deterioration).
(2) The silver halide emulsion layer in the light-sensitive material should not be chemically adversely affected, for example, no sensitivity change or fogging.
(3) In order not to leave harmful coloring on the photographic light-sensitive material, it must be completely decolorized in the photographic processing process or easily eluted from the photographic light-sensitive material.

  In particular, the problem of the sensitivity of the photosensitive material is important from the viewpoint of the exposure work at the developing station. If the sensitivity of the light-sensitive material is lowered, the safelight safety is improved accordingly. However, if the sensitivity is lowered, the time required for exposure increases, resulting in a decrease in workability. Therefore, a desirable mode is to reduce only the sensitivity to the safelight without reducing the sensitivity in the wavelength region that the photosensitive material is originally required.

  One method for introducing these colorants is to introduce a water-soluble dye into the photosensitive emulsion layer or the non-photosensitive water-soluble colloid layer. Examples of dyes used in such a method include oxonol dyes, other azo dyes, anthraquinone dyes, arylidene dyes, styryl dyes, triarylmethane dyes, merocyanine dyes, and cyanine dyes (for example, Patent Document 1). .

  As another introduction method, a method in which fine particles of colloidal silver are contained in a non-photosensitive hydrophilic colloid layer existing above and below the red-sensitive emulsion layer is known, while it exists above and below the red-sensitive emulsion layer. There has been proposed a method in which a solid fine particle dispersion of a dye that can be removed at the time of development processing is contained in a non-photosensitive hydrophilic colloid layer (for example, Patent Document 2). In particular, the method using a solid fine particle dispersion of a dye that can be removed during development processing can control the color tone of the colored layer, and there is no coexistence of sensitivity reduction in the safelight wavelength range and sensitivity maintenance in the wavelength range necessary for exposure. It is an excellent method that can be applied to a positive film for a movie that forms a sound track with silver obtained by development and silver.

On the other hand, as a study conducted from the viewpoint of simplifying the handling, a representative study conducted from a viewpoint different from the safelight safety is a study of simplifying and speeding up the development processing. Various approaches have been proposed as a light-sensitive material approach for speeding up development processing, but the main ones can be summarized in the following two points.
1) Increase the development speed.
2) Speed up the removal of unnecessary components.
A typical example of the former is development of a high silver chloride emulsion and high activation of a coupler, and in the latter, improvement of bleaching / fixing speed and development of a dye that is easy to decolorize.

  However, when adding a water-soluble dye or a solid fine particle dispersion of a dye necessary for safelight safety, a decrease in the elution rate of the dye during photographic processing is unavoidable, improving safetylight safety. It was difficult to achieve both reduction of coloration on the white background. Accordingly, there has been a demand for the development of a method for improving the safety of surflight which is highly effective by using less dye.

U.S. Pat. No. 4,078,933 JP 2002-169254 A

  An object of the present invention is to overcome the above-mentioned problems and to provide a silver halide color photographic light-sensitive material that is easy to handle. In particular, an object of the present invention is to provide a silver halide color print material for cinema which is excellent in safe light safety without imposing a load on sensitivity.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means. In particular, in the improvement of safelight safety, the safetylight safety can be remarkably enhanced by using two or more kinds of dyes having a specific structure in combination with the addition of a dye having absorption in the same wavelength region as that of safelight. I got the unexpected knowledge. The present invention has been made based on this finding.
That is, the present invention
(1) At least one layer of a yellow color-sensitive silver halide emulsion layer, a cyan color-sensitive silver halide emulsion layer, and a magenta color-sensitive silver halide emulsion layer on a transparent support, and non-photosensitive A silver halide color photographic light-sensitive material having at least one photosensitive hydrophilic colloid layer, wherein one of the silver halide emulsion layers or the non-photosensitive hydrophilic colloid layer contains an oxonol-based water-soluble dye and an indigo-based water-soluble dye. A silver halide color photographic light-sensitive material comprising at least any two dyes out of three kinds of dyes and phthalocyanine water-soluble dyes;
(2) Of the at least two kinds of dyes, one is an oxonol-based water-soluble dye, and the oxonol dye is represented by the following general formula (I): Silver color photographic material,
Formula (I)
A ¹ = L ¹ − (L ² = L ³ ) _n −A ²
(In the formula, A ¹ and A ² each independently represent an acidic nucleus, L ¹ , L ² and L ³ each independently represent a methine group, and n represents 0, 1, 2 or 3.)
(3) The silver halide color photographic material according to (2), wherein the oxonol-based water-soluble dye is represented by the following general formula (II):

(In the formula (II), R ₂₁ and R ₂₄ are each a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group. , Alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, sulfamoyl group, a sulfo group, an alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, a carbamoyl group or a cyano group, respectively R ₂₂ and R ₂₅ are a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group Aryl group, heterocyclic group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or An arylsulfonylamino group, a sulfamoyl group, a sulfo group, an alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, a carbamoyl group, or a cyano group, R ₂₃ and R ₂₆ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. M ₂ represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or pyridinium, provided that at least one of them in the molecule is ionic hydrophilic. Group as a substituent .)
(4) The silver halide color photographic light-sensitive material as described in (3), wherein R ₂₂ and R ₂₅ in the oxonol-based water-soluble dye as described in (3) are sulfo groups,
(5) Of the at least two dyes, one is an indigo water-soluble dye, and the indigo dye is represented by the following general formula (III): (1) to (4) The silver halide color photographic light-sensitive material according to any one of the above,

(In the formula (III), X ₃₁ and X ₃₂ each represent O, S, Se or NH, and Ar ₃₁ and Ar ₃₂ each represent a substituted arylene group, at least one of which is an ionic hydrophilic group. A functional group as a substituent.)
(6) Among the at least two dyes, one is a phthalocyanine-based water-soluble dye, and the phthalocyanine dye is represented by the following general formula (IV): The silver halide color photographic light-sensitive material according to any one of the above,

(In the formula (IV); X ₁ , X ₂ , X ₃ and X ₄ each independently represent —SO—Z and / or —SO ₂ —Z, where Z is a substituted or unsubstituted one. Y ₁ represents an alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group Group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alcohol Xoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group Represents a heterocyclic thio group, a phosphoryl group, an acyl group or an ionic hydrophilic group, and these groups may further have a substituent, provided that X ₁ , X ₂ , X ₃ , X ₄ , Y _1, at least one of Y _2, Y ₃ and Y _4, .A1～a4 having as a substituent an ionic hydrophilic group, b1.about.b4 is the X ₁ to X _4, Y ₁ to Y _4, respectively Represents the number of substituents, and a1 to a4 and b1 to b4 are each independently an integer of 0 to 4, provided that all of a1 to a4 are not simultaneously 0. M is a hydrogen atom Represents a metal element, metal oxide, metal hydroxide, or metal halide.)
{More preferably, it is a phthalocyanine-based water-soluble dye represented by the general formula (VI).

(In formula (VI); R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, Alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino Group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, Aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group Represents an acyl group or an ionic hydrophilic group, and these groups may further have a substituent, and Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently substituted or unsubstituted. An alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. At least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent, and l, m, n, p, q1, q2, q3, and q4 are each independently Represents an integer of 1 or 2. M is as defined in the general formula (IV).}
(7) The silver halide color photographic light-sensitive material as described in any one of (1) to (6), wherein the non-photosensitive hydrophilic colloid layer contains the at least two dyes. ,
(8) Any one of (1) to (7), wherein at least one layer of the non-photosensitive hydrophilic colloid layer contains a solid fine particle dispersion of a dye represented by the following general formula (V): Or a silver halide color photographic light-sensitive material according to claim 1;
General formula (V)
D- (W) z
(In the general formula (V), D represents a compound residue having a chromophore, W represents a dissociative hydrogen or a group having a dissociative hydrogen, and z represents an integer of 1 to 7) and (9 The silver halide color photographic light-sensitive material according to any one of (1) to (8), wherein the solid fine particle dispersion of the dye is prepared through a heat treatment step of 40 ° C. or higher. Is to provide.

  According to the present invention, a silver halide color photographic light-sensitive material that is easy to handle, excellent in safelight safety without lowering the sensitivity in the originally required wavelength region, and suitable as a silver halide color photographic light-sensitive material for movies, etc. Can be provided.

The silver halide color photographic light-sensitive material of the present invention will be described in detail below.
The present invention comprises at least one yellow color-sensitive silver halide emulsion layer, cyan color-sensitive silver halide emulsion layer, and magenta color-sensitive silver halide emulsion layer on a transmissive support, A silver halide color photographic light-sensitive material having at least one photosensitive hydrophilic colloid layer, wherein any one of the silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer contains an oxonol-based water-soluble dye and an indigo-based water-soluble dye. The dye contains at least any two dyes among the three kinds of water-soluble dyes and phthalocyanine water-soluble dyes.
First, the dye used in the present invention will be described.

  The dye used in the present invention is completely decolorized in the photographic processing process in order not to adversely affect the silver halide emulsion layer in the light-sensitive material and to leave no harmful coloring on the light-sensitive material. Needless to say, it is easy to elute from the photographic material.

  The state of the dye in the hydrophilic colloid film (silver halide emulsion layer, non-photosensitive hydrophilic colloid layer) is a molecular dispersion state that shows a waveform that is almost the same as the absorption waveform measured in a dilute solution. There is an association state that gives an absorption waveform different from the result of the solution. The embodiment of the present invention may be in any state as long as the absorption wavelength of the present invention is expressed, but it is preferably present in the molecular dispersion state in view of the effect of the present invention.

The absorption waveform of the dye in the present invention is such that a target dye is dissolved in a lime-processed gelatin aqueous solution to prepare a coating film in which 30 μmol of the dye is applied per 1 m ² , and this film is formed under the condition f described in JIS Z 8722. It is measured by measuring the absorption waveform with a spectrophotometer using an integrating sphere that satisfies the biological conditions.
₀ the wavelength of maximum absorption lambda of obtained absorption waveform, the wavelength lambda ₁ in a short-side corresponding to 1/2 of the density of the density of lambda _0, long wave corresponding to 1/2 of the density of the density of lambda ₀ the wavelength of the side and λ _2, λ ₀ -λ ₁ to short side half width at half maximum, defining respectively the lambda ₂ 1-? ₀ as long-wave half width at half maximum.

  In the dye absorption waveform of the present invention, the half width at half maximum is preferably within a predetermined range. More preferably, the waveform has a small half width at half maximum and absorption in a narrow wavelength region. Specifically, it has a maximum absorption in the range of 570 to 610 nm, and the half-value half width on the long wave side is 40 nm or less. When a dye having a wide half-width and a broad absorption waveform is used, a part of the absorption of the dye falls within the sensitivity range necessary for exposure, resulting in a decrease in necessary sensitivity, which is disadvantageous in exposure work. It becomes a photosensitive material.

  The addition amount of the dye of the present invention can be added at any addition amount that exhibits the effects of the present invention, but the absorption density at the maximum wavelength in the photosensitive material is 0 in any dye wavelength range. It is preferable to add in a range of 0.05 to 2.0, more preferably in a range of 0.1 to 1.5, and a range of 0.2 to 1.0. It is particularly preferable to add to.

The general formula (I) will be described in detail.
Formula (I)
A ¹ = L ¹ − (L ² = L ³ ) _n −A ²
(In the formula (I), A ¹ and A ² each independently represent an acidic nucleus, L ¹ , L ² and L ³ each independently represent a methine group, and n is 0, 1, 2 or 3 (preferably Represents 1 or 2).)

Hereinafter, the compound represented by formula (I) will be described in detail.
The acidic nucleus represented by A ¹ and A ² is preferably derived from a cyclic ketomethylene compound or a compound having a methylene group sandwiched between electron-withdrawing groups. Examples of cyclic ketomethylene compounds include 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolo Mention may be made of pyridine, hydroxypyridone, pyrazolidinedione, 2,5-dihydrofuran. These may have a substituent.

A compound having a methylene group sandwiched between electron-withdrawing groups can be represented as Z ¹ CH ₂ Z ² . Here, Z ¹ and Z ² each represent —CN, —SO ₂ R ¹¹ , —COR ¹¹ , —COOR ¹² , —CONHR ¹² , —SO ₂ NHR ¹² or —C [═C (CN) ₂ ] R ¹¹ . . R ¹¹ represents an alkyl group, an aryl group, or a heterocyclic group, R ¹² represents a hydrogen atom or a group represented by R ¹¹ , and each of these may have a substituent.

The methine group represented by L ¹ , L ² and L ³ may have a substituent, and the substituents are connected to each other to form a 5- or 6-membered ring (eg, cyclopentene, cyclohexene). May be.
In addition, the compound represented by the general formula (I) includes a carboxylic acid group, a sulfonamide group, a sulfamoyl group, a sulfonylcarbamoyl group, an acylsulfamoyl group, a phenolic hydroxyl group, and an enol group of an oxonol dye as water-soluble groups in the molecule. It is preferable to have 1 to 7 groups selected from the group consisting of

  The substituent which each group described above may have is not particularly limited unless it is a substituent that substantially dissolves the compound of the general formula (I) in water having a pH of 5 to 7. For example, the following substituents can be mentioned.

  Carboxylic acid group, C1-C10 sulfonamide group (for example, methanesulfonamide, benzenesulfonamide, butanesulfonamide, n-octanesulfonamide), C0-10 unsubstituted or alkyl- or aryl-substituted sulfamoyl group (For example, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, naphthylsulfamoyl, butylsulfamoyl), sulfonylcarbamoyl groups having 2 to 10 carbon atoms (for example, methanesulfonylcarbamoyl, propanesulfonylcarbamoyl, benzene) Sulfonylcarbamoyl), acylsulfamoyl groups having 1 to 10 carbon atoms (for example, acetylsulfamoyl, propionylsulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl),

A linear, branched or cyclic alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, butyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, Benzyl, phenethyl, 4-carboxybenzyl, 2-diethylaminoethyl), an alkenyl group having 2 to 8 carbon atoms (for example, vinyl, allyl), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, butoxy), halogen Atoms (for example, F, Cl, Br), C0-10 amino groups (for example, unsubstituted amino, dimethylamino, diethylamino, carboxyethylamino), C2-10 ester groups (for example, methoxycarbonyl) ), An amide group having 1 to 10 carbon atoms (for example, acetylamino, Nsamide), a carbamoyl group having 1 to 10 carbon atoms (for example, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl), an aryl group having 6 to 10 carbon atoms (for example, phenyl, naphthyl, hydroxyphenyl, 4-carboxyphenyl, 3 -Carboxyphenyl, 3,5-dicarboxyphenyl, 4-methanesulfonamidophenyl, 4-butanesulfonamidophenyl), aryloxy groups having 6 to 10 carbon atoms (for example, phenoxy, 4-carboxyphenoxy, 3-methylphenoxy) , Naphthoxy),

C1-C8 alkylthio group (for example, methylthio, ethylthio, octylthio), C6-C10 arylthio group (for example, phenylthio, naphthylthio), C1-C10 acyl group (for example, acetyl, benzoyl, propanoyl) ), A sulfonyl group having 1 to 10 carbon atoms (for example, methanesulfonyl, benzenesulfonyl), a ureido group having 1 to 10 carbon atoms (for example, ureido, methylureido), and a urethane group having 2 to 10 carbon atoms (for example, methoxycarbonyl). Amino, ethoxycarbonylamino), cyano group, hydroxyl group, nitro group, heterocyclic group (for example, 5-carboxybenzoxazole ring, pyridine ring, sulfolane ring, pyrrole ring, pyrrolidine ring, morpholine ring, piperazine ring, pyrimidine ring, furan Ring).

  The general formula (II) representing the oxonol-based water-soluble dye will be described in detail.

R ₂₁ and R ₂₄ are each a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, alkyloxycarbonyl group, aryl Oxycarbonyl group, acyl group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, sulfamoyl group, sulfo group, alkyl or An arylsulfinyl group, an alkyl or arylsulfonyl group, a carbamoyl group, or a cyano group is represented.

  More specifically, an alkyl group (a linear, branched, cyclic substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, such as cyclohexyl, cyclopentyl), an alkenyl group (It represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group, preferably a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, such as vinyl, allyl, prenyl), an alkynyl group (preferably A substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, such as ethynyl, pro Rugyl, trimethylsilylethynyl group), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl), a heterocyclic group (preferably 5 or A monovalent group obtained by removing one hydrogen atom from a 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably a 5- or 6-membered group having 3 to 10 carbon atoms For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, For example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy Si group (preferably a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy), acyloxy group (preferably formyloxy Groups, substituted or unsubstituted alkylcarbonyloxy groups having 2 to 10 carbon atoms, substituted or unsubstituted arylcarbonyloxy groups having 6 to 10 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy),

A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 10 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di- n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkyloxycarbonyl group (preferably a substituted or unsubstituted alkyloxycarbonyl group having 2 to 10 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxy Carbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 10 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, -T-butylphenoxycarbonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 10 carbon atoms, substituted or unsubstituted arylcarbonyl group having 6 to 10 carbon atoms, from 4 carbon atoms Heterocyclic carbonyl groups bonded to a carbonyl group at 10 substituted or unsubstituted carbon atoms, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl 2-furylcarbonyl), an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms, a substituted or unsubstituted anilino group having 6 to 15 carbon atoms, such as amino, methyl Amino, dimethylamino, anilino, N-methyl-anilino, diph Enylamino),

An acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 10 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 15 carbon atoms such as formylamino, acetylamino, Pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 10 carbon atoms, for example, Carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbo having 2 to 10 carbon atoms) A ruamino group, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms) A substituted or unsubstituted aryloxycarbonylamino group such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m- (n-octyloxy) phenoxycarbonylamino), sulfamoylamino group (preferably having 0 to 0 carbon atoms) 10 substituted or unsubstituted sulfamoylamino groups, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino),

Alkyl or arylsulfonylamino group (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 10 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 15 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenyl Sulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 10 carbon atoms, such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo An alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 10 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 15 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl P-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 15 carbon atoms, such as methyl Sulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), carbamoyl group (preferably, substituted or unsubstituted carbamoyl having 1 to 10 carbon atoms, such as carbamoyl, N-methylcarbamoyl) N, represents N- dimethylcarbamoyl, N, N- di -n- octylcarbamoyl, N- (methylsulfonyl) carbamoyl), a cyano group. In addition, carbon number means what remove | excluding the substituent on the group.

Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.
R ₂₂ and R ₂₅ are each a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, amino group, acylamino group, amino group Carbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, carbamoyl group or cyano Represents a group and has the same meaning as in the case of R ₂₁ and R ₂₄ , and the same applies to the preferred range and the substituent that the group may have.
R ₂₃ and R ₂₆ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and each may further have a substituent. Examples of R ₂₃ and R ₂₆ are the same as those described for R ₂₁ and R ₂₄ , and examples of substituents are also the same. Preferred substituents include ionic hydrophilic groups described later.
M ₂ represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or pyridinium. Of these, alkali metals and alkaline earth metals are preferable, and Na and K are particularly preferable. Examples of the ammonium group include ammonium, triethylammonium, and tetrabutylammonium, among which ammonium is preferable.
However, at least one of them in the molecule has an ionic hydrophilic group described later as a substituent.

  The general formula (III) representing the indigo water-soluble dye will be described in detail.

X ₃₁ and X ₃₂ each represent O, S, Se or NH; Ar ₃₁ and Ar ₃₂ each represent a substituted arylene group, preferably a substituted arylene group having 6 to 15 carbon atoms, such as phenylene, p- Tolylene, naphthylene and chlorophenylene. Further, any one of them has at least one ionic hydrophilic group described later as a substituent.

  The general formula (IV) representing the phthalocyanine-based water-soluble dye will be described in detail.

X ₁ , X ₂ , X ₃ and X ₄ each independently represent —SO—Z and / or —SO ₂ —Z, preferably —SO ₂ —Z. Here, Z is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, substituted or unsubstituted Represents a substituted heterocyclic group, and particularly preferred is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Among them, a substituted alkyl group, a substituted aryl group, a substituted Heterocyclic groups are most preferred.

In the general formula (IV), Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group. , Cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group , Sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio Group, phosphoryl group, acyl group or It represents an ionic hydrophilic group. Each group may further have a substituent.

  Among these, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, and an alkoxycarbonyl group are preferable, and in particular, a hydrogen atom, a halogen atom, A cyano group is preferred, and a hydrogen atom is most preferred.

At least _{one of} X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y ₃ and Y ₄ has an ionic hydrophilic group as a substituent. Examples of the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.

Examples of the substituent that Y ₁ , Y ₂ , Y ₃ , Y ₄ and Z can have include the following substituents.

  Halogen atom (for example, chlorine atom, bromine atom); linear or branched alkyl group having 1 to 12 carbon atoms, aralkyl group having 7 to 18 carbon atoms, alkenyl group having 2 to 12 carbon atoms, 2 to 2 carbon atoms 12 linear or branched alkynyl groups, a cycloalkyl group having 3 to 12 carbon atoms which may have a side chain, a cycloalkenyl group having 3 to 12 carbon atoms which may have a side chain ( Specific examples of the above group include, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl): aryl group (for example, phenyl, 4-t- Butylphenyl, 2,4-di-t-amylphenyl); heterocyclic groups (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, -Benzothiazolyl); alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy); aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy) 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy); acylamino groups (eg acetamide, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide); alkylamino groups (eg methyl Amino, butylamino, diethylamino, methylbutylamino);

Anilino group (eg, phenylamino, 2-chloroanilino); ureido group (eg, phenylureido, methylureido, N, N-dibutylureido); sulfamoylamino group (eg, N, N-dipropylsulfamoylamino) An alkylthio group (eg, methylthio, octylthio, 2-phenoxyethylthio); an arylthio group (eg, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio); an alkyloxycarbonylamino group (eg, , Methoxycarbonylamino); sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide); carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl) Sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N, N-diethylsulfamoyl); sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl); alkyl An oxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl); a heterocyclic oxy group (eg, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy);

An azo group (eg, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo); an acyloxy group (eg, acetoxy); a carbamoyloxy group (eg, N- Methylcarbamoyloxy, N-phenylcarbamoyloxy); silyloxy groups (eg, trimethylsilyloxy, dibutylmethylsilyloxy); aryloxycarbonylamino groups (eg, phenoxycarbonylamino); imide groups (eg, N-succinimide, N-phthalimid) A heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio); a sulfinyl group (for example, 3-phenoxypropyl) Sulfinyl); phosphonyl groups (eg, Enoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl); aryloxycarbonyl groups (eg phenoxycarbonyl); acyl groups (eg acetyl, 3-phenylpropanoyl, benzoyl); ionic hydrophilic groups (eg Carboxyl group, sulfo group, and quaternary ammonium group); other examples include cyano group, hydroxyl group, nitro group, and amino group.

a1 to a4, b1.about.b4 each represent the number of substituents of _{X 1 ~X 4, Y 1 ~Y} 4. A1 to a4 and b1 to b4 are each independently an integer of 0 to 4. However, all of a1 to a4 do not become 0 at the same time.

  Preferably, a1 and b1 each independently represent an integer of 0 to 4 satisfying a relationship of a1 + b1 = 4, and particularly preferable is a combination in which a1 is 1 or 2, and b1 is 3 or 2. Among them, a combination in which a1 is 1 and b1 is 3 is most preferable.

  Preferably, a2 and b2 each independently represents an integer of 0 to 4 satisfying the relationship of a2 + b2 = 4, and particularly preferable is a combination in which a2 is 1 or 2, and b2 is 3 or 2. Among them, a combination in which a2 is 1 and b2 is 3 is most preferable.

  Preferably, a3 and b3 each independently represents an integer of 0 to 4 satisfying a relationship of a3 + b3 = 4, and particularly preferable is a combination in which a3 is 1 or 2, and b3 is 3 or 2. Among them, the combination in which a3 is 1 and b3 is 3 is most preferable.

Preferably, a4 and b4 each independently represent an integer of 0 to 4 satisfying the relationship of a4 + b4 = 4, and particularly preferable is a combination in which a4 is 1 or 2, and b4 is 3 or 2. Among them, a combination in which a4 is 1 and b4 is 3 is most preferable.
M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
In addition to hydrogen atoms, preferable as M are metal elements such as Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi and the like can be mentioned. Of these, Cu, Ni, Zn, Al and the like are particularly preferable, and Cu is most preferable. Preferred examples of the metal oxide include VO and GeO. Further, preferred examples of the metal hydroxide include Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _{2 and the} like. Furthermore, examples of the metal halide include AlClSiCl ₂ , VCl, VCl ₂ , VOCl, FeCl, GaCl, and ZrCl.

  In addition, in the phthalocyanine compound represented by the general formula (IV), Pc (phthalocyanine ring) is dimerized (for example, Pc-ML-LM-Pc) or 3 via L (a divalent linking group). A monomer may be formed, and a plurality of M present at that time may be the same or different.

The divalent linking group represented by L includes an oxy group —O—, a thio group —S—, a carbonyl group —CO—, a sulfonyl group —SO ₂ —, an imino group —NH—, a methylene group —CH ₂ —, And a group formed by combining them is preferred.

Examples of the halogen atom represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include a fluorine atom, a chlorine atom and a bromine atom.

The alkyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkyl group having a substituent and an unsubstituted alkyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom and an ionic hydrophilic group. Examples of the alkyl group include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.

The cycloalkyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The alkenyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkenyl group having a substituent and an unsubstituted alkenyl group. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include a vinyl group and an allyl group.

The aralkyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.

The aryl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an aryl group having a substituent and an unsubstituted aryl group. As the aryl group, an aryl group having 6 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

The heterocyclic group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic group include a 2-pyridyl group, a 2-thienyl group, and a 2-furyl group.

The alkylamino group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkylamino group having a substituent and an unsubstituted alkylamino group. The alkylamino group is preferably an alkylamino group having 1 to 6 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.

The alkoxy group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkoxy group having a substituent and an unsubstituted alkoxy group. As an alkoxy group when a substituent is removed, an alkoxy group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

The aryloxy group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an alkoxy group and a cy group and an o-methoxyphenoxy group.

The amide group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an amide group having a substituent and an unsubstituted amide group. The amide group is preferably an amide group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the amide group include an acetamide group, a propionamide group, a benzamide group, and a 3,5-disulfobenzamide group.

The arylamino group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 12 carbon atoms when a substituent is removed. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.

The ureido group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

The sulfamoylamino group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino group.

The alkylthio group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkylthio group having a substituent and an unsubstituted alkylthio group. The alkylthio group is preferably an alkylthio group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group include a methylthio group and an ethylthio group.

The arylthio group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an arylthio group having a substituent and an unsubstituted arylthio group. The arylthio group is preferably an arylthio group having 6 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an alkyl group and an ionic hydrophilic group. Examples of the arylthio group include a phenylthio group and a p-tolylthio group.

The alkoxycarbonylamino group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

The sulfonamide group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a sulfonamide group having a substituent and an unsubstituted sulfonamide group. The sulfonamide group is preferably a sulfonamide group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonamide group include methanesulfonamide, benzenesulfonamide, and 3-carboxybenzenesulfonamide.

The carbamoyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

The sulfamoyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group and an aryl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group, a di- (2-hydroxyethyl) sulfamoyl group, and a phenylsulfamoyl group.

The alkoxycarbonyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

The heterocyclic oxy group represented by Y ₁ , Y ₂ , Y ₃ and Y _{4 includes} a heterocyclic oxy group having a substituent and an unsubstituted heterocyclic oxy group. The heterocyclic oxy group is preferably a heterocyclic oxy group having a 5-membered or 6-membered heterocyclic ring. Examples of the substituent include a hydroxyl group and an ionic hydrophilic group. Examples of the heterocyclic oxy group include a 2-tetrahydropyranyloxy group.

The azo group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an azo group having a substituent and an unsubstituted azo group. Examples of the azo group include a p-nitrophenylazo group.

The acyloxy group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an acyloxy group having a substituent and an unsubstituted acyloxy group. The acyloxy group is preferably an acyloxy group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

The carbamoyloxy group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

The silyloxy group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a silyloxy group having a substituent and an unsubstituted silyloxy group. Examples of the substituent include an alkyl group. Examples of the silyloxy group include a trimethylsilyloxy group.

The aryloxycarbonyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

The aryloxycarbonylamino group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

The imide group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an imide group having a substituent and an unsubstituted imide group. Examples of the imide group include an N-phthalimide group and an N-succinimide group.

The heterocyclic thio group represented by Y ₁ , Y ₂ , Y ₃ and Y _{4 includes} a heterocyclic thio group having a substituent and an unsubstituted heterocyclic thio group. The heterocyclic thio group preferably has a 5-membered or 6-membered heterocyclic ring. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic thio group include a 2-pyridylthio group.

The phosphoryl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a phosphoryl group having a substituent and an unsubstituted phosphoryl group. Examples of the phosphoryl group include a phenoxyphosphoryl group and a phenylphosphoryl group.

The acyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

The ionic hydrophilic group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a sulfo group, a carboxyl group and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.

  The alkyl group represented by Z includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms when a substituent is excluded. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom and an ionic hydrophilic group. Examples of the alkyl group include methyl, ethyl, butyl, n-propyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.

  The cycloalkyl group represented by Z includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

  The alkenyl group represented by Z includes a substituted alkenyl group and an unsubstituted alkenyl group. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include a vinyl group and an allyl group.

  The aralkyl group represented by Z includes an aralkyl group having a substituent and an unsubstituted aralkyl group. As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.

The aryl group represented by Z includes an aryl group having a substituent and an unsubstituted aryl group. As the aryl group, an aryl group having 6 to 12 carbon atoms when a substituent is removed is preferable. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl, m-sulfophenyl. Examples of the substituent include an alkyl group (R—), an alkoxy group (RO—), an alkylamino group (RNH—, RR′N—), a carbamoyl group (—CONHR), a sulfamoyl group (—SO ₂ NHR), A sulfonylamino group (—NHSO ₂ R), a halogen atom, and an ionic hydrophilic group are included (note that R and R ′ represent an alkyl group and a phenyl group, and these may also have an ionic hydrophilic group. Good).

The heterocyclic group represented by Z includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group, and may form a condensed ring with another ring. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. The heterocyclic group may form a condensed ring with another ring. Examples of the heterocyclic group include, but are not limited to, the substitution position of the heterocyclic ring, each independently, imidazole, benzimidazole, pyrazole, benzopyrazole, triazole, thiazole, benzothiazole, isothiazole, benzoisothiazole, Oxazole, benzoxazole, thiadiazole, pyrrole, benzopyrrole, indole, isoxazole, benzisoxazole, thiophene, benzothiophene, furan, benzofuran, pyridine, quinoline, isoquinoline, pyridazine, pyrimidine, pyrazine, cinnoline, phthalazine, quinazoline, quinoxaline, Triazine and the like are included. Examples of the substituent include an alkyl group (R—), an alkoxy group (RO—), an alkylamino group (RNH—, RR′N—), a carbamoyl group (—CONHR), a sulfamoyl group (—SO ₂ NHR), A sulfonylamino group (—NHSO ₂ R), a halogen atom, and an ionic hydrophilic group are included (note that R and R ′ represent an alkyl group and a phenyl group, and these may also have an ionic hydrophilic group. Good).

A particularly preferred combination as the phthalocyanine compound represented by the general formula (IV) is:
(A) X ₁ , X ₂ , X ₃ and X ₄ are —SO ₂ —Z.
(B) Z is independently a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group, and particularly preferably a substituted alkyl group or a substituted heterocyclic group, and among them, a substituted alkyl group. Most preferred.
(C) At least one of X ₁ , X ₂ , X ₃ , and X ₄ contains an ionic hydrophilic group as a substituent, and the substituent is a sulfo group, a carboxyl group, or a quaternary ammonium group. It is preferably a carboxyl group or a sulfo group, and particularly preferably a sulfo group.
(D) Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, a halogen atom, a cyano group or a sulfonyl group, preferably a hydrogen atom, a halogen atom or a sulfonyl group, Of these, a hydrogen atom or a sulfonyl group is most preferred.
(E) a1 to a4 are each independently an integer of 1 or 2, particularly preferably 1, b1 to b4 are each independently an integer of 3 or 2, and 3 is particularly preferable.
(F) Most preferably, M is Cu, Ni, Zn, or Al, especially Cu.

  Those having at least 4 ionic hydrophilic groups in one molecule of the phthalocyanine compound represented by the general formula (IV) are preferable. In particular, the ionic hydrophilic group is preferably a sulfo group. Most preferred are those having at least 4 groups.

  Since the phthalocyanine compound represented by the general formula (IV) has at least one ionic hydrophilic group in the molecule, it has good solubility or dispersibility in an aqueous medium.

  As for the preferred combination of substituents of the compound represented by the general formula (IV), a compound in which at least one of various substituents is the above preferred group is preferable, and more various substituents are the above preferred groups Are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

  Among the phthalocyanine compounds represented by the general formula (IV), a phthalocyanine compound having a structure represented by the following general formula (VI) is more preferable. Hereinafter, the phthalocyanine compound represented by the general formula (VI) of the present invention will be described in detail.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl Group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group , Alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide Group, heterocyclic thio group, phosphoryl group, acyl group Represents an ionic hydrophilic group. These groups may further have a substituent. Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group Represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent. l, m, n, p, q1, q2, q3, and q4 each independently represent an integer of 1 or 2. M has the same meaning as in the general formula (IV).
In the general formula (VI), Z ₁ , Z ₂ , Z ₃ and Z ₄ are each independently synonymous with Z in the general formula (IV), and preferred examples are also the same.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently Y ₁ , Y ₂ , Y ₃ and Y _{4 in the} general formula (IV). Each is synonymous, and the preferred examples are also the same.

  l, m, n, and p each independently represent an integer of 1 or 2 that satisfies 4 ≦ l + m + n + p ≦ 8, preferably 4 ≦ l + m + n + p ≦ 6, and most preferably 1 (l = M = n = p = 1).

  q1, q2, q3, and q4 are each independently an integer of 1 or 2, and it is particularly preferable that q1 = q2 = q3 = q4 = 2.

  M has the same meaning as M in formula (IV), and preferred examples are also the same.

Among the phthalocyanine compounds represented by the general formula (VI), particularly preferred combinations of substituents are as follows.
(A) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are each independently a hydrogen atom, a halogen atom or a cyano group, particularly a hydrogen atom or a halogen atom Among them, a hydrogen atom is most preferable.
(B) Z ₁ , Z ₂ , Z ₃ and Z ₄ are each independently preferably a substituted alkyl group, a substituted aryl group or a substituted heterocyclic group, particularly preferably a substituted alkyl group or a substituted heterocyclic group. A substituted alkyl group is most preferred.
(C) l, m, n, and p are each independently an integer of 1 or 2, particularly preferably l = m = n = p = 1.
(D) q1, q2, q3 and q4 each independently represents an integer of 1 or 2, and q1 = q2 = q3 = q4 = 2 is particularly preferred.
(E) M is preferably Cu, Ni, Zn, or Al, and most preferably Cu.

  In addition, as for the preferred combination of substituents of the compound represented by the general formula (VI), a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred as described above. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups described above.

The general formula (V) will be described in detail.
General formula (V)
D- (W) z
In the general formula (V), D represents a compound residue having a chromophore, W represents a dissociative hydrogen or a group having a dissociative hydrogen, and z represents an integer of 1 to 7.
The compound residue having a chromophore in D can be selected from a number of well-known dyes. Specific examples of these compounds include oxonol dyes, merocyanine dyes, cyanine dyes, arylidene dyes, azomethine dyes, triphenylmethane dyes, azo dyes, anthraquinone dyes, and indoaniline dyes.

W represents a dissociative hydrogen or a group having a dissociative hydrogen bonded to D directly or via a divalent linking group.
The divalent linking group between W and D includes an alkylene group, an arylene group, a heterocyclic residue, —CO—, —SO _n — (n = 0, 1, 2), —NR— (R is hydrogen) And a divalent group formed by combining these linking groups. Further, they are an alkyl group, an aryl group, an alkoxy group, an amino group, an acylamino group, a halogen atom. May have a substituent such as a hydroxyl group, a carboxy group, a sulfamoyl group, a carbamoyl group, or a sulfonamide group. Preferred examples include — (CH ₂ ) _n — (n = 1, 2, 3), —CH ₂ CH (CH ₃ ) CH ₂ —, 1,2-phenylene, 5-carboxy-1,3-phenylene, 1, 4-phenylene, 6-methoxy-1,3-phenylene, —CONHC ₆ H ₄ — and the like can be mentioned.

  The dissociative hydrogen represented by W or the group having dissociative hydrogen is non-dissociated when the dye represented by the general formula (V) is added to the silver halide photographic light-sensitive material of the present invention. The compound of the general formula (V) has the property of making the dye of the general formula (V) substantially water-insoluble. In the step of developing the photosensitive material, it is dissociated to make the compound of the general formula (V) substantially water-soluble. Has characteristics. Examples of the group having dissociable hydrogen represented by W include groups having a carboxylic acid group, a sulfonamide group, a sulfamoyl group, a sulfonylcarbamoyl group, an acylsulfamoyl group, a phenolic hydroxyl group, and the like. Examples of the dissociable hydrogen represented by W include hydrogen of an enol group of an oxonol dye.

A preferred range for z is 1-5, and a particularly preferred range is 1-3.
Among the compounds represented by the general formula (V), a compound having a dissociative hydrogen group in W is a group having a carboxylic acid group, and particularly a compound having an aryl group substituted with a carboxyl group. preferable.
Of the compounds represented by the general formula (V), more preferred are the compounds represented by the following general formula (VII) or general formula (I).
Formula (VII)
A ¹ = L ¹ − (L ² = L ³ ) _m −Q
In general formula (VII), A ¹ represents an acidic nucleus, Q represents an aryl group or a heterocyclic group, L ¹ , L ² , and L ³ each independently represent a methine group, and m represents 0, 1 or 2 Represents. However, the compound represented by the general formula (VII) has a carboxylic acid group, a sulfonamide group, a sulfamoyl group, a sulfonylcarbamoyl group, an acylsulfamoyl group, a phenolic hydroxyl group, and an enol group of an oxonol dye as a water-soluble group in the molecule. 1 to 7 groups (preferably carboxylic acid groups) selected from the group consisting of

Hereinafter, the compound represented by formula (VII) will be described in detail.
The acidic nucleus represented by A ¹ has the same meaning as A ¹ in the general formula (I), and preferred examples thereof are also the same.

A ¹ is preferably an acidic nucleus derived from the aforementioned compound having a methylene group sandwiched between electron-withdrawing groups.

  Examples of the aryl group represented by Q include a phenyl group and a naphthyl group. Each of these may have a substituent. Examples of the heterocyclic group represented by Q include pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, thiopyran. And oxodiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin, and coumarone. Each of these may have a substituent. As an example of a substituent, the substituent which each group of the compound of the said general formula (I) may have, a water-soluble group, and an ionic hydrophilic group are mentioned.

The methine groups represented by L ¹ , L ² and L ³ are each independently synonymous with L ¹ , L ² and L ^{3 in the} general formula (I).

  Specific examples of the compounds represented by the general formulas (I) to (VII) preferably used in the present invention are described below, but the present invention is not limited to these.

  The dyes used in the present invention include International Publication No. WO88 / 04794, European Publication Nos. 274,723A1, 276,566, 299,435, JP-A-52-92716, 55-155350, and 55- 155351, 61-205934, 48-68623, U.S. Pat.Nos. 2,527,583, 3,486,897, 3,746,539, 3,933,798, 4,130,429, 4,040,841, JP-A-3- It can be synthesized according to the method described in the specifications or publications of No. 282244, No. 3-7931, No. 3-167546, etc. or its method.

The solid fine particle dispersion of the dye used in the present invention can be prepared by a conventional method. Details of the production method are described in “Functional Pigment Application Technology” (published by CMC, 1991).
Media distribution is one of the common methods. In this method, a dye powder or a wet cake called wet cake, which is called a wet cake, is made into an aqueous slurry, and an arbitrary pulverizer (for example, ball mill, vibration ball mill, planetary ball mill, vertical sand mill, roller mill, pin mill, Using a coball mill, caddy mill, horizontal sand mill, attritor, etc.) and grinding by mechanical force in the presence of dispersion media (steel balls, ceramic balls, glass beads, alumina beads, zirconia silicate beads, zirconia beads, Ottawa sand, etc.) To do. Among these, beads having an average diameter of preferably 2 to 0.3 mm, more preferably 1 to 0.3 mm, and still more preferably 0.5 to 0.3 mm are used. In addition to these, a method of pulverizing with a jet mill, a roll mill, a homogenizer, a colloid mill or a dissolver, or a pulverizing method with an ultrasonic disperser can also be used.

  Further, as disclosed in U.S. Pat.No. 2,870,012, after dissolving in a uniform solution, a poor solvent is added to precipitate solid fine particles, or, for example, as disclosed in JP-A-3-182743, an alkaline solution It is also possible to use a method of precipitating solid fine particles by lowering the pH after being dissolved in the solution.

  When preparing these solid fine particle dispersions, it is preferable that a dispersion aid is present. Dispersing aids that have been disclosed in the past include alkyl phenoxy ethoxy sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfate ester salt, alkyl sulfosuccinate, sodium oleyl methyl taurate, naphthalene sulfonic acid. Denatured formaldehyde, polyacrylic acid, polymethacrylic acid, maleic acid acrylic acid copolymer, anionic dispersants such as carboxymethyl cellulose and cellulose sulfate, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. Nonionic dispersants, cationic dispersants, and betaine dispersants are used, and polyalkylene oxides represented by the following general formula (VIII-a) or (VIII-b) are used. Preferred.

  In general formulas (VIII-a) and (VIII-b), a and b each represent a value of 5 to 500. Preferable values of a and b are 10 to 200, respectively, and more preferable values of a and b are 50 to 150, respectively. A value of a and b within this range is preferable from the viewpoint of improving the uniformity of the coated surface.

  In the dispersion aid, the ratio of the polyethylene oxide part is preferably 0.3 to 0.9, more preferably 0.7 to 0.9, and still more preferably 0.8 to 0.9, in terms of mass ratio. The average molecular weight of the dispersion aid is preferably 1,000 to 40,000, more preferably 5,000 to 30,000, and still more preferably 8,000 to 20,000. Further, the HLB (hydrophilic / lipophilic balance) of the dispersion aid is preferably 7 to 30, more preferably 12 to 30, and still more preferably 18 to 30. A numerical value within this range is preferable in terms of improving the uniformity of the coated surface.

  These compounds are available as commercial products, for example, Pluronic (trade name) manufactured by BASF.

  Specific examples of the compound represented by formula (VIII-a) or (VIII-b) used in the present invention are described below.

In the present invention, the amount of the dispersion aid used with respect to the dyes that are preferably used is preferably 0.05 to 0.5, more preferably 0.1 to 0.3 in terms of mass ratio. When the amount of the dispersion aid used is within this range, it is preferable from the viewpoint of improving the uniformity of the coated surface.
Also, hydrophilic colloids such as polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polysaccharides and gelatin can be coexisted for the purpose of stabilizing the dispersion and reducing the viscosity when preparing the solid fine particle dispersion. In the present invention, it is particularly preferable that a compound represented by the general formula (IX) described later coexists.

  The solid fine particle dispersion preferably used in the present invention is preferably heat-treated before, during or after dispersion by a method as disclosed in JP-A-5-216166.

  The dye according to the present invention is preferably subjected to a heat treatment at 40 ° C. or higher (preferably 60 ° C. or higher) before being incorporated in the light-sensitive material to obtain the effects of the present invention. In the present invention, the heat treatment preferably applied to the dye dispersion includes a method performed before the step of finely dispersing the dye powder in a solid state, such as heating in a solvent, and water or a dye in the presence of a dispersant. There are a method in which the dispersion is carried out by applying a temperature without cooling when dispersed in another solvent, and a method in which the liquid after dispersion and the coating liquid are subjected to a heat treatment.

  When a plurality of solid fine particle dispersions containing the dye of the general formula (V) are used in a specific layer, it is preferable that at least one is heat-treated.

The pH during the dispersion and the heat treatment after the dispersion may be any conditions as long as the dispersion is stably present, preferably pH 2.0 or more and 8.0 or less, more preferably 2.0 or more and 6.5 or less, and still more preferably 2. .5 or more and less than 4.5. The pH during the heat treatment is preferably in this range from the viewpoint of improving the film strength of the coated product.
For adjusting the pH of the dispersion, for example, sulfuric acid, hydrochloric acid, acetic acid, citric acid, phosphoric acid, oxalic acid, carbonic acid, sodium hydrogen carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide or a buffer solution thereof can be used. .

  The temperature for the heat treatment varies depending on the heat treatment process, the size and shape of the powder or particles, the heat treatment conditions, the solvent, and so on. In the case of heat treatment with powder, 40 to 200 ° C. is appropriate, preferably 50 to 150 ° C., and in the case of heat treatment in a solvent, 40 to 150 ° C., preferably 50 to 150 ° C., dispersed. 40-90 ° C. is suitable for heat treatment during, preferably 50-90 ° C., and 40-100 ° C. is suitable for heat treatment of the dispersion after dispersion, preferably 50-95 ° C. More preferably, it is 60-95 degreeC, Most preferably, it is 70-95 degreeC. If the temperature of the heat treatment is lower than 40 ° C., the effect may be poor and may not be preferable.

  When the heat treatment is performed in a solvent, the type of the solvent is not limited as long as it does not substantially dissolve the dye. For example, water, alcohols (for example, methanol, ethanol, isopropyl alcohol, butanol, isoamyl amyl) Coal, octanol, ethylene glycol, diethylene glycol, ethyl cellosolve), ketones (eg, acetone, methyl ethyl ketone), esters (eg, ethyl acetate, butyl acetate), alkyl carboxylic acids (eg, acetic acid, propionic acid), nitriles ( For example, acetonitrile), ethers (for example, dimethoxyethane, dioxane, tetrahydrofuran), amides (for example, dimethylformamide) and the like can be mentioned.

  Further, even when these solvents alone dissolve the dye, they can be used if the dye does not substantially dissolve by mixing with water or other solvents or adjusting the pH.

  The time for the heat treatment is not general, and it takes a long time if the temperature is low, and a short time if the temperature is high. Although it can set arbitrarily so that heat processing can be implement | achieved within the range which has no influence on a manufacturing process, it is preferable that it is normally 1 hour-4 days.

In order to provide a layer containing dye fine particles in a photographic light-sensitive material, the fine particles thus obtained are dispersed in a suitable binder to prepare a substantially uniform solid dispersion of particles. It can be provided by coating on a desired support.
The binder is not particularly limited as long as it is a hydrophilic colloid that can be used in a photosensitive emulsion layer or a non-photosensitive layer, but usually a gelatin or a synthetic polymer such as polyvinyl alcohol or polyacrylamide is used.

  The fine particles in the solid dispersion preferably have an average particle size of 0.005 to 10 μm, preferably 0.01 to 1 μm, more preferably 0.01 to 0.7 μm. This range is preferable in terms of the non-aggregation property of the fine particles and the light absorption efficiency. The solid fine particle dispersion of the dye of the general formula (V) preferably used in the present invention can be used alone or in combination with a plurality of solid fine particle dispersions.

  Furthermore, the hydrophilic colloid layer (silver halide emulsion layer, non-photosensitive hydrophilic colloid layer) to which solid fine particles are added may be a single layer or a plurality of layers. For example, when adding a single solid fine particle dispersion to only one layer, dividing and adding to a plurality of layers, adding a plurality of solid fine particle dispersions to only one layer simultaneously, adding to separate layers, etc. As an example, it is not limited to the above.

Further, the solid fine particle dispersion can be incorporated in a necessary amount as an antihalation layer and can be added to the photosensitive silver halide emulsion layer to prevent irradiation.
The hydrophilic colloid layer containing the solid fine particle dispersion of the dye represented by formula (V) preferably used in the present invention is preferably provided between the support and the silver halide emulsion layer closest thereto. . Here, a non-photosensitive hydrophilic colloid layer other than the hydrophilic colloid layer containing the solid fine particle dispersion may be provided between the support and the silver halide emulsion layer closest thereto.

The solid fine particle dispersion of the dye preferably used in the present invention is contained in the non-photosensitive hydrophilic colloid layer in the silver halide photographic light-sensitive material according to the hue of the dye, and a plurality of the non-photosensitive layers are provided. In the light-sensitive material of the present embodiment, it can be contained in these plural layers.
0.1-50 mass% is suitable for the dye density | concentration in the solid fine particle dispersion used preferably of this invention, Preferably it is 2-30 mass%. A dye concentration within this range is preferred from the viewpoint of the viscosity of the dispersion. The preferred coating amount of the solid fine particle dye is about 0.05 to 0.5 g / m ² .

In the present invention, the compound represented by the following general formula (IX) is preferably contained in the same photographic constituent layer together with the solid fine particle dispersion.
General formula (IX)
P-((S) _m -R) _n
In general formula (IX), R represents a hydrogen atom, a hydrophobic group or a hydrophobic polymer, P includes at least one of the following structural units A, B and C, and the polymerization degree of P is 10 or more. It represents a polymer of 3500 or less. n represents 1 or 2. m represents 1 or 0.

Here, R ³¹ represents -H or an alkyl group having 1 to 6 carbon atoms, R ³² represents -H or an alkyl group having 1 to 10 carbon atoms, R ³³ represents -H or -CH _3, R ³⁴ represents H, —CH ₃ , —CH ₂ COOH (including ammonium salt or metal salt) or —CN, X represents —H, —COOH (including ammonium salt or metal salt) or —CONH ₂ ; Y represents —COOH (including ammonium salt or metal salt), —SO ₃ H (including ammonium salt or metal salt), —OSO ₃ H (including ammonium salt or metal salt), —CH ₂ SO ₃ H (ammonium including salts or metal _{salts), - CONHC (CH 3)} 2 CH 2 SO 3 containing H (ammonium salts or metal salts) or ^{_{-CONHCH 2 CH 2 CH 2 N +}} (CH 3) 3 Cl - represents a.

  Details of the compound represented by the general formula (IX) preferably used in the present invention (specific description, preferred limitations, exemplary compounds, amount used, synthesis method, etc.), page 24, 46 of JP-A-11-95371. Column 27 line 33 to page 33 column 63 line 2 (paragraph numbers 0090 to 0128), which is incorporated as part of the specification of the present invention.

The silver halide color photographic light-sensitive material of the present invention is processed by a usual development process.
In particular, in the processing of silver halide color photographic light-sensitive materials for movies, the positive light-sensitive materials for movies can be processed by the following processing steps conventionally used. In the case of the positive photosensitive material for movies of the present invention, the steps of (1) prebath bath and (2) water washing bath for removing the resin back layer can be reduced. Further, such a shortened processing step is preferable for simplification of processing.
In addition, when forming a sound track with a dye image, the steps (6) first fixing bath, (7) water washing bath, (11) sound development and (12) water washing can be eliminated, which greatly simplifies processing. This is a preferred embodiment. The silver halide light-sensitive material of the present invention can exhibit excellent performance even in such processing steps.
Further, in place of persulfuric acid conventionally used in a bleaching bath, a bleaching bath mainly composed of a PDTA-iron complex called UL bleach in the industry can be used. In this case, the bleaching acceleration bath process can be eliminated.

Standard processing (excluding drying) for conventional film positive photosensitive materials
(1) Prebath bath (2) Washing bath (3) Color development bath (4) Stop bath (5) Washing bath (6) First fixing bath (7) Washing bath (8) Bleaching acceleration bath (9) Bleaching bath (10) Washing bath (11) Sound development (painting development)
(12) Washing water (13) Second fixing bath (14) Washing bath (15) Stabilization bath

  In the present invention, among the above processing steps, the color development time (step (3) above) is 2 minutes 30 seconds or less (lower limit is preferably 6 seconds or more, more preferably 10 seconds or more, further preferably 20 seconds). Above, most preferably 30 seconds or more), more preferably 2 minutes or less (lower limit is the same as 2 minutes 30 seconds), the effect of the present invention is remarkably preferable.

Next, the photographic layer of the silver halide color photographic light-sensitive material of the present invention will be described.
The silver halide color photographic light-sensitive material of the present invention is a silver halide color photographic light-sensitive material having a transmission type support, and a plurality of silver halide emulsion layers having substantially different color sensitivities are formed on the support. And a silver halide color photographic material having at least one photosensitive layer. The present invention can be applied to color photographic light-sensitive materials for general use such as color positive film and movie positive film and movie.
In particular, it is preferably applied to a color positive photosensitive material for movies.

  In the present invention, the number and order of the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer are not particularly limited. Each of the yellow, cyan and magenta color-sensitive photosensitive silver halide emulsion layers is composed of a plurality of silver halide emulsion layers having the same color sensitivity and different sensitivities, even if the photosensitive silver halide emulsion layer is composed of one photosensitive silver halide emulsion layer. It may be.

There is no restriction between the color developability and color sensitivity of each color-sensitive photosensitive silver halide emulsion layer. For example, a color developable light-sensitive silver halide emulsion layer has color sensitivity in the infrared region. It doesn't matter.
Examples of typical layer order include a non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of the dye of the present invention, a yellow color-forming photosensitive silver halide emulsion layer, and a non-photosensitive hydrophilic layer in order from the support. Colloid layer (color mixing prevention layer), cyan color developing photosensitive silver halide emulsion layer, non-photosensitive hydrophilic colloid layer (color mixing preventing layer), magenta color developing photosensitive silver halide emulsion layer, non-photosensitive hydrophilic colloid layer (Protective layer). However, depending on the purpose, the order of installation may be changed, or the number of photosensitive silver halide emulsion layers or non-photosensitive hydrophilic colloid layers may be increased or decreased.

  In the present invention, gelatin is preferably used as the hydrophilic colloid. If necessary, other hydrophilic colloids can be used in place of gelatin at any ratio. Examples of these include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin or casein, cellulose derivatives (eg, hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfate), saccharides such as sodium alginate and starch derivatives. And a wide range of synthetic polymers such as poly (N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole).

  Examples of the silver halide grains used in the present invention include silver chloride, silver bromide, (iodo) silver chlorobromide, and silver iodobromide. In particular, in the present invention, silver chloride, silver chlorobromide, silver chloroiodide and silver chloroiodobromide having a silver chloride content of 95 mol% or more can be preferably used in order to speed up the development processing time. The silver halide grains in this emulsion are those having regular crystals such as cubes, octahedrons and tetradecahedrons, those having irregular crystal systems such as spheres and plates, twin planes, etc. Those having the above crystal defects or a composite system thereof may be used. Further, it is preferable to use tabular grains whose main plane is the (111) plane or the (100) plane in terms of speeding up color development and reducing processing color mixing. As for tabular high silver chloride emulsion grains having a main plane of (111) or (100), JP-A-6-138619, US Pat. Nos. 4,399,215, 5,061,617, 5,320,938, 5,264,337, It can be prepared by the methods disclosed in 5,292,632, 5,314,798, 5,413,904, International Publication WO94 / 22051 and the like.

  As the silver halide emulsion that can be used together in the present invention, a silver halide emulsion having an arbitrary halogen composition may be used. From the viewpoint of rapid processability, a salt (iodinated) salt having a silver chloride content of 95 mol% or more. Silver and silver salt (iodo) bromide are preferable, and a silver halide emulsion having a silver chloride content of 98 mol% or more is more preferable.

Silver halide grains in photographic emulsions have regular crystal shapes such as cubes, octahedrons, tetradecahedrons, crystal defects such as twin planes, as in the emulsions of the present invention, or Their composite form may also be used.
The grain size of the silver halide may be a fine grain having a grain size of about 0.2 μm or less or a large grain having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. Is preferably monodispersed for the purpose of accelerating development, and the coefficient of variation of the grain size of each silver halide grain is preferably 0.3 or less (preferably 0.3 to 0.05), Preferably, it is 0.25 or less (preferably 0.25 to 0.05). The variation coefficient here is represented by a ratio (s / d) between a statistical standard deviation value (s) and an average particle size (d).

  The silver halide photographic emulsion that can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pages 22 to 23, “I. Emulsion preparation and types”. No. 18716 (November 1979), page 648, No. 307105 (November 1989), pages 863 to 865, and Grafkide's "Physics and Chemistry of Photography", published by Paul Monter Glafkides, Chemie et Phisique Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Chemistry, Focal Press, 1966), "Production and Coating of Photoemulsions" by Zerikman et al. And the method described in Focal Press (VL Zelikman, et al., Making and Coating Photographic Emulsion, Focal Press, 1964) and the like.

Also preferred are monodisperse emulsions described in US Pat. Nos. 3,574,628, 3,655,394, and British Patent 1,413,748.
Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Gatoff, Photographic Science and Engineering, Vol. 14, pp. 248-257 (1970); US Pat. Nos. 4,434,226, 4,414,310, It can be easily prepared by the methods described in US Pat. Nos. 4,433,048, 4,439,520 and British Patent 2,112,157.

  The crystal structure may be uniform, the inside and outside may be composed of different halogen compositions, or a layered structure may be formed. Silver halides having different compositions may be bonded by epitaxial bonding, and may be bonded to a compound other than silver halide, such as rhodium silver or lead oxide. Also, a mixture of various crystal grains may be used.

  The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image types, the core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used, and the preparation method thereof is described in JP-A-59-133542. . Although the thickness of the shell of this emulsion varies depending on the development processing or the like, it is preferably 3 to 40 nm, and particularly preferably 5 to 20 nm.

As the silver halide emulsion, those subjected to physical ripening, chemical ripening and spectral sensitization are usually used. Additives used in such processes are described in RD No. 17643, No. 18716 and No. 307105, and the corresponding parts are summarized in the following table.
In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different in grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used.

The coated silver amount in the silver halide color photographic light-sensitive material of the present invention is preferably 6.0 g / m ² or less, more preferably 4.5 g / m ² or less, 2.0 g / m ² or less is most preferred. The applied silver amount is 0.01 g / m ² or more, preferably 0.02 g / m ² or more, more preferably 0.5 g / m ² or more.

In any one of the photographic constituent layers composed of a photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer (intermediate layer, protective layer, etc.) provided on the support, preferably a silver halide emulsion layer The 1-aryl-5-mercaptotetrazole compound is preferably added in an amount of 1.0 × 10 ^{−5 to} 5.0 × 10 ⁻² mol, and more preferably 1.0 × 10 ⁻⁴ to 1 per mol of silver halide. It is preferable to add 0.0 × 10 ⁻² mol. By adding in this range, the stain on the processed color photographic surface after the continuous processing can be further reduced.

As such a 1-aryl-5-mercaptotetrazole compound, an aryl group at the 1-position is preferably an unsubstituted or substituted phenyl group, and preferred specific examples of this substituent include acylamino groups (for example, acetylamino, -NHCOC ₅ H ₁₁ (n) etc.), ureido group (eg methylureido etc.), alkoxy group (eg methoxy etc.), carboxylic acid group, amino group, sulfamoyl group etc. A plurality (2 to 3 etc.) may be bonded. Further, the position of the substituent is preferably the meta or para position.
Specific examples thereof include 1- (m-methylureidophenyl) -5-mercaptotetrazole and 1- (m-acetylaminophenyl) -5-mercaptotetrazole.

The photographic additives that can be used or used in the present invention are described in the following Research Disclosure Journal (RD), and the description locations related to the following table are shown.
Type of additive RD17643 RD18716 RD307105
1) Chemical sensitizer, page 23, page 648, right column, page 866 2) Sensitivity enhancer, page 648, right column 3) Spectral sensitizer, pages 23-24, page 648, right column, pages 866-868, supersensitizer, page 649 Right column 4) Whitening agent page 24 647 page right column 868 page 5) Light absorber, 25-26 page 649 Right column 873 Filter dye, 650 page left column UV absorber 6) Binder page 26 page 651 left Column 873 to 874 7) Plasticizer, Lubricant 27 page 650 Right column 876 page 8) Coating aid, 26 to 27 page 650 Right column 875 to 876 Surface active agent 9) Antistatic agent page 27 650 Right column, pages 876-877
10) Matting agent 878-879 pages

In the silver halide color photographic light-sensitive material of the present invention, various dye-forming couplers can be used, but the following dye-forming couplers are particularly preferable.
Yellow coupler: coupler represented by formulas (I) and (II) of European Patent EP502,424A; coupler represented by formulas (1) and (2) of European Patent EP513,496A (particularly Y on page 18) -28); couplers represented by general formula (I) in claim 1 of JP-A-5-307248; represented by general formula (I) on lines 45 to 55 of column 1 of US Pat. No. 5,066,576 A coupler; a coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-74425; a coupler described in claim 1 on page 40 of European Patent EP498,381A1 (particularly D-35 on page 18); A coupler represented by the formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y-54 (page 41)); column 7, lines 36 to 58 of US Pat. No. 4,476,219 (II-17, 19 (column 17), II-24 (column 19)) represented by the formulas (II) to (IV).

Magenta coupler; JP-A-3-97737 (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13)); European Patent EP456,257 A- 4-63 (page 134), A-4-73, -75 (page 139); European Patent EP486,965, M-4, -6 (page 26), M-7 (page 27); -43611, paragraph 0024 M-45, JP-A-5-204106, paragraph 0036 M-1; JP-A-4-362631, paragraph 0237 M-22.
Cyan coupler: CX-1, 3, 4, 5, 11, 12, 14, 15 (pages 14 to 16) of JP-A-4-204843; C-7, 10 (page 35) of JP-A-4-43345 , 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); represented by the general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385 Coupler.
Polymer coupler: P-1, P-5 (page 11) of JP-A-2-44345.
Infrared coupler for forming a sound track: couplers described in JP-A-63-143546 and the publications cited therein.

As couplers in which the coloring dye has an appropriate diffusibility, those described in US Pat. No. 4,366,237, German Patent GB2,125570, European Patent EP96,873B, German Patent DE3,234,533 are preferable.
A coupler for correcting unwanted absorption of a coloring dye is a yellow colored cyan coupler represented by the formula (CI), (CII), (CIII), (CIV) described on page 5 of European Patent EP456,257A1 (Especially YC-86 on page 84), yellow colored magenta coupler ExM-7 (page 202, EX-1 (page 249), EX-7 (page 251), U.S. Pat. Magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10), US Pat. No. 4,837,136 (2) (column 8), expressed by the formula [C-1] of claim 1 of WO92 / 11575 The colorless masking couplers (especially exemplified compounds on pages 36 to 45) are preferred.

  Examples of compounds (including dye-forming couplers) that react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound: a compound represented by any one of formulas (I), (II), (III), and (IV) described on page 11 of European Patent EP378,236A1 (particularly T-101 (page 30)) ), T-104 (page 31), T-113 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), European Patent EP436,938A2 Compounds represented by formula (I) described on page 7 (especially D-49 (page 51)), compounds represented by formula (1) of JP-A-5-307248 (particularly paragraph (0027) of paragraph 0027) A compound represented by any one of formulas (I), (II) and (III) described on pages 5 to 6 of European Patent EP440,195A2 (particularly I- (1) on page 29); Release compounds: compounds represented by formulas (I) and (I ') on page 5 of EP 310,125A2 (especially (60) and (61) on page 61) and claims of JP-A-6-59411 1 compound represented by formula (I) (particularly, paragraph (7) of paragraph 0022); ligand-releasing compound: compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478 (particularly column 21) Compound on line 41); leuco dye releasing compound; US patent Compounds 1-6 of columns 3-8 of 4,749,641; fluorescent dye releasing compounds: compounds represented by COUP-DYE of claim 1 of US Pat. No. 4,774,181 (especially compounds 1-11 of columns 7-10); development acceleration Or compound release compounds: compounds of formula (1), (2), (3) in column 3 of US Pat. No. 4,656,123 (especially (I-22) of column 25) and European Patent EP450,637A2 ExZK-2, page 75, lines 36-38 of No. 1; a compound that releases a group that becomes a dye only after leaving: a compound represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (particularly, columns 25-36) Y-1 ~ Y-19).

As additives other than the dye-forming coupler, the following are preferable.
Oil-soluble organic compound dispersion medium: JP-A 62-215272, P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 (140- 144); Latex for impregnation with oil-soluble organic compound: Latex described in US Pat. No. 4,199,363; Oxidant scavenger for developing agent: represented by Formula (I) in columns 2 to 54 of US Pat. No. 4,978,606 Compounds (especially I- (1), (2), (6), (12) (columns 4-5), US Pat. No. 4,923,787, column 2, lines 5-10, especially compounds 1 (column 3 Stain inhibitor: European Patent EP298321A, page 4, lines 30 to 33, formulas (I) to (III), especially I-47, 72, III-1, 27 (pages 24 to 48); European Patent EP298321A A-6, 7, 20, 21, 23, 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 94, 164 (pages 69-118), United States Patents 5,122,444, columns 25-38, II-1 to III-23, especially III-10, European Patent EP471347A, pages 8-12, I-1 to III-4, especially II-2, U.S. Pat.No. 5,139,931 No. columns 32-40, A-1 to 48, especially A-39, 42; Materials that reduce the use of enhancers or color mixing inhibitors: European patent EP411324A, pages 5-24, I-1 to II-15, especially I-46; Formalin scavenger: European patent EP477932A, pages 24 to 29 SCV-1 to 28, especially SCV-8;

  Hardener: Compounds represented by formulas (VII) to (XII) in columns 13 to 23 of H-1, 4, 6, 8, 14, U.S. Pat. No. 4,618,573 on page 17 of JP-A 1-214845 (H-1 to 54), compound (H-1 to 76) represented by the formula (6) at the lower right of page 8 of JP-A-2-14852, particularly H-14, claim 1 of US Pat. No. 3,325,287 Development inhibitor precursor: P-24, 37, 39 (pages 6-7) of JP-A-62-168139; compounds described in claim 1 of US Pat. No. 5,019,492, in particular column 28 ~ 29; preservatives, antifungal agents: U.S. Pat. No. 4,923,790, columns 3 to 15, I-1 to III-43, especially II-1, 9, 10, 18, III-25; stabilizers, antifoggants US Pat. No. 4,923,793, columns 6-16, I-1 to (14), especially I-1, 60, (2), (13), US Pat. No. 4,952,483, compounds 25 to 32, compounds 1 to 65 36: Chemical sensitizer: Triphenylphosphine selenide, Compound 50 of JP-A-5-40324; Dye that can be used in combination: a-1 to b-20 on pages 15 to 18 of JP-A-3-156450, Especially a- 1, 12, 18, 27, 35, 36, b-5, V-1 to 23 on pages 27 to 29, especially V-1, FI-1 to F-II- on pages 33 to 55 of EP445627A 43, especially FI-11, F-II-8, III-36 on pages 17-28 of European Patent EP457153A, especially III-1, 3, 8-26 Dye-1 on WO88 / 04794 A microcrystalline dispersion of 124, compounds 1 to 22 on pages 6 to 11 of EP 319999A, in particular compound 1, compounds D-1 to 87 represented by formulas (1) to (3) of EP 519306A 3 to 28), compounds 1 to 22 represented by formula (I) in US Pat. No. 4,268,622 (columns 3 to 10), compounds (1) to formula (I) represented by US Pat. No. 4,923,788 (31) (columns 2 to 9); UV absorber: compounds (18b) to (18r), 101 to 427 (pages 6 to 9) represented by formula (1) in JP-A-46-3335, Europe Patent EP520938A compounds (3) to (66) (pages 10 to 44) represented by formula (I) and compounds HBT-1 to HBT-10 (page 14) represented by formula (III), European patent Compounds (1) to (31) represented by formula (1) of EP521823 (columns 2 to 9).

  The silver halide color photographic light-sensitive material of the present invention contains fluorine atoms in the layer farthest from the support having the emulsion layer or the layer farthest from the support having no emulsion layer, or both. A compound can be preferably used. Of these, the compounds described in Japanese Patent Application No. 2001-308855 are preferably used.

In the silver halide color photographic light-sensitive material of the present invention, the total hydrophilic colloid layer on the side having the emulsion layer preferably has a total film thickness of 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, 16 μm or less is particularly preferable.
The total film thickness is 0.1 μm or more, preferably 1 μm or more, and more preferably 5 μm or more.
The film swelling speed T1 / 2 is preferably 60 seconds or less, and more preferably 30 seconds or less. T1 / 2 is defined as the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when processed for 3 minutes at 35 ° C with a color developer is defined as the saturated film thickness. . Film thickness means the film thickness measured at 25 ° C and 55% relative humidity (2 days), and T1 / 2 is photographic science and engineering (A.Green et al.) Photogr. Sci. Eng), Vol. 19, 2, pp. 124-129. T1 / 2 can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating.

Further, the swelling rate is preferably 180 to 280%, and more preferably 200 to 250%.
Here, the swelling rate is a scale representing the amount of equilibrium swelling when the silver halide photographic light-sensitive material of the present invention is immersed in 35? Distilled water and swollen.
Swell ratio (unit:%) = total film thickness during swelling / total film thickness during drying × 100
Is defined.
The swelling ratio can be adjusted to the above range by adjusting the amount of gelatin hardener added.

Hereinafter, the support will be described.
In the present invention, a transparent support is preferable, and a plastic film support is more preferable.
Examples of the plastic film support include polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, polycarbonate, polystyrene, and polyethylene.

  Among these, a polyethylene terephthalate film is preferable, and a biaxially stretched and heat-set polyethylene terephthalate film is particularly preferable from the viewpoint of stability and toughness.

Although there is no restriction | limiting in particular as thickness of the said support body, 15-500 micrometers is common, especially 40-200 micrometers is preferable from points, such as a handleability and versatility, and 85-150 micrometers is the most preferable.
The transmissive support preferably means a substrate that transmits 90% or more of visible light, and contains dyed silicon, alumina sol, chromium salt, zirconium salt, etc. as long as it does not substantially interfere with light transmission. It may be.

In order to firmly adhere the photosensitive layer to the surface of the plastic film support, the following surface treatment is generally performed. The same surface treatment is generally performed on the surface on which the antistatic layer (back layer) is formed.
(1) Directly after surface activation treatment such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxygen treatment, etc. A method of obtaining adhesion by applying a photographic emulsion (photosensitive layer forming coating solution);
(2) After these surface treatments, there are two methods: a method in which an undercoat layer is provided and a photographic emulsion layer is applied thereon.

  Of these, the method (2) is more effective and widely used. In any of these surface treatments, a slightly polar group is formed on the surface of the support that was originally hydrophobic, a thin layer that is a negative factor for surface adhesion is removed, It seems to increase the crosslink density and increase the adhesive strength. As a result, the affinity with the polar group of the component contained in the undercoat layer solution increases and the fastness of the adhesive surface increases. It is considered that the adhesion between the undercoat layer and the support surface is improved.

A non-photosensitive layer containing conductive metal oxide particles is preferably provided on the surface of the plastic film support on which the photosensitive layer is not provided.
As the binder for the non-photosensitive layer, acrylic resin, vinyl resin, polyurethane resin and polyester resin are preferably used. The non-photosensitive layer of the present invention is preferably hardened, and examples of the hardener include aziridines, triazines, vinyl sulfones, aldehydes, cyanoacrylates, peptides, epoxies, and melamines. Although used, a melamine compound is particularly preferable from the viewpoint of firmly fixing the conductive metal oxide particles.

The material of the conductive metal oxide particles includes ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₃ and V ₂ O _5, and complex oxides thereof, and these Examples of the metal oxide further include metal oxides containing different atoms.

As the metal oxide, SnO ₂ , ZnO, Al ₂ O ₃ , TiO ₂ , In ₂ O ₃ , MgO, and V ₂ O ₅ are preferable, and SnO ₂ , ZnO, In ₂ O ₃ , TiO _2, and V ₂ are further preferable. O ₅ is preferred, and SnO ₂ and V ₂ O ₅ are particularly preferred. Examples of containing a small amount of different atoms include Zn or Al, In, TiO ₂ Nb or Ta, In ₂ O ₃ Sn, and SnO ₂ Sb, Nb or halogen elements. An element doped with 0.01 to 30 mol% (preferably 0.1 to 10 mol%) of the element can be used. If the amount of the different element added is less than 0.01 mol%, sufficient conductivity cannot be imparted to the oxide or composite oxide. If it exceeds 30 mol%, the degree of blackening of the particles increases, and charging Since the prevention layer is darkened, it is not suitable for a photosensitive material. Accordingly, the material of the conductive metal oxide particles is preferably a material containing a small amount of a different element with respect to the metal oxide or the composite metal oxide. Also preferred are those containing an oxygen defect in the crystal structure.

The conductive metal oxide particles should have a volume ratio of 50% or less with respect to the entire non-photosensitive layer, but preferably 3 to 30%. The coating amount preferably conforms to the conditions described in JP-A-10-62905.
When the volume ratio exceeds 50%, dirt is likely to adhere to the surface of the processed color photograph. When the volume ratio is less than 3%, the antistatic ability does not function sufficiently.

  The particle diameter of the conductive metal oxide particles is preferably as small as possible in order to reduce light scattering as much as possible, but should be determined using the ratio of the refractive index of the particles to the binder as a parameter, and Mie's theory Can be obtained using In general, the average particle size is 0.001 to 0.5 μm, preferably 0.003 to 0.2 μm. Here, the average particle size is a value including not only the primary particle size of the conductive metal oxide particles but also the particle size of the higher order structure.

  When the metal oxide fine particles are added to the coating solution for forming the antistatic layer, they may be added and dispersed as they are, but they are dispersed in a solvent such as water (including a dispersant and a binder as necessary). It is preferably added in the form of a dispersion.

  The non-photosensitive layer preferably contains a cured product of the binder and the hardener as a binder for dispersing and supporting the conductive metal oxide particles. In the present invention, from the viewpoint of maintaining a good working environment and preventing air pollution, it is preferable to use water-soluble binders and hardeners, or use them in an aqueous dispersion state such as an emulsion. Moreover, it is preferable that a binder has any group of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group so that a crosslinking reaction with a hardening agent is possible. A hydroxyl group and a carboxyl group are preferred, and a carboxyl group is particularly preferred. The content of the hydroxyl group or carboxyl group in the binder is preferably 0.0001 to 1 equivalent / 1 kg, particularly preferably 0.001 to 1 equivalent / 1 kg.

Hereinafter, the resin preferably used as the binder will be described.
As acrylic resin, acrylic acid; acrylic acid esters such as alkyl acrylate; acrylamide; acrylonitrile; methacrylic acid; methacrylic acid esters such as alkyl methacrylate; homopolymer of any monomer of methacrylamide and methacrylonitrile Or a copolymer obtained by polymerization of two or more of these monomers. Among these, homopolymers of monomers of acrylic acid esters such as alkyl acrylates and methacrylic acid esters such as alkyl methacrylates, or copolymers obtained by polymerization of two or more of these monomers Is preferred. For example, a homopolymer of any one of acrylic acid esters and methacrylic acid esters having an alkyl group having 1 to 6 carbon atoms, or a copolymer obtained by polymerization of two or more of these monomers. .

  The acrylic resin is mainly composed of a monomer having any one of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group so that a crosslinking reaction with the hardener is possible with the above composition as a main component. It is preferable that the polymer is obtained in the above manner.

  Examples of the vinyl resin include polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl polymer, polyvinyl butyral, polyvinyl methyl ether, polyolefin, ethylene / butadiene copolymer, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, vinyl chloride / A (meth) acrylic acid ester copolymer and an ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / (meth) acrylic acid ester copolymer) can be mentioned. Among these, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl polymer, polyolefin, ethylene / butadiene copolymer and ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / acrylic ester copolymer). preferable.

  The vinyl resin is polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl holmaral, polyvinyl butyral, polyvinyl methyl ether, and polyvinyl acetate so that a crosslinking reaction with a hardener is possible. The other polymer is a polymer obtained by partially using a monomer having any one of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group.

Examples of the polyurethane resin include polyhydroxy compounds (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane), aliphatic polyester polyols obtained by reaction of polyhydroxy compounds and polybasic acids, polyether polyols (eg, Polyurethane derived from poly (oxypropylene ether) polyol, poly (oxyethylene-propylene ether) polyol), polycarbonate-based polyol, and polyethylene terephthalate polyol, or a mixture thereof and polyisocyanate can be given.
In the polyurethane resin, for example, the hydroxyl group remaining unreacted after the reaction between polyol and polyisocyanate can be used as a functional group capable of crosslinking reaction with the hardener.

As the polyester resin, generally used is a polymer obtained by reacting a polyhydroxy compound (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane) with a polybasic acid.
In the polyester resin, for example, after the reaction between the polyol and the polybasic acid is completed, the hydroxyl group and carboxyl group remaining unreacted can be used as functional groups capable of crosslinking reaction with the hardener. Of course, a third component having a functional group such as a hydroxyl group may be added.
Among the above polymers, acrylic resins and polyurethane resins are preferable, and acrylic resins are particularly preferable.

The melamine compound preferably used as a hardener includes a compound containing two or more (preferably three or more) methylol groups and / or alkoxymethyl groups in the melamine molecule and a melamine resin which is a condensation polymer thereof. Examples include melamine and urea resin.
Examples of the initial condensate of melamine and formalin include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine and the like. Sumitex Resin) M-3, MW, MK, and MC (manufactured by Sumitomo Chemical Co., Ltd., all trade names), but are not limited thereto.

  Examples of the condensation polymer include hexamethylol melamine resin, trimethylol melamine resin, trimethylol trimethoxymethyl melamine resin, and the like. Commercially available products include MA-1 and MA-204 (manufactured by Sumitomo Bakelite Co., Ltd., both trade names), BECKAMINE MA-S, becamine APM and becamine J-101 (Dainippon Ink Chemical Co., Ltd.) Product name), Euroid 344 (trade name, manufactured by Mitsui Toatsu Chemicals Co., Ltd.), Oka Resin M31 and Oka Resin PWP-8 (product names manufactured by Oka Shinko Co., Ltd., both). However, it is not limited to these.

As a melamine compound, it is preferable that the functional group equivalent shown by the value which divided molecular weight by the number of functional groups in 1 molecule is 50-300. Here, the functional means a methylol group and / or an alkoxymethyl group. If this value exceeds 300, the cured density is small and a high strength cannot be obtained. If the amount of the melamine compound is increased, the coating property is lowered. If the curing density is low, scratches are likely to occur. Moreover, when the grade to harden | cure is low, the force holding an electroconductive metal oxide will also fall. If the functional group equivalent is less than 50, the curing density is increased, but the transparency is impaired, and even if the amount is reduced, it does not improve.
The addition amount of the aqueous melamine compound is 0.1 to 100% by mass, preferably 10 to 90% by mass with respect to the polymer.

If necessary, the antistatic layer can be used in combination with a matting agent, a surfactant, a slipping agent and the like.
Examples of the matting agent include oxides such as silicon oxide, aluminum oxide, and magnesium oxide having a particle diameter of 0.001 to 10 μm, and polymers or copolymers such as polymethyl methacrylate and polystyrene.

Examples of the surfactant include arbitrary anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.
Examples of the slip agent include phosphate esters of higher alcohols having 8 to 22 carbon atoms or amino salts thereof; palmitic acid, stearic acid, behenic acid and esters thereof; and silicone compounds.

The thickness of the antistatic layer is preferably 0.01 to 1 μm, more preferably 0.01 to 0.2 μm. If the thickness is less than 0.01 μm, it is difficult to uniformly apply the coating agent, and thus uneven coating tends to occur on the product. If it exceeds 1 μm, the antistatic performance and scratch resistance may be inferior.
A surface layer is preferably provided on the antistatic layer. The surface layer is provided mainly for improving the slipping property and scratch resistance and for assisting the detachment preventing function of the conductive metal oxide particles of the antistatic layer.

  Examples of the material for the surface layer include (1) wax, resin and rubber-like ones or copolymers of 1-olefinic unsaturated hydrocarbons such as ethylene, propylene, 1-butene and 4-methyl-1-pentene. Products (for example, polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer and propylene / 1-butene copolymer), (2) A rubbery copolymer of two or more kinds of the 1-olefin and a conjugated or non-conjugated diene (for example, an ethylene / propylene / ethylidene norbornene copolymer, an ethylene / propylene / 1,5-hexadiene copolymer, and Isobutene / isoprene copolymer), (3) a copolymer of 1-olefin and conjugated or non-conjugated diene (for example, ethylene / Tadiene copolymers and ethylene / ethylidene norbornene copolymers), (4) 1-olefins, especially copolymers of ethylene and vinyl acetate and complete or partially saponified products thereof, and (5) 1-olefins alone or copolymerized. Examples thereof include, but are not limited to, a graft polymer obtained by grafting the above conjugated or non-conjugated diene or vinyl acetate onto a polymer, and a completely or partially saponified product thereof. The above compounds are described in JP-B-5-41656.

  Among these, polyolefins having a carboxyl group and / or a carboxylate group are preferable. Usually used as an aqueous solution or aqueous dispersion.

  Water-soluble methylcellulose having a methyl group substitution degree of 2.5 or less may be added to the surface layer, and the addition amount is preferably 0.1 to 40% by mass with respect to the total binder forming the surface layer. The water-soluble methylcellulose is described in JP-A-1-210947.

  The surface layer may be formed on the antistatic layer by a well-known coating method such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, or extrusion coating. It can form by apply | coating the coating liquid (aqueous dispersion or aqueous solution) containing etc.

  The thickness of the surface layer is preferably 0.01 to 1 μm, more preferably 0.01 to 0.2 μm. When the thickness is less than 0.01 μm, it is difficult to uniformly apply the coating agent, and thus uneven coating tends to occur on the product.

  The pH of the film in the silver halide color photographic light-sensitive material of the present invention is preferably 4.5 to 6.5, more preferably 4.6 to 6.5, still more preferably 5.5 to 6.4. When the coating pH is higher than 6.5 in a long-time sample, the sensitization of the cyan image and the magenta image due to safelight irradiation is large. The yellow image density greatly changes with the time change until development. Either case is a practical problem.

The coating pH in the silver halide color photographic light-sensitive material of the present invention is the pH of all photographic layers obtained by coating the coating solution on the support and does not necessarily match the pH of the coating solution. The coating pH can be measured by the following method as described in JP-A-61-245153. That is,
(1) 0.05 ml of pure water is dropped on the surface of the light-sensitive material coated with the silver halide emulsion. next,
(2) After standing for 3 minutes, the coating pH is measured with a surface pH measurement electrode (GS-165F, trade name, manufactured by Toa Denpa). The coating pH can be adjusted using an acid (for example, sulfuric acid or citric acid) or an alkali (for example, sodium hydroxide or potassium hydroxide) as necessary.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

Example 1
[Preparation of support]
Subjecting a primer on the emulsion paint設面side, an acrylic resin layer containing a side opposite to the below of the conductive polymer (0.05g / m ²⁾ and tin oxide fine particles (0.20g / m ²⁾ of emulsion paint設面the A coated polyethylene terephthalate film support (thickness: 120 μm) was prepared.

[Preparation of emulsion]
The following red-sensitive emulsion (silver chlorobromide emulsion) was prepared.
It was prepared by adding an aqueous silver nitrate solution and a mixed aqueous solution of sodium chloride and potassium bromide by a control double jet method known in the art. The iridium content was adjusted to 2 × 10 ⁻⁷ mol / mol silver. Sensitizing dyes (A) to (C) represented by the structural formula described later were added to the emulsion as described below and spectrally sensitized.
Red-sensitive sensitizing dye (A): 4.5 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (B): 0.2 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (C): 0 .1 × 10 ⁻⁵ mol / mol silver Further, gold chloride is sensitized optimally using chloroauric acid and triethylthiourea, and then Cpd-A represented by the structural formula described later is converted to 1 mol of silver halide. 9.0 × 10 ⁻⁴ mol was added per hit.
The resulting emulsion had a cubic shape, an average grain size of 0.23 μm, a grain size distribution of 0.11, and a halogen composition of Br / Cl = 25/75.

[Preparation of emulsion layer coating solution]
Solvent (Solv-A) 130 ml and ethyl acetate 180 ml were dissolved in 116 g of coupler (ExC). This solution was emulsified and dispersed in 560 g of an 18% gelatin aqueous solution containing 100 ml of a 10% sodium dodecylbenzenesulfonate solution. This dispersion was mixed and dissolved with the emulsion, and a coating solution was prepared so as to have the following composition. In addition, sodium 1-oxy-3,5-dichloro-s-triazate was used as a hardener.

[Layer structure]
The layer structure of the sample used in this experiment is shown below. (The numbers indicate the coating amount per m ² (g / m ² ).)
[Support]
Polyethylene terephthalate film [emulsion layer]
Silver chlorobromide emulsion (above) 0.40
Coupler (ExC) 0.72
Solvent (Solv-A) 0.94
Gelatin 2.81
[Protective layer]
Gelatin 1.3
Acrylic modified polymer of polyvinyl alcohol (modified degree 17%) 0.17
Liquid paraffin 0.03

Sample 101 was produced as described above.
[Production of Samples 102 to 137]
Next, samples 102 to 137 were prepared by introducing the water-soluble dye of the present invention or the comparative dye as shown in Table 1 to the sample 101. The water-soluble dye was introduced by adding it to the emulsion layer coating solution. The structure of the comparative dye used in this example is shown below.

[Sample exposure and development]
For the samples 101 to 137 produced as described above, two types of light, red light and safelight light (produced by passing white light through No. 8 safelight glass manufactured by Eastman Kodak Company), are used. Imagewise exposure was performed with a wedge. The exposed sample was subjected to color development by an ECP-2D process announced by Eastman Kodak Company.
ECP-2D process (excluding sound development process)
<Process>
Process name Processing temperature (℃) Processing time (seconds) Replenishment amount
(Per ml 35mm x 30.48m)
1. Development 39.0 ± 0.1 180 690
2. Stop 27 ± 1 40 770
3. Washing with water 27 ± 3 40 1200
4). First fixing 27 ± 1 40 200
5). Washing with water 27 ± 3 40 1200
6). Bleach 27 ± 1 60 200
7). Washing with water 27 ± 3 40 1200
8). Second fixing 27 ± 1 40 200
9. Washing with water 27 ± 3 60 1200
10. Rinse 27 ± 3 10 400
11. Dry

<Processing liquid formulation>
Development tank solution showing composition per liter Replenisher
Kodak Anti
Calcium No. 4
(Product Name) 1.0ml 1.4ml
Sodium sulfite 4.35g 4.50g
CD-2 (trade name) 2.95 g 6.00 g
Sodium carbonate 17.1g 18.0g
Sodium bromide 1.72 g 1.60 g
Sodium hydroxide --- 0.6g
Sulfuric acid (7N) 0.62ml ―――
Stop Tank fluid Replenisher
Sulfuric acid (7N) 50ml 50ml
Fixing tank solution Replenisher (first ammonium thiosulfate (58%) 100ml 170ml
2nd common) Sodium sulfite 2.5g 16.0g
Sodium bisulfite 10.3g 5.8g
Potassium iodide 0.5g 0.7g
Bleaching tank solution Replenisher
Proxel GXL (trade name) 0.07ml 0.10ml
Aqueous ammonia (28%) 54.0 ml 64.0 ml
PDTA 44.8g 51.0g
Ammonium bromide 23.8g 30.7g
Acetic acid (90%) 10.0 ml 14.5 ml
Anhydrous iron nitrate 53.8g 61.2g
Rinse tank fluid Replenisher
Kodak Stabilizer Additive (trade name)
0.14ml 0.17ml
Dearside 702 (trade name)
0.7ml 0.7ml
In the above, CD-2 used in the developing process is a developing agent, and Proxel GXL used in the bleaching process and Dearcide 702 used in the rinsing process are antifungal agents.

[Sample evaluation]
The developed sample is subjected to density measurement through a red filter using an HPD type automatic density measuring machine manufactured by Fuji Photo Film Co., Ltd., and the relationship between exposure amount and color density (so-called sensitometry curve) is obtained. It was. On this sensitometric curve, the sensitivity was defined as the logarithm of the reciprocal of the exposure amount necessary to increase the color density by Dmin + 1.0. Next, for each of the red light exposure sample and the safelight light exposure sample, the difference between the sensitivity of each sample and each sensitivity in the sample 101 was taken, and the relative sensitivity (represented as ΔS (R) and ΔS (SL)) was calculated. When the relative sensitivity is positive, the sensitivity is higher than that of the sample 101, and when the relative sensitivity is negative, the sensitivity is lower than that of the sample 101. Furthermore, the difference between ΔS (R) and ΔS (SL) was shown for each sample. As this value is larger, the decrease in sensitivity to red light is smaller, and the decrease in sensitivity to safelight light is larger. Thus, favorable results are obtained in improving the safetylight safety.

  From the results in Table 1, when the dyes of the present invention are used in combination (samples 114 to 117, samples) compared to when each dye is used alone (samples 102 to 106, samples 110 to 113, and samples 118 to 121). It can be seen that 122-137) is superior in safe light safety. In particular, it can be seen that a higher effect can be obtained when three kinds of dyes of the present invention are used in combination (samples 131 to 137). In addition, when a dye other than the present invention is used in combination, the safety light safety improving effect cannot be obtained (samples 107 to 109). From the above, it can be seen that the safelight safety improving effect is exhibited only when the dye of the present invention is used in combination.

Example 2
[Preparation of silver halide emulsion]
-Preparation of blue-sensitive silver halide emulsion-
Large emulsion (BO-01)
(Cube, particle size 0.71 μm, particle size distribution 0.09, halogen composition Br / Cl = 3/97)
It was prepared by adding a silver nitrate aqueous solution and a mixed aqueous solution of sodium chloride and potassium bromide by a control double jet method known in the art. The iridium content was adjusted to 4 × 10 ⁻⁷ mol / mol silver. To this emulsion, sensitizing dyes (A ′) to (C ′) represented by the structural formula described later were added as follows.
Blue sensitizing dye (A ′); 3.5 × 10 ⁻⁵ mol / mol silver Blue sensitizing dye (B ′); 1.9 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (C ′); 1 .8 × 10 ^-5 mol / mol Ag was further optimally gold-sulfur sensitization using chloroauric acid and triethylthiourea.

Medium size emulsion (BM-01)
(Cube, particle size 0.52 μm, particle size distribution 0.09, halogen composition Br / Cl = 3/97)
It was prepared by adding a silver nitrate aqueous solution and a mixed aqueous solution of sodium chloride and potassium bromide by a control double jet method known in the art. The iridium content was adjusted to 6 × 10 ⁻⁷ mol / mol silver. To this emulsion, sensitizing dyes (A ′) to (C ′) represented by the structural formula described later were added as follows.
Blue sensitizing dye (A ′); 6.9 × 10 ⁻⁵ mol / mol silver Blue sensitizing dye (B ′); 2.3 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (C ′); 2 .Times.10.sup.- ⁵ mol / mol silver Further, gold sulfur was sensitized optimally using chloroauric acid and triethylthiourea.

Small emulsion (BU-01)
(Cube, particle size 0.31 μm, particle size distribution 0.08, halogen composition Br / Cl = 3/97)
The preparation of BM-01 emulsion was the same as BM-01 except that the grain formation temperature was lowered.
Sensitizing dyes (A ′) to (C ′) represented by the structural formula described below were added as follows.
Blue sensitizing dye (A ′): 8.5 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (B ′): 4.1 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (C ′): 3 .7 × 10 ^-5 mol / mol silver

-Preparation of red-sensitive silver halide emulsion-
Large size emulsion (RO-01)
(Cube, particle size 0.23 μm, particle size distribution 0.11, halogen composition Br / Cl = 25/75)
It was prepared by adding an aqueous silver nitrate solution and a mixed aqueous solution of sodium chloride and potassium bromide by a control double jet method known in the art. The iridium content was adjusted to 2 × 10 ⁻⁷ mol / mol silver. To this emulsion, sensitizing dyes (D ′) to (F ′) represented by the structural formula described later were added as follows and spectrally sensitized.
Red-sensitive sensitizing dye (D ′): 4.6 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (E ′): 0.2 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (F ′ ): 0.2 × 10 ⁻⁵ mol / mol silver Further, gold chloride is sensitized optimally using chloroauric acid and triethylthiourea, and then Cpd-71 represented by the structural formula described below is halogenated. 9.0 × 10 ⁻⁴ mol was added per 1 mol of silver.

Medium size emulsion (RM-01)
(Cube, particle size 0.174 μm, particle size distribution 0.12, halogen composition Br / Cl = 25/75)
The sensitizing dyes (D ′) to (F ′) represented by the structural formulas described later were used as described below in the same manner as RO-01 except that the particle formation temperature was changed.
Red-sensitive sensitizing dye (D ′): 7.1 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (E ′): 1.0 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (F ′ ): 0.4 × 10 ⁻⁵ mol / mol silver

Small emulsion (RU-01)
(Cube, particle size 0.121 μm, particle size distribution 0.13, halogen composition Br / Cl = 25/75)
The sensitizing dyes (D ′) to (F ′) represented by the structural formulas described later were used as described below in the same manner as RO-01 except that the particle formation temperature was changed.
Red-sensitive sensitizing dye (D ′): 8.9 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (E ′): 1.3 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (F ′ ): 0.5 × 10 ⁻⁵ mol / mol silver

-Preparation of green sensitive silver halide emulsion-
Large emulsion (GO-01)
(Cube, particle size 0.20 μm, particle size distribution 0.11, halogen composition Br / Cl = 3/97)
It was prepared by adding an aqueous silver nitrate solution and a mixed aqueous solution of sodium chloride and potassium bromide by a control double jet method known in the art. The iridium content was adjusted to 2 × 10 ⁻⁷ mol / mol silver. To this emulsion, sensitizing dyes (G ′) to (J ′) represented by the structural formula described later were added as follows and spectrally sensitized.
Green sensitive sensitizing dye (G ′): 2.8 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (H ′): 0.8 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (I ′ ): 1.2 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (J ′): 1.2 × 10 ⁻⁴ mol / mol silver Further, using chloroauric acid and triethylthiourea, Gold sulfur sensitized.

Medium size emulsion (GM-01)
(Cube, particle size 0.146 μm, particle size distribution 0.12, halogen composition Br / Cl = 3/97)
Except having changed the particle formation temperature, it was carried out similarly to GO-01, and used the sensitizing dye (G ')-(J') represented by the structural formula mentioned later as follows.
Green sensitive sensitizing dye (G ′): 3.8 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (H ′): 1.3 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (I ′ ): 1.4 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (J ′): 1.2 × 10 ⁻⁴ mol / mol silver

Small emulsion (GU-01)
(Cube, particle size 0.102 μm, particle size distribution 0.10, halogen composition Br / Cl = 3/97)
Except having changed the particle formation temperature, it was carried out similarly to GO-01, and used the sensitizing dye (G ')-(J') represented by the structural formula mentioned later as follows.
Green sensitive sensitizing dye (G ′): 5.1 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (H ′): 1.7 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (I ′ ): 1.9 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (J ′): 1.2 × 10 ⁻⁴ mol / mol silver

[Preparation of dye solid fine particle dispersion]
The methanol wet cake of the compound (V-40) was weighed so that the net amount of the compound was 240 g, 48 g of the compound (VIII-12) was weighed as a dispersion aid, and water was added to make 4000 g. A circulating sand grinder mill (UVM-2) (manufactured by IMEX K.K.) is filled with 1.7 liters of zirconia beads (0.5 mm diameter), discharged at a rate of 0.5 liter / min and a peripheral speed of 10 m / s. Milled for hours. Thereafter, the dispersion was diluted so that the compound concentration was 3% by mass, and a compound (Pm-1) represented by the following structural formula was added by 3% by mass with respect to the dye (referred to as Dispersion A). The average particle size of this dispersion was 0.45 μm.
Further, a dispersion containing 5% by mass of compound (V-4) (referred to as dispersion B) was obtained in the same manner.

[Preparation of Sample 201]
On the support, each layer having the composition as shown below was applied in multiple layers to prepare Sample 201 which is a multilayer color photographic light-sensitive material.

-Layer structure-
The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Further, 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardener.

Support / polyethylene terephthalate film (same as used in Example 1)

First layer (antihalation layer (non-photosensitive hydrophilic colloid layer))
・ Gelatin 1.03
・ Dispersion A (as dye coating amount) 0.10
・ Dispersion B (as dye coating amount) 0.03

Second layer (blue sensitive silver halide emulsion layer)
A 3: 1: 6 mixture of silver chlorobromide emulsion BO-01, emulsion BM-01, and emulsion BU-01 (silver molar ratio).
0.57
Gelatin 2.71
-Yellow coupler (ExY ') 1.19
・ (Cpd-41) 0.0006
・ (Cpd-42) 0.01
・ (Cpd-43) 0.05
・ (Cpd-44) 0.003
・ (Cpd-45) 0.012
・ (Cpd-46) 0.001
・ (Cpd-54) 0.08
・ Solvent (Solv-21) 0.26

Third layer (color mixing prevention layer)
・ Gelatin 0.59
・ (Cpd-49) 0.02
・ (Cpd-43) 0.05
・ (Cpd-53) 0.005
・ (Cpd-61) 0.02
-Solvent (Solv-21) 0.06
・ Solvent (Solv-23) 0.04
-Solvent (Solv-24) 0.002

Fourth layer (red-sensitive silver halide emulsion layer)
A 2: 2: 6 mixture of silver chlorobromide emulsion RO-01, emulsion RM-01 and emulsion RU-01 (silver molar ratio)
0.40
Gelatin 2.79
・ Cyan coupler (ExC ') 0.80
・ (Cpd-47) 0.06
・ (Cpd-48) 0.06
・ (Cpd-50) 0.03
・ (Cpd-52) 0.03
・ (Cpd-53) 0.03
・ (Cpd-57) 0.05
・ (Cpd-58) 0.01
・ Solvent (Solv-21) 0.53
・ Solvent (Solv-22) 0.28
・ Solvent (Solv-23) 0.04

5th layer (color mixing prevention layer)
・ Gelatin 0.56
・ (Cpd-49) 0.02
・ (Cpd-43) 0.05
・ (Cpd-53) 0.005
・ (Cpd-64) 0.005
-Solvent (Solv-21) 0.06
・ Solvent (Solv-23) 0.04
-Solvent (Solv-24) 0.002

Sixth layer (green sensitive silver halide emulsion layer)
-1: 3: 6 mixture of silver chlorobromide emulsions GO-01, GM-01, GU-01 (silver molar ratio)
0.49
・ Gelatin 1.55
・ Magenta coupler (ExM ') 0.70
・ (Cpd-49) 0.012
・ (Cpd-51) 0.001
・ (Cpd-52) 0.02
・ Solvent (Solv-21) 0.15

7th layer (protective layer)
・ Gelatin 0.97
・ Acrylic resin (average particle size 2 μm) 0.002
・ (Cpd-52) 0.03
・ (Cpd-55) 0.005
・ (CPd-56) 0.08
The compounds used here are shown below.

  Sample 201 was produced as described above.

[Preparation of Samples 202 to 219]
Next, as shown in Table 2, samples 202 to 219 to which the compound of the present invention was added were prepared. At this time, the amount of Cpd-65 added was adjusted so that the sensitivity to red light of each sample (definition will be described later) is ± 0.02 with respect to the sample 201.
Cpd-65 was added to the third layer, and the compound of the present invention was added to the fourth layer.

[Preparation of processing solution]
The same ECP-2D process as used in Example 1 was prepared. Next, for the purpose of creating a development processing state that is in a running equilibrium, an image is developed so that about 30% of the coated silver amount is developed for all the prepared samples, and the exposed samples are colored by the above processing process. Continuous processing (running test) was carried out until the amount of replenisher in the developing bath reached twice the tank capacity.

[Sample evaluation]
After preparing the sample, it was aged for 2 weeks at room temperature, and the following evaluation test was performed.
<Evaluation of sensitivity to red light>
Each sample was subjected to sensitometric exposure with red light using an optical meter (FWH type manufactured by Fuji Photo Film Co., Ltd., light source color temperature 3200K) through an optical wedge with an optical density changing 0.2 per 5 mm. The exposed sample was subjected to color development with the processing solution after the running test. With respect to the obtained processed sample, the Status A density was measured with an X-rite 310 densitometer, and the density value was plotted against the logarithmic value of the exposure amount to prepare a so-called sensitometry curve. The logarithmic value of the exposure amount with respect to a point giving a density of 1.0 on this curve was taken as sensitivity. As shown in Table 2, Sample 201 to Sample 219 were prepared in a coating amount of (Cpd-65) such that the sensitivity to red light of all the samples was in the range of ± 0.02 with respect to Sample 201.
<Evaluation of sensitivity to safelight>
Using a low-pressure sodium lamp as the light source, and irradiating the light from there uniformly for 10 minutes from the emulsion surface side of the sample, the above-mentioned processing is performed, and the optical density of the cyan color image is measured by the X-rire310 densitometer. Measured at Other samples were also irradiated under the condition that the optical density of the sample 201 was 0.40, and the optical density of the cyan color image was obtained and evaluated as the safe light sensitivity. It can be said that the smaller the value, the higher the safelight safety and the easier to handle.

[Evaluation results]
When the compound of the present invention is used alone as in Samples 201 to 204, the safety light safety is hardly improved compared to the unused one. However, as shown in samples 205 to 219, it can be seen that when two or more compounds are used in accordance with the present invention, the safety light safety can be significantly improved. In particular, it can be seen that when three types are used in combination as in Samples 213 to 219, a higher effect can be obtained.

Claims (8)

  The transparent support has at least one layer of a yellow color-sensitive silver halide emulsion layer, a cyan color-sensitive silver halide emulsion layer, and a magenta color-sensitive silver halide emulsion layer, and has a non-photosensitive hydrophilic property. A silver halide color photographic light-sensitive material having at least one colloid layer, wherein one of the silver halide emulsion layers or the non-light-sensitive hydrophilic colloid layer contains an oxonol-based water-soluble dye, an indigo-based water-soluble dye, and a phthalocyanine A silver halide color photographic light-sensitive material comprising at least any two dyes among three water-soluble dyes. 2. The silver halide color photograph according to claim 1, wherein one of the at least two dyes is an oxonol-based water-soluble dye, and the oxonol dye is represented by the following general formula (I): Photosensitive material.
Formula (I)
A ¹ = L ¹ − (L ² = L ³ ) _n −A ²
(In the formula, A ¹ and A ² each independently represent an acidic nucleus, L ¹ , L ² and L ³ each independently represent a methine group, and n represents 0, 1, 2 or 3.) 3. The silver halide color photographic light-sensitive material according to claim 2, wherein the oxonol-based water-soluble dye is represented by the following general formula (II).

(In the formula (II), R ₂₁ and R ₂₄ are each a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group. , Alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, sulfamoyl group, a sulfo group, an alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, a carbamoyl group or a cyano group, respectively R ₂₂ and R ₂₅ are a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group Aryl group, heterocyclic group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or An arylsulfonylamino group, a sulfamoyl group, a sulfo group, an alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, a carbamoyl group, or a cyano group, R ₂₃ and R ₂₆ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. M ₂ represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or pyridinium, provided that at least one of them in the molecule is ionic hydrophilic. Group as a substituent .) 4. The silver halide color photographic material according to claim 3, wherein R ₂₂ and R ₂₅ in the oxonol-based water-soluble dye according to claim 3 are sulfo groups. One of the at least two types of dyes is an indigo-based water-soluble dye, and the indigo-based dye is represented by the following general formula (III). A silver halide color photographic light-sensitive material as described in 1.

(In the formula (III), X ₃₁ and X ₃₂ each represent O, S, Se or NH, and Ar ₃₁ and Ar ₃₂ each represent a substituted arylene group, at least one of which is an ionic hydrophilic group. A functional group as a substituent.) 6. The method according to claim 1, wherein one of the at least two dyes is a phthalocyanine-based water-soluble dye, and the phthalocyanine dye is represented by the following general formula (IV): The silver halide color photographic light-sensitive material described.

(In the formula (IV); X ₁ , X ₂ , X ₃ and X ₄ each independently represent —SO—Z and / or —SO ₂ —Z, where Z is a substituted or unsubstituted one. Y ₁ represents an alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group Group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alcohol Xoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group Represents a heterocyclic thio group, a phosphoryl group, an acyl group or an ionic hydrophilic group, and these groups may further have a substituent, provided that X ₁ , X ₂ , X ₃ , X ₄ , Y _1, at least one of Y _2, Y ₃ and Y _4, .A1～a4 having as a substituent an ionic hydrophilic group, b1.about.b4 is the X ₁ to X _4, Y ₁ to Y _4, respectively Represents the number of substituents, and a1 to a4 and b1 to b4 are each independently an integer of 0 to 4, provided that all of a1 to a4 are not simultaneously 0. M is a hydrogen atom Represents a metal element, metal oxide, metal hydroxide, or metal halide.)   7. The silver halide color photographic light-sensitive material according to claim 1, wherein the non-photosensitive hydrophilic colloid layer contains the at least two dyes. 8. The solid fine particle dispersion of a dye represented by the following general formula (V) is further contained in at least one layer of the non-photosensitive hydrophilic colloid layer. The silver halide color photographic light-sensitive material described.
General formula (V)
D- (W) z
(In general formula (V), D represents a compound residue having a chromophore, W represents a dissociative hydrogen or a group having a dissociative hydrogen, and z represents an integer of 1 to 7.)