JPH0581025B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, the present invention relates to a silver halide photographic light-sensitive material, and more particularly, it contains a cyan coupler having excellent dispersion stability, and a halogen-based material that provides a dye image formed with good storage stability. This invention relates to silver chemical color photographic materials. [Background of the Invention] In order to form a dye image using a silver halide color photographic light-sensitive material, an aromatic primary amine color developing agent is usually used to remove the halogen in the exposed silver halide color photographic light-sensitive material. When silver halide grains are reduced, they are themselves oxidized, and this oxidized product reacts with a coupler previously contained in the silver halide color photographic light-sensitive material to form a dye. Generally, three types of couplers are used that form three dyes, yellow, magenta, and cyan, in order to perform color reproduction by the subtractive color method. Each coupler is usually dissolved in a substantially water-insoluble high-boiling organic solvent or in this solvent, if necessary, in combination with an auxiliary solvent, and added to the silver halide emulsion. The basic properties required for each coupler are:
First of all, it has high solubility in high-boiling organic solvents, has good dispersibility and dispersion stability in silver halide emulsions, does not easily precipitate, and has good photographic properties, and the dye images obtained are Examples include having durability against light, heat, moisture, etc. In particular, in cyan couplers, improvement of heat-humidity resistance (fading resistance) has become an important issue in recent years. Conventionally known cyan couplers include 2,5-diacylaminophenol cyan couplers in which the 2- and 5-positions of phenol are substituted with acylamino groups; for example, as disclosed in U.S. Pat.
Specification No. 2895826, Japanese Unexamined Patent Application Publication No. 112038/1983, No. 53-
No. 109630 and No. 55-163537. Among these, 2,5-
Diacylaminophenol cyan coupler is
Although it is often used because it provides cyan dye images with good dark fading properties, it is generally extremely poor in photofading properties of colored dye images and yellowing of unreacted cyan coupler due to light (hereinafter referred to as photo Y stain). There was a drawback. With regard to this photobleaching property, there is a phenomenon in which the color changes to pink, especially in low-density areas, which may cause the problem of amplifying visual fading. Depending on the coupler, these tendencies may become particularly noticeable when processed with a color developing solution that does not contain benzyl alcohol, and are a major hindrance to practical application. Furthermore, as described in Japanese Patent Publication No. 49-11572,
2-acylamino-5-ethylphenol cyan couplers are also known as couplers with good dark fading properties, but they not only have insufficient dark fading properties compared to the 2,5-diacylaminophenol cyan couplers. In particular, when processed with a color developing solution that does not contain benzyl alcohol, both dark fading and light fading properties deteriorated in some cases. As a means for improving the photobleaching properties of phenolic cyan couplers, for example, Japanese Patent Application Laid-open No. 151149/1983 proposes the combined use of a benzotriazole compound. However, this compound is not practical because it has a large precipitation property and is only effective against photobleaching against ultraviolet rays. It is also known to increase the amount of a conventionally used high-boiling organic solvent such as dibutyl phthalate, which slightly improves photobleaching, but does not improve photographic properties such as color tone. Problems such as adverse effects and deterioration of dark fading properties arose. Furthermore, there is almost no effect of suppressing optical Y stain. Furthermore, JP-A-57-173835 discloses that a 2,5-diacylaminophenol cyan coupler in which the 2-position of the phenol is substituted with an orthosulfonamide phenylacylamino group is used as a high-boiling organic solvent having a specific dielectric constant. A method has been proposed to improve the color tone and color fastness of pigments by dispersing them using a benzyl alcohol-free color developer. They are not preferable because they have low color development when processed and also have deteriorated light fastness. As described above, it has been difficult to achieve both dark fading resistance and light fastness of cyan dye images. Furthermore, in view of recent environmental regulations, there has been a push towards lower pollution in processing, and if we assume that one of the directions in this direction will be the removal of benzyl alcohol, the above dilemma will become particularly serious. I end up. However, currently no technology has been proposed to overcome this dilemma, and improvements have been strongly desired. In view of the above-mentioned current situation, the present inventors have conducted various studies and as a result have discovered the present invention. [Object of the Invention] A first object of the present invention is to provide a silver halide photographic light-sensitive material capable of having a cyan dye image with improved dark fading resistance and light fastness at the same time. A second object of the present invention is to provide a silver halide photographic material that can have a cyan dye image that exhibits high image storage stability even when processed with a color developing solution that does not contain benzyl alcohol. A third object of the present invention is to provide a silver halide photographic material in which discoloration of cyan dye images, particularly in low density areas, is eliminated. A fourth object of the present invention is to provide a silver halide photographic material in which the fastness of a cyan dye image is improved in light fading without deteriorating dark fading. A fifth object of the present invention is to provide a silver halide photographic material capable of forming a dye image with improved image storage stability without adversely affecting photographic properties. The sixth object of the present invention is to contain a cyan coupler dispersed using a high boiling point organic solvent that can be dispersed extremely stably, so that the cyan coupler has good dispersion stability and does not cause precipitation failure. An object of the present invention is to provide a silver halide photographic material. [Specific Structure of the Invention] The object of the present invention is to provide at least one
In a silver halide photographic light-sensitive material having a silver halide emulsion layer, at least one layer of the silver halide emulsion layer contains a cyan dye image-forming coupler represented by the following general formula [] and/or [] and a cyan dye image-forming coupler represented by the following general formula [] and/or []. This was achieved by a silver halide photographic material characterized by containing the compound represented by [ ] in the form of oil droplets.

[Formula] (In the formula, R ₁ represents an aryl group, a cycloalkyl group, or a heterocyclic group. _{R 2} represents an alkyl group or an aryl group. _{R 3} represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. (Z ₁ represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.)

[Formula, R ₄ represents an alkyl group, R ₅ represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, or an arylsulfonyl group, and R ₆ represents an arylsulfonyl group. Represents a hydrogen atom, a halogen atom, or an alkyl group. _Z2 represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.)

(In the formula, R ₇ and R ₈ represent an alkyl group having 3 to 15 carbon atoms, and m and n represent integers of 0 to 4.) In the present invention, R of the general formula [] The aryl group represented by ₁ is, for example, a phenyl group or a naphthyl group, and preferably a phenyl group. R ₁
The heterocyclic group represented by is, for example, a pyridyl group or a furan group. The cycloalkyl group represented by R ₁ is, for example, a cyclopropyl group or a cyclohexyl group. These groups represented by R ₁ include those having single or multiple substituents; for example, typical substituents introduced into phenyl groups include halogen atoms (e.g. fluorine, chlorine, bromine, etc.) , alkyl groups (e.g. methyl group, ethyl group,
propyl group, butyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), alkylsulfonamide group (e.g. methylsulfonamide group, octylsulfonamide group, etc.), Arylsulfonamide groups (e.g., phenylsulfonamide groups, naphthylsulfonamide groups, etc.), alkylsulfamoyl groups (e.g., butylsulfamoyl groups, etc.), arylsulfamoyl groups (e.g., phenylsulfamoyl groups, etc.), Alkyloxycarbonyl group (e.g. methyloxycarbonyl group, etc.),
Aryloxycarbonyl group (e.g. phenyloxycarbonyl group, etc.), aminosulfonamide group,
Examples include an acylamino group, a carbamoyl group, a sulfonyl group, a flufinyl group, a sulfoxy group, a sulfo group, an aryloxy group, an alkoxy group, a carboxyl group, an alkylcarbonyl group, an arylcarbonyl group, and an aminocarbonyl group. Two or more of these substituents may be substituted with the phenyl group. Preferred groups represented by R ₁ include unsubstituted phenyl group or halogen atom, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group,
It is a phenyl group having one or more arylsulfamoyl groups, alkylsulfonyl groups, arylsulfonyl groups, alkylcarbonyl groups, arylcarbonyl groups, or cyano groups as substituents. The alkyl group represented by R ₂ is linear or branched, and includes, for example, a methyl group, ethyl group, propyl group, butyl group, and octyl group. _R2
The aryl group represented by is preferably a phenyl group. In the present invention, preferred cyan couplers represented by the general formula [] are compounds represented by the following general formula ['].

embedded image In the general formula [′], R ₇ represents a phenyl group. This phenyl group includes those having single or multiple substituents, and typical substituents introduced include halogen atoms (e.g. fluorine, chlorine, bromine, etc.), alkyl groups (e.g. methyl group, ethyl group, etc.). group, propyl group, butyl group, octyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), alkylsulfonamide group (e.g. methylsulfonamide group, octylsulfone group) amide group, etc.), arylsulfonamide group (e.g., phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.). (eg, methyloxycarbonyl group, etc.), an alkyloxycarbonyl group (eg, methyloxycarbonyl group, etc.), and an aryloxycarbonyl group (eg, phenyloxycarbonyl group, etc.). Two or more of these substituents may be substituted with the phenyl group. Preferred groups represented by R ₇ include an unsubstituted phenyl group or a halogen atom (preferably fluorine or bromine), an alkylsulfonamide group (preferably o
-methylsulfonamide group, p-octylsulfonahad group, o-dodecylsulfonamide group),
Arylsulfonamide group (preferably phenylsulfonamide group), alkylsulfamoyl group (preferably butylsulfamoyl group), arylsulfamoyl group (preferably phenylsulfamoyl group), alkyl group (preferably methyl group,
trifluoromethyl group), alkoxy group (preferably methoxy group, ethoxy group) as a substituent.
It is a phenyl group having one or more. R ₈ is an alkyl group or an aryl group. Alkyl groups or aryl groups include those having single or multiple substituents, and typical examples of these substituents include halogen atoms (e.g. fluorine,
chlorine, bromine, etc.), hydroxyl group, carboxyl group, alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), aralkyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group) group, ethoxy group), aryloxy group, alkylsulfonamide group (e.g. methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide group (e.g. phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfonamide group moyl group (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), alkyloxycarbonyl group (e.g., methyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, etc.) carbonyl group, etc.), aminosulfonamide group (e.g., dimethylaminosulfonamide group, etc.), alkylsulfonyl group, arylsulfonyl group, alkylcarbonyl group, arylcarbonyl group, aminocarbonylamide group, carbamoyl group, sulfinyl group, etc. can. Two or more types of these substituents may be introduced. Preferred groups represented by R ₈ include n=0
When n=1 or more, it is an alkyl group, and when n=1 or more, it is an aryl group. A more preferable group represented by R ₈ is an alkyl group having 1 to 22 carbon atoms (preferably a methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group) when n=0.
and when n=1 or more, phenyl group, or alkyl group (preferably t-butyl group, t-amyl group, octyl group), arylsulfonamide group (preferably phenylsulfonamide group), aminosulfonamide It is a phenyl group having one or more substituents of a group (preferably a dimethylaminosulfonamide group) or an alkyloxycarbonyl group (preferably a methyloxycarbonyl group or a butyloxycarbonyl group). R ₉ represents an alkylene group. Straight chain or branched carbon atoms 1 to 20, even carbon atoms 1 to 12
represents an alkylene group. R ₁₀ is a hydrogen atom or a halogen atom (fluorine,
chlorine, bromine or iodine). Preferably it is a hydrogen atom. n is 0 or a positive integer, preferably 0 or 1. X is -O-, -CO-, -COO-, -OCO-, -
Represents a divalent group such as SO ₂ NR''-, -NR'SO ₂ NR''-, -S-, -SO- or -SO ₂ - group. Here, R′,
R'' represents a substituted or unsubstituted alkyl group.
X is preferably -O-, -S-, -SO-, _-SO2
- is a group. Z ₃ is a hydrogen atom, a halogen atom, or an aromatic primary
Represents a group that can be separated by reaction with an oxidized product of a class amine color developing agent. Preferred are chlorine atom and fluorine atom. Typical specific examples of the cyan coupler represented by the formula [] are shown below, but the invention is not limited thereto.

[ka]

[ka]

[ka] (a-1)

[ka] (a-2)

[ka] (a-3)

[ka] (a-4)

[ka] (a-5)

[ka] (a-6)

[ka] (a-7)

[ka] (a-8)

[ka] (a-9)

[ka] (a-10)

[ka] (a-11)

[ka] (a-12)

[ka] (a-13)

[ka] (a-14)

[ka] (a-15)

[ka] (a-16)

[ka] (a-17)

[ka] (a-18)

[ka] (a-19)

[ka] (a-20)

[ka] (b-1)

[ka] (b-2)

[ka] (b-3)

[ka] (b-4)

[ka] (b-5)

[ka] (b-6)

[ka] (b-7)

[ka] (b-8)

[ka] (b-9)

[ka] (b-10)

[ka] (b-11)

[ka] (b-12)

[ka] (b-13)

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

In the present invention, the cyan coupler represented by the general formula [] is more preferably one represented by the following general formula [']. General formula [′]

[Image Omitted] In the formula, R ₁₁ and R ₁₂ are the same or different and represent a hydrogen atom, an alkyl group (for example, a methyl group,
ethyl group, propyl group, butyl group, amyl group, octyl group, dodecyl group, etc.), and an alkoxy group (eg, methoxy group, ethoxy group, etc.). However, the total number of carbon atoms of R ₁₁ and R ₁₂ is 8 to 16. More preferably, R ₁₁ and R ₁₂ are each a butyl group or an amyl group. R ₁₃ is a hydrogen atom or an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, octyl group, etc.). Preferred are a hydrogen atom, an ethyl group, and a butyl group. R′ ₅ has the same meaning as R ₅ in the general formula [ ]. That is, alkyl groups (e.g. methyl, ethyl, propyl, butyl, dodecyl, etc.), aryl groups (e.g. phenyl, etc.), alkoxy groups (e.g. methoxy, ethoxy, etc.), aryloxy groups (e.g. phenyloxy) ), an alkylthio group (e.g., methylthio group, ethylthio group, etc.), an arylthio group (e.g., phenylthio group, etc.), an alkylsulfonyl group (e.g., methanesulfonyl group, ethanesulfonyl group, etc.), or an arylsulfonyl group (e.g., benzenesulfonyl group, etc.). _R'5 is preferably an alkyl group, more preferably a methyl group or an ethyl group. m represents an integer from 0 to 2. Z ₄ represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. In the formulas [], [], [′] and [′], the aromatic primary represented by Z ₁ , Z ₂ , Z ₃ and Z ₄
Groups that can be released by reaction with the oxidized form of a class amine color developing agent are well known to those skilled in the art, and can modify the reactivity of the coupler or can be released from the coupler to improve silver halide color photographic sensitization. It works advantageously by performing functions such as development inhibition, bleaching inhibition, and color correction in the coating layer or other layers containing the coupler in the material. Typical examples include alkoxy groups, aryloxy groups, arylazo groups, thioethers, carbamoyloxy groups, acyloxy groups, imido groups, sulfonamide groups, thiocyano groups, or heterocyclic groups (e.g., oxazolyl, diazolyl, triazolyl, tetrazolyl). etc.).
A particularly preferred example of Z is a hydrogen atom or a chlorine atom. Typical specific examples of the cyan coupler represented by the formula [] are shown below, but the invention is not limited thereto.

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[Chemical formula] The cyan couplers represented by the general formulas [] and [] according to the present invention may be used alone or in combination, and the amount added is per mole of silver halide as the total amount of cyan couplers. The range is preferably 2×10 ⁻³ mol to 1 mol, more preferably 1×10 ⁻² to 8×10 ⁻¹ mol. Also,
When the cyan coupler represented by the general formula [] according to the present invention and the cyan coupler represented by the general formula [] are used together, the ratio is 10% of the cyan coupler represented by the general formula [] to the cyan coupler represented by the general formula []. ~90 mol% is preferred, more preferably
It is 20 to 90 mol%. Note that the cyan coupler represented by the general formula [] and/or [] according to the present invention can be used in combination with other cyan couplers. In the general formula [], R ₇ and R ₈ represent an alkyl group having 3 to 15 carbon atoms, preferably an alkyl group having 5 to 8 carbon atoms. The alkyl group may be either a straight chain alkyl group or a branched chain alkyl group. Specific examples of preferred alkyl groups include n-amyl group, t-
amyl group, n-hexyl group, 1-ethylpentyl group, n-heptyl group, 1-methylbutyl group, n-
Examples include octyl group. In the general formula [ ], m and n are each 0 to
It represents an integer of 4, preferably an integer of 1 to 4. The substituent having two ester groups may be in any of the ortho, meta, and para positions, but it is preferably bonded to the meta and para positions. Typical specific examples of the compound represented by the general formula [] are shown below, but the invention is not limited thereto.

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

【formula】

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

【formula】

[ka]

[ka]

[ka]

[ka]

embedded image These compounds can be synthesized, for example, by the method described in Japanese Patent Publication No. 56-1616. The amount of the compound represented by the general formula [] according to the present invention may be any amount depending on the case, but
10 to 300 for the cyan coupler according to the present invention.
% by weight is preferred, and a range of 20 to 150% by weight is particularly preferred. In the silver halide photographic light-sensitive material of the present invention, the cyan dye image-forming coupler represented by the general formula [] and/or [] according to the present invention and the compound represented by the general formula [] according to the present invention are incorporated into oil droplets. It is contained in the silver halide emulsion layer as a silver halide emulsion layer. In the present invention, containing as oil droplets in a silver halide emulsion means the general formula [ ] according to the present invention.
and/or a cyan coupler represented by []. If necessary, other hydrophobic additives can be used in combination with the compound represented by the general formula [] described below. Solubility in water with a boiling point of approximately 150℃ or higher is 10%
Dissolve in the following high boiling point organic solvents in combination with low boiling point and/or water-soluble organic solvents as necessary, and use a stirrer, homogenizer, colloid, etc. in a hydrophilic binder such as gelatin solution using a surfactant. After emulsifying and dispersing it using a dispersion means such as a mill, a flow mixer, or an ultrasonic device, it is added to the desired silver halide emulsion, coated on a support, and in the dried layer, the The cyan coupler represented by the general formula [] and/or [] according to the invention does not precipitate and is dissolved and contained in the compound represented by the general formula [] according to the invention and/or a high boiling point organic solvent that can be used in combination. means that The compound represented by the general formula [] according to the present invention can also be used in combination with other high-boiling point organic solvents. High boiling point organic solvents that can be used in combination with the present invention will be described below. Examples of high-boiling organic solvents that can be used in combination with the present invention include esters such as phthalic esters and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds. Also, preferably the vapor pressure at 100℃ is 0.5mm.
It is a high boiling point organic solvent below Hg. Even more preferred are phthalic acid esters or phosphoric acid esters in the high-boiling organic solvent. Note that the organic solvents that can be used in combination may be a mixture of two or more. The high boiling point organic solvent used in combination in the present invention is
Preferably, dialkyl phthalate or phosphoric acid ester represented by the following general formula [a] or [b] is used.

[Formula] In the formula, R ₅ and R ₆ each represent an alkyl group.

[Formula] In the formula, R ₇ , R ₈ and R ₉ each represent an alkyl group or an aryl group (for example, a phenyl group). Each group represented by R ₅ , R ₆ , R ₇ , R ₈ and R ₉ above is:
It also includes those with substituents. Typical specific examples of the high boiling point organic solvent represented by the general formula [a] or [b] are listed below, but the present invention is not limited thereto. (Exemplary compound) (a-1)

【formula】 (a-2)

【formula】 (a-3)

【formula】 (a-4)

【formula】 (a-5)

【formula】 (a-6)

【formula】 (a-7)

【formula】 (a-8)

【formula】 (a-9)

【formula】 (a-10)

[Formula] (a-11)

【formula】 (a-12)

【formula】 (a-13)

【formula】 (a-14)

【formula】 (a-15)

[ka] (a-16)

【formula】 (a-17)

【formula】 (a-18)

【formula】 (a-19)

【formula】 (a-20)

【formula】 (b-1)

【formula】 (b-2)

【formula】 (b-3)

【formula】 (b-4)

【formula】 (b-5)

【formula】 (b-6)

【formula】 (b-7)

【formula】 (b-8)

【formula】 (b-9)

【formula】 (b-10)

【formula】 (b-11)

【formula】 (b-12)

【formula】 (b-13)

[Formula] The amount of the high boiling point organic solvent that can be used in combination with the present invention is the same as that of the general formula [] according to the present invention, that is, 10 to 10% for the cyan coupler according to the present invention.
It is preferably 300% by weight, and more preferably from 20 to 150% by weight. As a method for emulsifying and dispersing the cyan dye-forming coupler according to the present invention using a high boiling point organic solvent that can be used in combination with the present invention, a conventionally known emulsifying and dispersing method for hydrophobic compounds can be used. For example, cyan dye-forming couplers, compounds of general formula [ ],
After mixing and dissolving a high boiling point organic solvent that can be used in combination with a dye image stabilizer and a mixing inhibitor as necessary, and further using a low boiling point organic solvent as necessary,
Mixed with an aqueous gelatin solution containing a surfactant,
Then, the mixture can be emulsified and dispersed using a high-speed rotating mixer, a colloid mill, an ultrasonic dispersion machine, or the like. In addition to the compounds represented by the general formulas [] and/or [] and [] according to the present invention, compounds represented by the following general formulas [a] to [c] may be used in combination for the purpose of preventing fading.

embedded image In the formula, R ₇ and R ₈ each represent an alkyl group. R ₉ is an alkyl group, -NHR' ₉ group, -SR' ₉ group (R' ₉ represents a monovalent organic group), or -
_COOR''9 group ( _R''9 represents a hydrogen atom or a monovalent organic group). m represents an integer from 0 to 3.

[Chemical formula] In the formula, R ₁₁ is a hydrogen atom, a hydroxyl group, an oxyl radical group, -SOR' ₁₁ group, -SO ₂ R' ₁₁ group (R' ₁₁
represents an alkyl group or an aryl group. ), alkyl group, hydroxyalkyl group, alkenyl group,
Alkynyl group, benzyl group or _-COR''11 group ( _R''11 represents a hydrogen atom or a monovalent organic group.)
represents. R ₁₂ , R′ ₁₂ , and R″ ₁₂ each represent an alkyl group. R ₁₃ and R ₁₄ each represent a hydrogen atom or an -OCOR group (R represents a monovalent organic group). Alternatively, R ₁₃ and R ₁₄ may jointly form a heterocyclic group. n represents an integer of 0 to 4.

[Chemical formula] In the formula, R ₁₅ , R ₁₆ and R ₁₇ may be the same or different, and each represents a hydrogen atom, a halogen atom,
Represents a hydroxyl group, nitro group, alkyl group, aryl group, alkoxy group, aryloxy group or alkenyl group. In the present invention, R ₇ and R ₈ of general formula [a]
The alkyl group represented by is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 3 to 8 carbon atoms and branched at the α position. Particularly preferably R ₇ and R ₈ are t-butyl groups,
or a t-pentyl group. The alkyl group represented by R ₉ is linear or branched, and includes, for example, a methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, nonyl group, dodecyl group, octadecyl group, and the like.
When this alkyl group has a substituent, these substituents include a halogen atom, hydroxyl group, nitro group, cyano group, aryl group (e.g. phenyl group, hydroxyphenyl group, 3,5-di-
t-butyl-4-hydroxyphenyl group, 3,5
-di-t-pentyl-4-hydroxyphenyl group, etc.), amino group (e.g. dimethylamino group, diethylamino group, 1,3,5-triazinylamino group, etc.), alkyloxycarbonyl group (e.g. methoxycarbonyl group) , ethoxycarbonyl group, propyloxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g. phenoxy carbonyl group, etc.), carbamoyl group (for example, alkylcarbamoyl group such as methylcarbamoyl group, ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group, heptylcarbamoyl group, arylcarbamoyl group such as phenylcarbamoyl group, cyclohexylcarbamoyl group etc.) Examples include heterocyclic groups such as an alkylcarbamoyl group), an isocyanuryl group, and a 1,3,5-triazinyl group. The amino group represented by R ₉ is, for example, an alkylamino group such as a dimethylamino group, a diethylamino group, or a methylethylamino group, an arylamino group such as a phenylamino group or a hydroxylphenylamino group, a cycloalkylamino group such as a cyclosexyl group, 1, 3,
It includes heterocyclic amino groups such as 5-triazinylamino group and isocyanuryl group. _R′9 and R″ ₉
The monovalent organic group represented by is, for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a decyl group, a dodecyl group, a hexadecyl group, an octadecyl group, etc.), an aryl group (for example, a phenyl group). , naphthyl group, etc.), cycloalkyl group (eg, cyclohexyl group, etc.), and heterocyclic group (eg, 1,3,5-triazinyl group, isocyanuryl group, etc.). When these organic groups have a substituent, examples of the substituent include a halogen atom (e.g., fluorine, chlorine, bromine, etc.), a hydroxy group, a nitro group, a cyano group, an amino group, an alkyl group (e.g., a methyl group, ethyl group, i-propyl group, t-butyl group, t-amyl group, etc.), aryl group (e.g., phenyl group, tolyl group, etc.), alkenyl group (e.g., allyl group, etc.), alkyl erbonyloxy group (e.g., methylcarbonyl group, etc.), oxy group, ethylcarbonyloxy group, benzylcarbonyloxy group, etc.), arylcarbonyloxy group (eg, benzoyloxy group, etc.). In the present invention, compounds represented by the general formula [a] are preferably compounds represented by the following general formula [a'].

embedded image In the formula, R ₂₅ and R ₂₆ are each a linear or branched alkyl group having 3 to 8 carbon atoms, especially t
-Represents a butyl group or a t-pentyl group. R ₂₇ is k
represents a valent organic group. k represents an integer from 1 to 6. ] Examples of the k-valent organic group represented by R ₂₇ include methyl group, ethyl group, propyl group, butyl group,
Pentyl group, octyl group, hexadecyl group, methoxyethyl group, chloromethyl group, 1,2-dipromoethyl group, 2-chloroethyl group, benzyl group,
Alkyl groups such as phenethyl groups, alkenyl groups such as allyl groups, propenyl groups, butenyl groups, polyunsaturated hydrocarbon groups such as ethylene, trimethylene, propylene, hexamethylene, 2-chlorotrimethylene, glyceryl, diglyceryl, penta Unsaturated hydrocarbon groups such as erythrityl and dipentaerythrityl, alicyclic hydrocarbon groups such as cyclopropyl, cyclohexyl, and cyclohexenyl groups, phenyl group, p-octylphenyl group, 2,4-dimethylphenyl group, 2, 4-di-t-butylphenyl group, 2,4-di-t-pentylphenyl group, p-
Aryl groups such as chlorophenyl group, 2,4-dibromophenyl group, naphthyl group, 1,2-, 1,
3- or 1,4-phenylene group, 3,5-dimethyl-1,4-phenylene group, 2-t-butyl-
Arylene groups such as 1,4-phenylene group, 2-chloro-1,4-phenylene group, naphthalene group,
Examples include 1,3,5-trisubstituted benzene groups. In addition to the above-mentioned groups, _R27 further includes a k-valent organic group in which any of the above groups is bonded via an -O-, -S-, or _-SO2- group. More preferably _R27 is a 2,4-di-t-butylphenyl group, a 2,4-di-t-pentylphenyl group, a p-octylphenyl group, a p-dodecylphenyl group, a 3,5-di- -t-butyl-4-hydroxylphenyl group, 3,5-di-t-pentyl-
It is a 4-hydroxylphenyl group. Preferably, k is an integer of 1 to 4. Specific compounds represented by the general formula [] are listed below, but are not limited thereto.

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

【formula】

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

In the present invention, the alkyl group represented by R ₁₁ in the general formula [b] has 1 to 12 carbon atoms,
The alkenyl group or alkynyl group has 2 to 4 carbon atoms, and preferable groups represented by _R11 include a hydrogen atom, an alkyl group (such as a methyl group, an ethyl group, a propyl group, a butyl group, a chloromethyl group, hydroxymethyl group, benzyl group, etc.),
an alkenyl group (e.g., vinyl group, allyl group, isopropenyl group, etc.), an alkynyl group (e.g., ethynyl group, propynyl group, etc.), or a _-COR''11 group, where _R''11 is, for example, an alkyl group (e.g., a methyl group, ethyl group, propyl group, butyl group, benzyl group, etc.), alkenyl group (e.g. vinyl group, allyl group, isopropenyl group, etc.), alkynyl group (e.g. ethynyl group, propynyl group, etc.), aryl group (e.g. phenyl group, tolyl group, etc.) etc.). The alkyl groups represented by R ₁₂ , R′ ₁₂ and R″ ₁₂ are preferably linear or branched alkyl groups having 1 to 5 carbon atoms, and particularly preferably a methyl group. R ₁₃ and R ₁₄ , 1 denoted by R
Examples of valent organic groups include alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, octyl, dodecyl, octadecyl, etc.), alkenyl groups (e.g., vinyl), alkynyl groups ( Examples include ethynyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), alkylamino group (eg, ethylamino group, etc.), arylamino group (eg, anilino group), and the like. The heterocyclic group formed jointly by R ₁₃ and R ₁₄ is
for example

【formula】

[Formula] etc. R ₂₈ is a hydrogen atom, an alkyl group, a cycloalkyl group, or a phenyl group. ), etc. In the present invention, compounds represented by the general formula [b] are preferably those represented by the following general formula [b']. General formula [b′]

[Chemical formula] R ₂₉ is an alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, benzyl group, etc.), an alkenyl group (e.g., vinyl group, allyl group, isopropenyl group, etc.), an alkynyl group ( For example, ethynyl group, propynyl group, etc.), acyl group (eg, formyl group, acetyl group, propionyl group, butyryl group, acryloyl group, propioloyl group, methicryloyl group, crotonoyl group, etc.). More preferred groups for R ₂₉ are methyl, ethyl, vinyl, allyl, propynyl, benzyl, acetyl, propionyl, acryloyl, methacryloyl, and crotonoyl. Specific compounds represented by general formula [b] are listed below, but are not limited thereto. (b-1)

【formula】 (b-2)

[ka] (b-3)

【formula】 (b-4)

【formula】 (b-5)

[ka] (b-6)

【formula】 (b-7)

[Formula] (b-8)

【formula】 (b-9)

【formula】 (b-10)

【formula】 (b-11)

[ka] (b-12)

[ka] (b-13)

[ka] (b-14)

[ka] (b-15)

[ka] (b-16)

[ka] (b-17)

[ka] (b-18)

[ka] (b-19)

[ka] (b-20)

[ka] (b-21)

[ka] (b-22)

[ka] (b-23)

[ka] (b-24)

[ka] (b-25)

[ka] (b-26)

[ka] (b-27)

[ka] (b-28)

In the general formula [c], examples of the halogen atom represented by R ₁₅ , R ₁₆ and R ₁₇ include a fluorine atom, a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred. an alkyl group represented by R ₁₅ , R ₁₆ and R ₁₇ ;
The alkoxy group preferably has 1 to 20 carbon atoms, and the alkenyl group preferably has 2 to 20 carbon atoms, and these may be linear or branched. Moreover, these alkyl groups, alkenyl groups, and alkoxy groups may have substitutions. Examples of substituents include aryl, cyano, halogen atom, heterocycle, cycloalkyl, cycloalkenyl, spiro compound residue, bridged hydrocarbon compound residue, as well as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl. Those substituted via a carbonyl group, and further substituted via a hetero atom (specifically, those substituted via an oxygen atom such as hydroxy, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, etc.) nitro, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido, etc. substituted through the nitrogen atom, alkylthio, arylthio , heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, etc., which are substituted via a sulfur atom, and phosphonyl, which is substituted via a phosphorus atom. Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, sec-butyl group, n
-butyl group, n-amyl group, sec-amyl group, t
Examples include -amyl group, α,α-dimethylbenzyl group, octyloxycarbonylethyl group, methoxy group, ethoxy group, octyloxy group, allyl group, and the like. an aryl group represented by R ₁₅ , R ₁₆ and R ₁₇ ;
Examples of the aryloxy group include phenyl group,
A phenyloxy group is particularly preferred, and it may have a substituent (eg, an alkyl group, an alkoxy group, etc.). Specifically, for example, phenyl group, 4-t
-butylphenyl group, 2,4-di-t-amyl phenyl group, etc. Among the groups represented by R ₁₆ and R ₁₇ , a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group are preferred, and a hydrogen atom, an alkyl group, and an alkoxy group are particularly preferred. Among the groups represented by R ₁₅ , hydrogen electrons, halogen atoms, alkyl groups, and alkoxy groups are particularly preferred. Specific compounds represented by general formula [c] are listed below, but are not limited thereto. (c-1)

【formula】 (c-2)

【formula】 (c-3)

【formula】 (c-4)

【formula】 (c-5)

[Formula] (c-6)

【formula】 (c-7)

[Formula] (c-8)

【formula】 (c-9)

[C] (c-10)

【formula】 (c-11)

【formula】 (c-12)

【formula】 (c-13)

【formula】 (c-14)

[C] (c-15)

【formula】 (c-16)

【formula】 (c-17)

[C] (c-18)

[Formula] When the compounds represented by the above general formulas [a], [b] and [c] are contained in the silver halide emulsion layer, the general formulas [] and /
or 5 to 200 parts by weight, or even 10 to 100 parts by weight, for 100 parts by weight of the cyan coupler represented by [ ]
Preferably, parts by weight are used. In the silver halide photographic light-sensitive material according to the present invention, for the purpose of rapid processing, the following general formula [a]
A dye image can be formed in the presence of the compounds represented by [b].

[Formula] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent an alkyl group, and R ₁ and R ₂ and/or R ₃ and R ₄
may be bonded to each other to form a nitrogen-containing heterocycle with a nitrogen atom. R ₅ represents a halogen atom, an alkyl group or an alkoxy group, and n ₁ represents an integer of 0 to 4. When n ₁ is an integer of 2 to 4, R ₅ may be the same or different. ) In the general formula [a], the alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ may be linear or branched, and is preferably an alkyl group having 1 to 4 carbon atoms; Groups include those having substituents, such as hydroxy groups, alkoxy groups (e.g. methoxy groups, edoxy groups, etc.), sulfonamide groups (e.g. alkylsulfonamide groups such as methanesulfonamide groups, benzenesulfonamide groups). (eg, arylsulfonamide group, etc.), aryl group (eg, phenyl group, etc.), and the like. Examples of the alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, and hydroxymethyl group. ,β
-hydroxymethyl group, β-methoxyethyl group,
Examples include methanesulfonamidoethyl group.
The nitrogen-containing heterocyclic nucleus formed by R ₁ and R ₂ and/or R ₃ and R ₄ may further contain an oxygen atom, a nitrogen atom, a sulfur atom, etc., such as a pyrrolidine nucleus, a piperidine nucleus, a morpholine nucleus, etc. can be mentioned. Examples of the halogen atom represented by R ₅ in the general formula [] include a bromine atom and a chlorine atom, examples of an alkyl group include a methyl group and an ethyl group, and examples of an alkoxy group include a methoxy group. , ethoxy group, etc. _R5
The alkyl group and alkoxy group represented by include those having a substituent. Specific examples of the compound represented by the general formula [a] used in the present invention are shown below, but the present invention is not limited thereto. a-1

【formula】 a-2

【formula】 a-3

【formula】 a-4

【formula】 a-5

【formula】 a-6

【formula】 a-7

【formula】 a-8

【formula】 a-9

【formula】 a-10

【formula】 a-11

【formula】 a-12

【formula】 a-13

[Formula] These compounds, with some exceptions, are known (for example, described in JP-A-50-15554, JP-A-58-120248, etc.), and those skilled in the art can easily synthesize them. be able to. For the synthesis of these compounds,
For example, Bent, Dessloch, James, Laby, Sterner, Bitstum, Biesberger; Journal of American Chemical Society;
Fassott, James, Ruby, Sterner, Vittum,
Weissberger; J.Am.Chem.Soc.)] 73 , 3100
(1951) and [Bent, Brown, Gressmanes,
Harnish; Photo Science Engineering, (Bent, Brown, Glesmaness, Harnish;
Phot. Sci. Eng, ) 8, 125 (1964), etc.

[Formula, R ₆ and R ₇ each represent a hydrogen atom or an alkyl group, and R ₆ and R ₇ may be bonded to each other to form a nitrogen-containing heterocycle. _{R 8} is a halogen atom or an alkyl group. group or an alkoxy group, and n ₂ represents an integer of 0 to 4. When n ₂ is an integer of 2 to 4, R ₈ may be the same or different.) In the general formula [b], R ₆ and The alkyl group represented by R ₇ may be linear or branched, and is preferably an alkyl group having 1 to 6 carbon atoms,
These alkyl groups include those having substituents, such as hydroxy groups, alkoxy groups (e.g. methoxy groups, ethoxy groups, etc.),
Examples include sulfonamide groups (for example, alkylsulfonamide groups such as methanesulfonamide groups, arylsulfonamide groups such as benzenesulfonamide groups), and the like. Examples of the alkyl group represented by R ₆ and R ₇ include methyl group, ethyl group, butyl group, hexyl group, hydroxymethyl group, β-hydroxyethyl group, methoxymethyl group, β-methanesulfonamidoethyl group, etc. Can be mentioned. The nitrogen-containing heterocyclic nucleus formed by R ₆ and R ₇ may further contain an oxygen atom, a nitrogen atom, a sulfur atom, etc., and examples thereof include a pyrrolidine nucleus, a piperidine nucleus, a piperazine nucleus, a morpholine nucleus, and the like. Examples of the halogen atom represented by R ₈ include a bromine atom and a chlorine atom, examples of an alkyl group include a methyl group and an ethyl group, and examples of an alkoxy group include a methoxy group and an ethoxy group. Can be mentioned. The alkyl group and alkoxy group represented by R ₈ include those having a substituent. When n ₂ is 2 to 4, R ₈ may be the same or different. Specific examples of the compound represented by the general formula [b] used in the present invention are shown below, but the present invention is not limited thereto. b-1

【formula】 b-2

【formula】 b-3

【formula】 b-4

【formula】 b-5

【formula】 b-6

【formula】 b-13

【formula】 b-14

【formula】 b-15

【formula】 b-16

【formula】 b-17

【formula】 b-18

[Formula] These compounds are described, for example, in US Pat. No. 2,286,678,
Same No. 2483374, Same No. 2776313, Same No. 3060225,
British Patent No. 928671, Berichte der Deutsche Chemischen Gesellschaft No. 16
Volume No. 724 (Berichte der Deutschen
Chemischen Gesellschaft) Same magazine, Volume 34, No. 2125
Page, Chemische Berichte, Volume 92, Page 3223 (Chemische Berichte), Fotographik.
Science and Engineering Volume 12 No.
41 pages (Photographic Science and Engineering)
and Journal of the Chemical Society, Vol. 1947, p. 182.
Chemical Society) etc.

[Formula] (wherein, X represents a hydrogen atom or a hydrolyzable group, R ₉ represents an aryl group, R ₁₀ , R ₁₁ ,
R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkyl group or an aryl group. ) In the general formula [c], X represents a hydrogen atom or a hydrolyzable group, and the hydrolyzable group represented by X is preferably an acetyl group. X is preferably a hydrogen atom. Examples of the aryl group represented by R ₉ in the general formula [c] include phenyl group and naphthyl group, with phenyl group being preferred. This aryl group includes those having substituents, such as alkyl groups (for example, methyl, ethyl, propyl, etc.), halogen atoms (chlorine, bromine, etc.), alkoxy groups (methoxy,
ethoxy group, etc.), a sulfonyl group, and an amide group (methylamide group, ethylamide group, etc.). The alkyl group represented by R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ in general formula [c] is preferably an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a butyl group, etc.). Can be mentioned. This alkyl group includes those having a substituent, and examples of the substituent include a hydroxyl group, an amino group, and an acyloxy group. Also R ₁₀ , R ₁₁ , R ₁₂
Examples of the aryl group for R ₁₃ include a phenyl group and an aphthyl group. This aryl group includes those having substituents, such as alkyl groups (methyl group, ethyl group, propyl group, etc.), halogen atoms (chlorine atom, bromine atom, etc.),
Examples include alkoxy groups (methoxy groups, ethoxy groups, etc.) and hydroxyl groups. Typical specific examples of the compound represented by the general formula [c] used in the present invention are shown below, but the compound of the present invention is not limited thereto. c-1

【formula】 c-2

【formula】 c-3

【formula】 c-4

【formula】 c-5

【formula】 c-6

【formula】 c-7

【formula】 c-8

【formula】 c-9

【formula】 c-10

【formula】 c-11

【formula】 c-12

【formula】 c-13

【formula】 c-14

【formula】 c-15

【formula】 c-16

【formula】 c-17

【formula】 c-18

【formula】 c-19

【formula】 c-20

【formula】 c-21

【formula】 c-22

【formula】 c-23

【formula】 c-24

【formula】 c-25

【formula】 c-26

【formula】 c-27

【formula】 c-28

【formula】 c-29

【formula】 c-30

【formula】 c-31

【formula】 c-32

【formula】 c-33

【formula】 c-34

【formula】 c-35

【formula】 c-36

【formula】 c-37

【formula】 c-38

【formula】 c-39

【formula】 c-40

【formula】 c-41

【formula】 c-42

【formula】 c-43

【formula】 c-44

【formula】 c-45

【formula】 c-46

【formula】 c-47

【formula】 c-48

[Formula] Compounds represented by general formula [c] are commercially available, but US Patent No. 2688024,
No. 2704762, JP-A-56-64339 and JP-A-57
It can be synthesized according to No.-211147.

[Formula] (wherein A and B each represent a secondary amino group bonded to the carbon atom of the mother nucleus through a nitrogen atom,
Y represents a sulfur atom or an oxygen atom. ) In the general formula [d], the secondary amino group bonded to the carbon atom of the mother nucleus represented by A and B with a nitrogen atom can contain various aliphatic or aromatic components, and A and B are mutually exclusive. They may be the same or different. The above A and B can be specifically represented by -NH-R ₁₄ and -NH-R ₁₅ , respectively, where R ₁₄ and R ₁₅ are each an aliphatic group or an aromatic group, and R ₁₄ and R ₁₅ is preferably an electron donating group. Specific examples of the groups represented by R ₁₄ and R ₁₅ include alkyl groups, alkenyl groups, and aryl groups, and these alkyl groups, alkenyl groups, and aryl groups also include those having substituents. Examples of these substituents include alkoxy groups (eg, methoxy group, ethoxy group, etc.), alkylthio groups (eg, methylthio group, ethylthio group, etc.), and the like. R ₁₄ and R ₁₅ are, for example, a methyl group,
Ethyl group, propyl group, butyl group, methoxymethyl group, β-methoxyethyl group, β-ethoxyethyl group, thylthioethyl group, ethylthiomethyl group,
Examples include allyl group, phenyl group, methoxyphenyl group, ethoxyphenyl group, methylthiophenyl group, and ethylthiophenyl group. Specific examples of the compound represented by the general formula [d] used in the present invention are shown below, but the present invention is not limited thereto. d-1 2,5-bis(methylamino)-1,
3,4-thiadiazole d-2 2-methylamino-5-ethylamino-1,3,4-thiadiazole d-3 2,5-bis(ethylamino)-1,
3,4-thiadiazole d-4 2,5-bis(n-butylamino)-
1,3,4-thiadiazole d-5 2-allylamino-5-methylamino-1,3,4-thiadiazole d-6 2-(2-ethoxyethylamino)-5
-methylamino-1,3,4-thiadiazole d-7 2,5-bis(phenylamino)-1,
3,4-thiadiazole d-8 2,5-bis(2-methoxyethylamino)-1,3,4-thiadiazole d-9 2-(2-ethoxyethylamino)-5
-(2-methoxyethylamino)-1,
3,4-thiadiazole d-10 2,5-bis(2-ethoxyethylamino)-1,3,4-thiadiazole d-11 2-(2-methoxyethylamino)-5
-phenylamino-1,3,4-thiadiazole d-12 2-(p-methoxyphenylamino)-
5-(2-methoxyethylamino)-1,
3,4-thiadiazole d-13 2-(3-methylthiopropylamino)
-5-(2-methoxyethylamino)-
1,3,4-thiadiazole d-14 2,5-bis(methylamino)-1,
3,4-oxadiazole d-15 2,5-bis(ethylamino)-1,
3,4-Oxadiazole An example of the method for producing the diazole compound represented by the above general formula [d] is described in JP-A-53-61334 [P.C., Guha, Journal of American Chemical Society, ( PC
Guha, Journal of American Chemical
Society)], 45 , p.1036 (1928), and [Journal of Medical Chemistry,
(Journal of Medical Chemistry, vol.15, No.
3, p. 315 (1972), etc. In the present invention, general formulas [a], [b],
Color development may be carried out in the presence of the compound represented by [c] or [d], but the presence here means that it is present at the time of color development; It may be contained in the color developer, or it may be contained in the color developing solution in advance. Furthermore, it may be included in advance in both the silver halide photographic light-sensitive material and the color developing solution. When adding a compound represented by the general formula [a], [b], [c] or [d] to a silver halide color light-sensitive material, the amount added depends on the halogen composition of the silver halide emulsion, the amount of silver, etc. Although it varies widely depending on the amount, approximately per mole of silver halide
The amount is 0.001 mol to 1 mol, preferably 0.002 mol to 0.2 mol. In addition, when there are two or more photosensitive silver halide emulsion layers, generally ² ×
10 ⁻⁵ mol to 2×10 ⁻³ mol, preferably 5×10 ⁻⁵
It can be contained within the range of mol to 5×10 ^-3 mol. General formula [a], [b], [c] or [
The compound represented by [d] may be added to any layer constituting the silver halide color photographic light-sensitive material, such as each photosensitive emulsion layer, subbing layer, intermediate layer, protective layer, etc., and is generally added to the subbing layer. It is preferable to add it to the lowest layer in contact with the undercoat layer (the layer closest to the support side), or to the lowest layer (the emulsion layer closest to the support side) among the light-sensitive emulsion layers. In order to add the compound represented by the general formula [a], [b], [c] or [d] of the present invention to a predetermined photographic constituent layer of a silver halide color photographic light-sensitive material, the photographic constituent layer is formed. or directly dispersed in a hydrophilic colloid solution, e.g. methanol,
It may be added to the hydrophilic colloid solution after being dissolved in one or a mixture of two or more suitable solvents such as ethanol, isopropanol, acetone, methyl ethyl ketone, dimethylformamide, dioxane, and ethyl acetate. Alternatively, after dissolving in one or a mixed solvent of two or more high boiling point organic solvents such as dibutyl phthalate, dioctyl phthalate, dimethyl phthalate, tri-o-cresyl phosphate, and trioctyl phosphate, hydrophilic colloids It may be emulsified and dispersed in a solution. Furthermore, when this compound is added to the photosensitive silver halide emulsion layer, it can be emulsified and dispersed simultaneously with the coupler and then added to the coating solution. The timing of adding the compound represented by the general formula [a], [b], [c] or [d] of the present invention to the coating solution is as follows: It may be carried out at any time after the preparation of the photosensitive silver halide emulsion. When the photosensitive silver halide emulsion is a surface latent image type emulsion that mainly forms a latent image on the grain surface, it may be prepared at any time after chemical ripening and optical sensitization. Further, when the photosensitive silver halide emulsion is an internal latent image type emulsion that mainly forms latent images inside the grains, it may be carried out at any time after the silver halide emulsion has been prepared and optically sensitized. In addition, general formulas [a], [
The compound represented by [b], [c] or [d] may be added to the non-photosensitive emulsion layer at any time before coating this emulsion layer, but it is preferably added immediately before coating. Further, general formulas [a], [
When adding the compound represented by [b], [c] or [d] to the color developer, the amount added is 1 to 500 mg, more preferably 10 to 500 mg per color developer.
~300mg range. [a], [b], [c] used in the present invention
Or, in order to add the compound represented by [d] to a color developing solution, it is dissolved in one or a mixture of two or more suitable solvents such as methanol, ethanol, isopropanol, acetone, dimethylformamide, etc. It can be added to the developer. Each structural unit forming a dye image in the present invention consists of a single emulsion layer or multiple emulsion layers that are sensitive to a certain region of the spectrum. The layers necessary for silver halide color photographic materials, including the layers of image-forming units described above, can be arranged in various orders as known in the art. A typical multicolor silver halide color photographic light-sensitive material comprises a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer with a cyan coupler forming at least one cyan dye image, at least one agenta dye image forming unit; A magenta dye image forming unit consisting of at least one green sensitive silver halide emulsion layer having a magenta coupler forming a dye image, at least one blue sensitive silver halide emulsion having a yellow coupler forming at least one yellow dye image. It consists of a support supporting a yellow dye image-forming structural unit consisting of layers. Examples of the yellow coupler preferably used in the present invention include those represented by the following general formula (E).

embedded image In the formula, R ₁ represents an alkyl group or an aryl group, R ₂ represents an aryl group, and X represents a hydrogen atom or a group that is eliminated during the color development reaction. R ₁ is a linear or branched alkyl group (e.g. butyl group) or aryl group (e.g. phenyl group), preferably an alkyl group (especially t-butyl group), and R ₂ is an aryl group (e.g. phenyl group). The alkyl group and aryl group represented by R ₁ and R ₂ include those having a substituent, and the aryl group of R ₂ is substituted with a halogen atom, an alkyl group, etc. is preferred. X is preferably a group represented by the following general formula (F) or (G), and of general formula (F), a group represented by general formula (F') is particularly preferable.

[Formula] In the formula, Z ₁ represents a group of nonmetallic atoms that can form a 4- to 7-membered ring. In the general formula (G) -O-R ₁₁ , R ₁₁ represents an aryl group, a heterocyclic group or an acyl group, and an aryl group is preferred.

[Formula] In the formula, Z ₂ is

[Formula] represents a group of nonmetallic atoms that can form a 4- to 6-membered ring. A preferred yellow coupler according to the present invention in the general formula (E) is represented by the following general formula (E').

embedded image In the formula, R ₁₄ represents a hydrogen atom, a halogen atom, or an alkoxy group, and a halogen atom is preferable. In addition, R ₁₅ , R ₁₆ and R ₁₇ are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group,
represents an alkoxy group, an aryl group, a carboxy group, an alkoxycarbonyl group, a carbamyl group, a sulfon group, a sulfamyl group, an alkylsulfonamido group, an acylamido group, a ureido group, or an amino group, and R ₁₅ and R ₁₆ are each a hydrogen atom; R ₁₇ is preferably an alkoxycarbonyl group, an acylamido group or an alkylsulfonamide group. Further, X represents a group having the same meaning as that shown in the above general formula (E), and is preferably the above general formula (F) or (G), or more preferably the above general formula (F). ') can be mentioned. Preferred specific examples of the yellow coupler of the present invention represented by the general formula (E') are shown below, but the yellow coupler of the present invention is not limited thereto.

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[C] These couplers are manufactured by British Patent No. 1077874,
Japanese Patent Publication No. 45-40757, Japanese Patent Publication No. 1031-1977, Japanese Patent Publication No. 47-47-
No. 26133, No. 48-94432, No. 50-87650, No. 51
−3631, No. 52-115219, No. 54-99433, No. 52-115219, No. 54-99433, No.
No. 54-133329, No. 56-30127, U.S. Patent No.
No. 2875057, No. 3253924, No. 3265506, No.
No. 3408194, No. 3551155, No. 3551156, No.
No. 3664841, No. 3725072, No. 3730722, No.
No. 3891445, No. 3900483, No. 3929484, No. 3929484, No. 3900483, No. 3929484, No.
No. 3933500, No. 3973968, No. 3990896, No.
No. 4012259, No. 4022620, No. 4029508, No. 4029508, No.
No. 4057432, No. 4106942, No. 4133958, No. 4133958, No. 4106942, No. 4133958, No.
No. 4269936, No. 4286053, No. 4304845, No. 4269936, No. 4286053, No. 4304845, No.
No. 4314023, No. 4336327, No. 4356258, No. 4314023, No. 4336327, No. 4356258, No.
It is described in No. 4386155, No. 4401752, etc. In the silver halide photographic light-sensitive material of the present invention, couplers represented by the following general formulas [a] and [a] can be preferably used as the magenta dye image-forming coupler.

[In the formula, Ar represents an aryl group, Ra ₁ represents a hydrogen atom or a substituent, and Ra ₂ represents a substituent. Y is a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent, and W is -NH
-, -NHCO- (N atom is bonded to the carbon atom of the pyrazolone nucleus) or -NHCONH-, and m is an integer of 1 or 2. ] Specific example of [a]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

In the magenta coupler represented by the formula: Za represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Za may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, Ra represents a hydrogen atom or a substituent. Examples of the substituent represented by Ra include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group,
Aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, organic hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamido group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryl Examples include oxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group.

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[Chemical formula] The magenta couplers represented by the general formulas [a] and [a] used in the present invention are, for example, U.S. Pat.
No. 3062653, No. 3127269, No. 3311476, No. 3152896, No. 3419391, No. 3519429,
Same No. 3555318, Same No. 3684514, Same No. 3888680,
Same No. 3907571, Same No. 3928044, Same No. 3930861,
Specifications of JP-A-49-29639, JP-A-49-111631, JP-A-49-129538, etc.
No. 50-13041, No. 52-58922, No. 55-
No. 62454, No. 55-118034, No. 56-36043, No. 57
-35858, 60-23855, British Patent No.
1247493, Belgian Patent No. 769116, Belgian Patent No.
No. 792525, specifications of West German Patent No. 2156111, Japanese Patent Publication No. 46-60479, Japanese Patent Publication No. 125732-1988, Japanese Patent Publication No. 59-125-
No. 228252, No. 59-162548, No. 59-171956, No. 59-171956, No. 59-162548, No. 59-171956, No.
Publications No. 60-33552 and No. 60-43659, West German patents
It is described in the specifications of No. 1070030 and US Pat. No. 3,725,067. Two or more of the above yellow and magenta couplers may be contained in the same blue-sensitive, green-sensitive, and silver halide emulsion layers, respectively. Also, the same coupler may be included in two or more different layers having the same color sensitivity. These yellow and magenta couplers are generally 2 x 10 ^-3 mol to 1 mol, preferably 1 x 10 ^-2 mol to 8 x 10 ^-1 mol, per mol of silver in the emulsion layer.
Used in the molar range. The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative film, a positive film, or a color photographic paper, but especially when used as a color photographic paper for direct viewing, the method of the present invention can be used. The effects of this will be effectively demonstrated. The silver halide photographic material of the present invention, including this color photographic paper, may be for monochrome use or for multicolor use. In the case of multicolor silver halide photographic light-sensitive materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers, and a non-light-sensitive layer are usually used. Although the structure has a structure in which a suitable number of layers and layer order are laminated on a support, the number and order of layers may be changed as appropriate depending on the important performance and purpose of use. The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention (hereinafter simply referred to as the silver halide emulsion of the present invention) includes silver bromide, silver iodobromide, silver iodochloride, silver salts, etc. Any of those used in conventional silver halide emulsions, such as silver bromide and silver chloride, can be used. The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different. In the silver halide emulsion, halogen ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. Further, while taking into consideration the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by adding them sequentially or simultaneously while controlling the pH and pAg in the mixing pot. After growth, a conversion method may be used to change the silver halide composition of the grains. When producing the silver halide emulsion of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary. The silver halide grains used in the silver halide emulsion of the present invention are formed by cadmium salt, zinc salt, lead salt,
Metal ions can be added using thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts or complex salts to be included inside the particles and/or on the surface of the particles, and placed in an appropriate reducing atmosphere. In some cases, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces. In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, the method described in Research Disclosure No. 17643 can be used. The silver halide grains used in the silver halide emulsion of the present invention may consist of uniform layers inside and on the surface, or may consist of different layers. The silver halide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains. The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of [100] plane to [111] plane can be used. or,
The particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions. The silver halide emulsion of the present invention is chemically sensitized by a conventional method. In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensing methods can be used alone or in combination. The silver halide emulsion of the present invention uses a dye known as a sensitizing dye in the photographic industry.
Can be optically sensitized to a desired wavelength range. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good. The silver halide emulsion of the present invention may be used during chemical ripening and/or for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials and/or maintaining stable photographic performance. When finished,
and/or after chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers may be added. As the binder (or protective colloid) for the silver halide emulsion of the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins,
Hydrophilic colloids such as sugar derivatives, cellulose derivatives, synthetic hydrophilic polymeric substances such as single or copolymers can also be used. The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention can be hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. Filmed. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution. A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic material of the present invention. The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion can be used. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. The oil-in-water emulsification dispersion method is
A method of dispersing a hydrophobic compound such as a coupler can be applied, and it is usually dissolved in a high boiling point organic solvent with a boiling point of 150°C or higher, in combination with a low boiling point and/or water-soluble organic solvent as necessary, and a gelatin aqueous solution etc. Using a surfactant in a hydrophilic binder and dispersing means such as a stirrer, homogenizer, colloid mill, flow mixer, and ultrasonic device,
After being emulsified and dispersed, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion. Examples of high-boiling oil agents include organic solvents with a boiling point of 150°C or higher, such as phenol derivatives, phthalates, phosphates, citric esters, benzoic esters, alkylamides, fatty acid esters, and trimesic esters that do not react with the oxidized form of the developing agent. is used. Anionic surfactants, nonionic surfactants, Cationic surfactants can be used. Between the emulsion layers of the color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers),
Color antifoggants are used to prevent color turbidity, deterioration of sharpness, and noticeable graininess due to migration of oxidized products of developing agents or electron transfer agents. The color antifoggant may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers. In the color light-sensitive material using the silver halide emulsion of the present invention, an image stabilizer can be used to prevent deterioration of the dye image. Ultraviolet absorbers are added to the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. It may be included. A color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development. The silver halide emulsion layer and/or other hydrophilic colloid layer of a silver halide photosensitive material using the silver halide emulsion of the present invention reduces the gloss of the photosensitive material, improves the ease of writing, and provides a layer between the photosensitive materials. A matting agent can be added to prevent sticking. A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention. An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion of the present invention. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer. The photographic emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention may be used to improve coating properties, prevent static electricity, improve slipperiness, emulsification dispersion, prevent adhesion, and (promote development, hardening, etc.). Various surfactants are used for the purpose of improving photographic properties (such as film formation and sensitization). The light-sensitive material using the silver halide emulsion of the present invention has a photographic emulsion layer, and other layers are baryta layers or α
- Paper laminated with olefin polymer, etc.
Flexible reflective support such as synthetic paper, cellulose acetate,
It can be applied to films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics. The silver halide material of the present invention can be used directly or after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary. It may be coated via one or more subbing layers (to improve wear resistance, hardness, antihalation properties, friction properties, and/or other properties). When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously. The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten lamps, fluorescent lamps, mercury lamps,
Xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser lights, light emitting diode lights, electron beams, X-rays, γ
Any known light source can be used, such as light emitted from a phosphor excited by rays, alpha rays, or the like. Exposure times include not only exposure times of 1 millisecond to 1 second, which are normally used in cameras, but also exposure times shorter than 1 microsecond, such as those using cathode ray tubes or xenon flash lamps.
Exposures of 100 microseconds to 1 microsecond can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently. In the treatment method of the present invention, treatment baths known in the art may be combined as necessary, and any treatment steps can be used. Examples of treatment steps preferably used in the present invention are listed below. 1 Color development-bleach-fixing-water washing 2 Color development-bleach-fixing-stabilization 3 Color development-bleaching-fixing-water washing 4 Color development-bleaching-fixing-stabilization Note that the water washing steps that may be included between each processing bath are as follows: Omitted. Among the treatment steps 1 to 4 above, 1 to 2 are preferred from the viewpoint of speeding up and reducing pollution. The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds generally contain approximately
Concentrations from 0.1g to about 30g, preferably color developer 1
It is used at a concentration of about 1 g to about 15 g. For rapid development, the amount is more preferably 4 g or more, particularly preferably 6 g to 15 g. A particularly useful primary aromatic amino color developer is an N,N'-dialkyl-p-phenylenediamine compound, in which the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, and N,N'-dimethyl-p-phenylenediamine hydrochloride. salt, 2-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,
Examples include N'ethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, and the like. In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention further contains various components that are normally added to color developers, such as sodium hydroxide and sodium carbonate. , alkali agents such as potassium carbonate, alkali metal sulfites, hydroxyamines, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, etc. may be optionally contained. You can also do it. The pH of the color developer is usually 7 or higher,
Generally in the range of 10-13. For rapid development, pH is preferably 10.5 or higher. The color development temperature is usually 15°C or higher, generally in the range of 20°C to 50°C. For quick development
The temperature is preferably 30°C or higher, more preferably 35°C or higher. In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. As the bleaching agent used in the bleaching process, a metal complex salt of an organic acid is used, and the metal complex salt is
It has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. Its composition is aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. Coordinated with metal ions such as iron, cobalt, and copper. The most preferred organic acids used to form such metal complexes of organic acids include:
Mention may be made of polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid Sodium Acetate Salt The bleaching agent used contains a metal complex salt of an organic acid as described above as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.
In addition, PH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions may be added as appropriate. . Furthermore, the fixing solution and bleach-fixing solution contain sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, and borax. , sodium hydroxide, potassium hydroxide,
It may contain one or more PH buffers consisting of various salts such as sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. Further, a bleaching accelerator may be included. When the process of the present invention is carried out without replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath. In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent may be added. For example, hydrogen peroxide, bromate, persulfate, etc. can be used as appropriate. The temperatures of the bleaching, fixing and bleach-fixing baths are also usually above 15°C, generally in the range of 20°C to 50°C, but preferably above 30°C for rapid processing. In this case, the processing time is generally within 2 minutes, but it can be changed depending on the temperature, bleaching ability and fixing ability. For rapid processing, it is preferably used within 90 seconds. Although the stabilizing treatment can be added after the water washing step, from the viewpoint of speeding up, a water washing substitute stabilizing solution is preferable. The water-washing alternative stabilizer may contain an anti-bacterial agent, an ammonium compound, a chelating agent, and the like. These specific conditions are described in Japanese Patent Application Laid-Open No. 58-134636.
You can refer to the publication number, etc., but the processing temperature is 20
℃~45℃ is preferred. The water used in the washing step may be either so-called "reserved water" or "running water", but efficient upstream water is preferable. Furthermore, the method for reducing the amount of washing water and the multistage countercurrent treatment method described in JP-A-57-8543 and JP-A-58-134636 can also be used. [Examples] The present invention will be explained in more detail below with reference to specific examples, but the embodiments of the present invention are not limited thereto. [Example 1] Samples were prepared with the layer configuration shown in Table 1 below.

[Table] Each sample was prepared by changing the composition of the coupler dispersion used in Layer 1 as shown in Table 2.
A more detailed sample preparation method is shown below. 40 g of the couplers according to the present invention and comparative couplers shown in Table 2 are heated and dissolved in a mixed solvent of 30 ml of the high boiling point organic solvent shown in the table and 100 ml of ethyl acetate, and this solution is mixed with a 5% aqueous gelatin solution containing sodium dodecylbenzenesulfonate. After adding to 300ml,
Emulsification and dispersion was performed using an ultrasonic homogenizer, and the resulting dispersion was mixed with 500 g of photosensitive silver chlorobromide emulsion, and layer 1 was prepared by coating and drying on polyethylene-coated paper. Layer 2 was also created in accordance with the method shown for layer 1 above. However, the amount of coupler applied in layer 1 was 6.0 mg/100 cm ² . These samples 1 to 25 were subjected to optical wedge exposure with red light using a sensitometer (Model KS-7, manufactured by Konishiroku Photo Industry Co., Ltd.), and then subjected to the following treatments. Standard processing steps (processing temperature and processing time) [1] Color development 38°C 3 minutes 30 seconds [2] Bleach fixing 33°C 1 minute 30 seconds [3] Washing process 25-30°C 3 minutes [4] Drying 75~ 80°C for about 2 minutes However, the following color developing solutions [A] and [B] were used for color development. Processing solution composition (color developer [A] composition) Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3- Methyl-4-amino-N-ethyl-N-
(β-Methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to bring the total amount to 1, pH 10.20 Adjust to. Color developer [B] composition The composition was the same as color developer [A] except that it did not contain benzyl alcohol. (Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and water Add to make the total amount 1. The following image storage test was conducted on each of the samples obtained as described above, and the results are shown in Table 2. [Image Preservability Test] The dye residual rate was expressed as a percentage (%) of the density D after the following test relative to the initial density D ₀ =1.0 before the test. That is, it was expressed as: Dye residual rate (%)=D/D ₀ ×100. (Dark fading test conditions) 85°C, 60% RH, 2 weeks (bright fading test conditions) Xenon fade meter 200 hours The structures of the comparative couplers and comparative high boiling point organic solvents used in the table are shown below. (Comparison cyan coupler)

[ka] High boiling point organic solvent for comparison DOP: Dioctyl phthalate (Example a-11) TOP: Trioctyl phosphate (Example b-7) DBP: Dibutyl phthalate (Example a-9)

[Table] From the second result, Comparative Samples 1 to 3 are inferior in dark fading, Comparative Samples 3 and 8 have extremely low bright fading, and Comparative Sample 10 has both bright and dark fading. It was insufficient. In other words, it is clear that these comparative samples cannot satisfy both dark fading properties and light fading properties at the same time. Furthermore, if a color developing solution containing no benzyl alcohol is used, it is undesirable because it deteriorates the color developing solution. On the other hand, the sample according to the present invention, that is, the combination of the specific cyan coupler according to the present invention and a specific high-boiling point organic solvent, improves the bright fading property without deteriorating the dark fading property, or improves the bright fading property without deteriorating the bright fading property. It is clear that the dark fading property has been improved, and some have even improved both at the same time, producing effects that could not even be predicted from the prior art. Furthermore, as in Samples 17 and 18, it can be seen that there is no problem even if high boiling point organic solvents other than those of the present invention are used in combination. <Example 2> A coating solution for each layer was prepared so as to have the layer structure shown in Table 3 below, and was coated sequentially from the support side to prepare a multilayer silver halide photographic material, which was used as Comparative Sample 1.

[Table] The structures of the ultraviolet absorbers used in Table 3 are shown below.

[ka]

Samples 2 to 11 were prepared in the same manner as Comparative Sample 1, except that the cyan coupler dispersion composition of the fifth layer and the compounds further added to the second layer in Comparative Sample 1 were changed as shown in Table 4. The obtained sample was subjected to exposure, processing, and image storage test in the same manner as in Example 1, except that the color developer [B] in Example 1 was changed to the following color developer [C] and the development time was changed to 1 minute. The results obtained are also shown in Table 4. Color developer [C] composition Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 50g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-methyl-4-amino-N-ethyl -N-
(β-Methanesulfonamidoethyl)-aniline sulfate 8g Fluorescent brightener (4,4'-diaminostilbensulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Auxiliary developer (c-6) 100mg Add water to total amount was set to 1, and the pH was adjusted to 11.0.

[Table] From the results in Table 4, compared to comparative sample 1,
In No. 11, the improvement effect of the present invention was rather amplified in the multilayer silver halide photographic light-sensitive material, and the results were almost satisfactory. Furthermore, it is clear that the samples according to the present invention did not show any deterioration even after rapid processing using color developer [C] and showed good results. <Example 3> Color developer [A] used in Example 2
and 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)- in [C]
Instead of aniline sulfate, 3-methyl-4-amino-N-ethyl-N-hydroxyethyl-aniline sulfate, 3-methyl-4-amino-N-ethyl-N-(2-methoxyethyl)-aniline -p-
Color developing solutions [D] and [E] were prepared with the same composition except that toluene sulfonate was used in equimolar amounts. A test was conducted in the same manner as in Example 2 except that the above color developing solutions [D] and [E] were used, and almost the same results as in Example 2 were obtained.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formula [] and/or [ A cyan dye image-forming coupler represented by ] and a compound represented by the following general formula [] are contained as oil droplets,
A silver halide photographic light-sensitive material characterized in that the silver halide photographic light-sensitive material is processed in a color developing solution containing no benzyl alcohol. General formula [] [In the formula, R ₁ represents an aryl group, cycloalkyl group, or heterocyclic group. R ₂ represents an alkyl group or an aryl group. _{R 3} represents a hydrogen atom, a halogen atom, an alkyl group, or Represents an alkoxy group. Z ₁ represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.) General formula [] [C] (In the formula, R ₄ represents an alkyl group, R ₅ represents an alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, or arylsulfonyl group, and R ₆ represents a hydrogen atom, a halogen atom, or an alkyl group. (Z ₂ represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.) General formula [] [C] (In the formula, R ₇ and _R8 represent an unsubstituted alkyl group having 3 to 15 carbon atoms, m and n are 0 to 4
represents an integer. )