JPS62178259A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To simultaneously improve the dark fading characteristic and fastness to light of a cyan dye image by incorporating a cyan dye image forming coupler having specific structure and compd. having specific structure in the form of oil drops into >=1 layers of emulsion layers. CONSTITUTION:The cyan dye image forming coupler expressed by the formula I and/or formula II as well as the compd. expressed by the formula III are incorporated in the form of oil drops into >=1 layers of the emulsion layers. R1 is an aryl group, etc., R2 is an alkyl group, etc., R3 is an H atom, halogen atom, etc., R4 is an alkyl group, R5 is an alkyl group, etc., R6 is an H atom, halogen atom, etc. Z1, Z2 are an H atom, halogen atom, etc. or the group which can be desorbed by the reaction with the oxidant of an arom. primary amine color developing agent. R7, R8 are an alkyl group having 3-15C. m, n are 0-4. The defect of the chlotriadine film hardening agent which deteriorates the shelf life of the red sensitive emulsion layer is thereby overcome and the unnecessary coloration is prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it contains a cyan coupler having excellent dispersion stability, and improves the storage stability of a dye image formed. The present invention relates to a silver halide color photographic light-sensitive material which has good properties.

[Background of the Invention] In order to form a dye image using a co-silver halide color photographic light-sensitive material, an aromatic primary amine color developing agent is usually used to reduce the halogenation in the exposed silver halide color photographic light-sensitive material. When silver particles 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 then added to the silver halide emulsion.

The basic properties required of each coupler are firstly that it has high solubility in high-boiling organic solvents, has good dispersibility and dispersion stability in silver halide emulsions, and does not easily precipitate. In addition, the resulting dye image has fastness to light, heat, moisture, etc. In particular, in cyan couplers, improvement of heat and humidity resistance (fading resistance) has become an important issue in recent years.

Conventionally known cyan couplers include 2 and 5, in which the 2- and 5-positions of the phenol are substituted with acylamino groups.
- diacylaminophenol cyan couplers, such as U.S. Pat.
and 55-163537.

Among these, 2,5-diacylaminophenol is widely used as a cyan coupler because it can provide cyan dye images with good fading resistance. However, there was a drawback that the yellowing (hereinafter referred to as optical Y stain) caused by this process was extremely poor. 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,
A 2-acylamino-5-ethylphenol cyan coupler is also known as a coupler with good dark fading resistance, but it not only has insufficient dark fading resistance compared to the 2,5-diacylaminophenol cyan coupler. 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 light 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 orthosulfonamidophenylacylamino group is treated with a high-boiling organic solvent having a specific dielectric constant. A method has been proposed to improve the color tone and fastness of dyes by dispersing them using benzyl alcohol. It is not preferable because it has low color development and also deteriorates 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.

The present inventors have conducted various studies in view of the above-mentioned current situation, 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 that forms a dye image with improved image storage stability without adversely affecting photographic properties.

A sixth object of the present invention is to contain a cyan coupler dispersed using a high boiling point organic solvent that can be extremely stably dispersed,
Therefore, it is an object of the present invention to provide a silver halide photographic material in which cyan coupler has good dispersion stability and does not cause precipitation failure.

[Specific Structure of the Invention] The object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least 111I of the silver halide emulsion layer has the following general formula: This was achieved by a silver halide photographic material containing a cyan dye image-forming coupler represented by [I] and/or [II] and a compound represented by the following general formula [11] as oil droplets. .

(In the formula, R1 represents an aryl group, a cycloalkyl group, or a heterocyclic group. R2 represents an alkyl group or an aryl group. R3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group.

Zl 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 [I[] t (wherein, R4 represents an alkyl group, R5 is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a,
It represents an alkylthio group, an arylthio group, an alkylsulfonyl group or an arylsulfonyl group, and R6 represents a hydrogen atom, a halogen atom or an alkyl group. Z2 represents a hydrogen atom, a group that can be separated by a halogen atom method or by reaction with an oxidized product of an aromatic primary amine color developing agent.

) general formula [I The aryl group represented by R1 in ] is, for example, a phenyl group or a naphthyl group, preferably a phenyl group. The heterocyclic group represented by R1 is, for example, a pyridyl group or a furan group. The cycloalkyl group represented by R1 is, for example, a cyclopropyl group or a cyclohexyl group. These groups represented by R1 include those having single or multiple substituents. For example, typical substituents introduced into the phenyl group include halogen atoms (e.g. fluorine, chlorine, bromine, etc.), alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), droxyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), alkylsulfonamide group (e.g. methylsulfone group). amide group, octylsulfonamide group, etc.), arylsulfonamide group (e.g. phenylsulfonamide group,
naphthylsulfonamide group, etc.), alkylsulfamoyl group (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoylaryloxycarbonyl group (e.g., phenyloxycarbonyl group, etc.), aminosulfonamide group) , an acylamino group, a carbamoyl group, a sulfonyl group, a sulfinyl group, a sulfoxy group, a sulfo group, an aryloxy group, an alkoxy group, a carboxylalkylcarbonyl group, an arylcarbonyl group, and an aminocarbonyl group.

Two or more of these substituents may be substituted with a phenyl group. Preferred groups represented by R1 include an unsubstituted phenyl group or a halogen atom, an alkylsulfonamide group, an arylsulfonamide group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and an alkylcarbonyl group. arylcarbonyl group, or cyano group as a substituent.

The alkyl group represented by R2 is linear or branched, and includes, for example, a methyl group, ethyl group, propyl group, butyl group, and octyl group. The aryl group represented by R2 is preferably a phenyl group.

In the present invention, preferred cyan couplers represented by the general formula [I] are compounds represented by the following general formula [T'].

General formula [E'] In the general formula [E'] 1, R7 represents a phenyl group.

This phenyl group includes those having single or multiple substituents, and the typical substituents to be introduced include halogen atoms (e.g. fluorine, chlorine, bromine, etc.), alkyl groups (e.g. methyl group, ethyl group, etc.). , 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, octylsulfonamide group) base, etc.),
Arylsulfonamide group (e.g., phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), alkyloxy Examples include a carbonyl group (eg, methyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, phenyloxycarbonyl group, etc.). Two or more of these substituents may be substituted with a phenyl group. Preferred groups represented by R7 include an unsubstituted phenyl group or a halogen atom (preferably fluorine or bromine), an alkylsulfonamide group (preferably an O-methylsulfonamide group, a p-octylsulfonamide group, or an O-dodecyl group). sulfonamide group)
, arylsulfonamide group (preferably phenylsulfonamide group), alkylsulfamoyl group (preferably butylsulfamoyl group), arylsulfamoyl group (preferably phenylsulfamoyl group), alkyl group (preferably methyl A phenyl group having one or more substituents with an alkoxy group (preferably a methoxy group or an ethoxy group).

R8 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 groups, carboxyl groups, and alkyl groups. (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, ethoxy group), aryloxy group, alkylsulfonamide group (e.g. methylsulfonamide group) group, octylsulfonamide group, etc.), arylsulfonamide group (e.g., phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl M (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), sulfamoyl group, etc.), alkyloxycarbonyl group (e.g., methyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, etc.), aminosulfonamide group (e.g., dimethylaminosulfonamide group, etc.),
Examples include an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group, an aminocarbonylamide group, a carbamoyl group, and a sulfinyl group. Two or more types of these substituents may be introduced.

Preferred groups represented by R8 are an alkyl group when n=Q and an aryl group when n-1 or more. R
A more preferable group represented by 8 is n=o
When , it is an alkyl group having 1 to 22 carbon atoms (preferably a methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group), and when it is n-1 or more, it is a phenyl group or an alkyl group ( (preferably t-butyl group, t-amyl group, octyl group), arylsulfonamide group (preferably phenylsulfonamide group), aminosulfonamide group (preferably dimethylaminosulfonamide group), alkyloxycarbonyl group (preferably It is a phenyl group having one or more substituents (methyloxycarbonyl group, butyloxycarbonyl group).

R9 represents an alkylene group. It represents a straight chain or branched alkylene group having 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.

R+o is a hydrogen atom or a halogen atom (fluorine, chlorine,
bromine or iodine). Preferably it is a hydrogen atom.

n is O or a positive integer, preferably O or 1.

X G, t-0-1-CO-1-COO-1-OC0-
2-8O2NR"-1-NR'SO2NR"-1-S
Represents a divalent group of -1-8O- or -3O2-. Here, R' and R" represent a substituted or unsubstituted alkyl group. X is preferably -0-1-S-1-SO-1-
8O2- group.

z3 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.

Preferred are chlorine atom and fluorine atom.

Typical specific examples of the cyan coupler represented by the formula CD are shown below in the margins, but the invention is not limited to these.

C+zH2s(n) (n)C12H25SOzNH In the present invention, the cyan coupler represented by the general formula [1[] is more preferably the following general formula 1% general formula [■'] where Rh and R12 are the same or different,
It represents a hydrogen atom, an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, amyl group, octyl group, dodecyl group, etc.), or an alkoxy group (eg, methoxy group, ethoxy group, etc.).

However, the total number of carbon atoms of R11 and R12 is 8 to 16. More preferably, RH and RI2 are each a butyl group or an amyl group.

R1:I is a hydrogen atom or an alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, octyl group, etc.)
It is.

Preferred are a hydrogen atom, an ethyl group, and a butyl group.

R15 has the same meaning as R5 in the general formula [I[].

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.) and R15 is preferably an alkyl group, more preferably a methyl group or an ethyl group.

m represents an integer from 0 to 2. z4 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 formulas [I], [■ko, [Work′] and [■′],
The groups represented by Zl, Z2, Z3 and Z4 which can be separated by reaction with the oxidized product of an aromatic primary amine color developing agent are well known to those skilled in the art and can modify the reactivity of the coupler. or by separating from the coupler and exerting functions such as development inhibition, bleaching inhibition, and color correction in the coating layer or other layers containing the coupler in the silver halide color photographic light-sensitive material. be.

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., oxacylyl, 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 formula [II] are shown below, but the invention is not limited thereto.

The cyan couplers represented by the general formulas [I] and [I[] 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 coupler. 2 X 10-'' mol-1 mol is preferred, more preferably 1 X 10-2 mol-8
X is in the range of 10-1 mol. Furthermore, the cyan coupler represented by the general formula [Equation 1] and the general formula [1[
] When a cyan coupler represented by the formula [I] is used in combination, the ratio is that of the cyan coupler of the general formula [I] to the cyan coupler of the general formula [I].
] The cyan coupler is preferably 10 to 90 mol%, more preferably 20 to 90 mol%.

In addition, general formula [I] and/or [II] according to the present invention
The cyan coupler represented by ] can be used in combination with other cyan couplers.

In the general formula [■], R7 and R8 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-hebutyl group, 1-methylbutyl group, n
-octyl group and the like.

In the general formula [11[], ■ and n each represent an integer of 0 to 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 rose positions.

Typical specific examples of compounds represented by the general formula ([11] are shown below in the margins, but the invention is not limited to these. 0 (I[l-1) (I[[-2) (I[[- 3) (III-4) 0COCH(CH2)2C)El 2H5 CH20COCH(CH2)2CH3 2Hs zHs 2H5 (Ill-18) (III-19) (III-20) (III-21) (III-22) (nu -23) (I[l-24) OCOCH(CH2)3CH3 2H5 (It-25) C&0COCH(CH2)3CH3 2H5 These compounds can be synthesized, for example, by the method described in Japanese Patent Publication No. 1616/1983. can.

The amount of the compound represented by the general formula [I[[] according to the present invention may be any amount depending on the case, but it is preferably 10 to 300% by weight, more preferably 20 to 150% by weight, based on the cyan coupler according to the present invention. A range of % 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 [I] and/or [II] according to the present invention and the cyan dye image-forming coupler according to the present invention represented by the general formula [I] The compound is contained in the silver halide emulsion layer as oil droplets.

In the present invention, containing the cyan coupler represented by the general formula [I] and/or [I] in the silver halide emulsion as oil droplets in the silver halide emulsion as well as other hydrophobic additives as necessary. Using a compound represented by the general formula [1[[], in this case, the following general formula [1[[]
Dissolved in other high-boiling organic solvents with a boiling point of about 150° C. or higher and a solubility in water of 10% or less that can be used in combination with the compound, if necessary in combination with a low-boiling point and/or water-soluble organic solvent,
After emulsifying and dispersing a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device, the desired halogenation is carried out. The cyan coupler represented by the general formula [I] and/or [I[] according to the present invention does not precipitate in the layer that is added to a silver emulsion, coated on a support, and dried. It means that the compound is dissolved in the compound represented by the general formula [1[I] and/or the high boiling point organic solvent that can be used in combination.

The compound represented by the general formula [1 [[] 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.

Preferably, the vapor pressure at 100°C is 0.51R.
It is a high boiling point organic solvent of IIIHIJ or less. More preferably, phthalate esters in the high-boiling organic solvent,
Or phosphoric acid esters. Note that the organic solvents that can be used in combination may be a mixture of two or more.

The high boiling point solvent used in combination in the present invention is preferably a dialkyl phthalate or phosphoric acid ester represented by the following general formula [IVal or [IVb].

General formula [IVal In the formula, R5 and R6 each represent an alkyl group.

General Formula [IVb] In the formula, R7, Ra and R9 each represent an alkyl group or an aryl group (for example, a phenyl group).

Each group represented by R5, R6, R7, R8 and R9 above is
It also includes those with substituents.

Typical specific examples of the high boiling point organic solvent represented by the general formula [IVal or [rVb] are listed below, but the present invention is not limited thereto.

The following margins (exemplary compounds) (ffa, -1) (IVjL -
2) (糎-3) (icb-4) (ike-5) low-6) (誼, -7) (corner-8) (ffa,
-IQ) (Brain-11). ,H.

C, I-1.

(Brain-12) (Sieve-13) (Lice-14,) (I'ii -1) (1@-
2) (saturated, -a) (π-4) (
Spoon-5) (Spoon-6) (yB-+o) (Ik-/J) OC+oHz+(n) (IYa-12) The amount is preferably the same as that of the general formula [11], that is, 10 to 300% by weight relative to the cyan coupler according to the present invention, and more preferably 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, a cyan dye-forming coupler, a compound of the general formula [I [ After mixing and dissolving the mixture, it can be mixed with an aqueous gelatin solution containing a surfactant, and then emulsified and dispersed using a high-speed rotation mixer, colloid mill, or ultrasonic dispersion machine.

General formula [I] and/or [■] and [
In addition to the compound represented by [III], compounds represented by the following general formulas [Va] to [VC] may be used in combination for the purpose of preventing discoloration.

In the general formula [Va], R7 and R8 each represent an alkyl group. R9 is an alkyl group, -NHR'q group, -SR'9 group (R'9 represents a monovalent organic group), or -〇 〇 OR''9 group (R''s is a hydrogen atom or a monovalent organic group). represents an organic group). m represents an integer from O to 3.

General formula [vbl In the formula, R11 is a hydrogen atom, a hydroxyl group, an oxyl radical group, -S OR'++ group, -8ChR't+ group (
R'11 represents an alkyl group or an aryl group. ),
Alkyl group, hydroxyalkyl group, alkenyl group, alkynyl group, benzyl group or -COR"t+ group (R"
++ represents a hydrogen atom or a monovalent organic group. ). Rj2, R'12 and R"+2 each represent an alkyl group. R+3n and RI4 each represent a hydrogen atom or a 100OR"' group (R"/ represents a monovalent organic group). Alternatively, R13 and R+4 may jointly form a heterocyclic group. n represents an integer of 0 to 4.

General formula [VC] In the formula, R+5, R+s and R17 may be the same or different, and each is a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an alkenyl group. represents.

In the present invention, the alkyl group represented by R7 and R8 in the general formula [Va ] preferably has 1 to 12 carbon atoms.
an alkyl group, more preferably an alkyl group having 3 to 8 carbon atoms and branched at the α position. Particularly preferred R7 and R8 are t-butyl group or [-pentyl group.

The alkyl group represented by R9 is linear or branched, such as methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, nonyl group, dodecyl group,
Such as octaacyl group.

When this alkyl group has a substituent, these substituents include a halogen atom, a hydroxyl group, a nitro group,
Cyano group, aryl group (e.g. phenyl group, hydroxyphenyl group, 3.5-di[-butyl-4-hydroxyphenyl M, 3.5-di-t-pentyl-4-hydroxyphenyl group, etc.), amino group ( For example, dimethylamino group, diethylamino group, 1,3.5-triazinylamino group, etc., alkyloxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group) carbonyl group, octadecyloxycarbonylphenoxycarbonyl group, etc.), carbamoyl group (e.g., methylcarbamoyl group, ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group, heptylcarbamoyl group, etc.), arylcarbamoyl group such as phenylcarbamoyl group, cycloalkylcarbamoyl groups such as cyclohexylcarbamoyl groups)
, incyanuryl group, and 1.3.5-triazinyl group. The amino group represented by R9 is
For example, alkylamino groups such as dimethylamino group, diethylamine group, and methylethylamino group; arylamino groups such as phenylamino group and hydroxylphenylamino group; cycloalkylamino groups such as cyclohexyl group; 1.
It includes heterocyclic amino groups such as 3.5-triazinylamino group and isocyanuryl group. The monovalent organic group represented by R's and R''9 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.) , aryl group (e.g. phenyl group, naphthyl group, etc.), cycloalkyl group (e.g. cyclohexyl group, etc.)
It includes heterocyclic groups (eg, 1,3,5-)-riazinyl group, isocyanuryl group, etc.). When these organic groups have a substituent, examples of the substituent include halogen atoms (e.g. fluorine, chlorine, bromine, etc.), hydroxyl groups,
Nitro group, cyano group, amino group, alkyl group (e.g. methyl group, ethyl group, 1-propyl group, t-butyl group,
-amyl group, etc.), aryl group (e.g., phenyl group, tolyl group, etc.), alkenyl group (e.g., allyl group, etc.), alkylcarbonyloxy group (e.g., methylcarbonyloxy group, ethylcarbonyloxy group, benzylcarbonyloxy group, etc.), Examples include arylcarbonyloxy groups (eg, benzoyloxy groups, etc.).

In the present invention, compounds represented by the general formula [Va] are preferably compounds represented by the following general formula [va'].

General formula [va'] In the formula, R25 and R26 each have 3 to 3 carbon atoms.
It represents eight straight-chain or branched alkyl groups, especially thi-butyl group and t-pentyl group. R27 does not represent a divalent organic group. k represents an integer from 1 to 6. ] Examples of the monovalent organic group represented by R27 include methyl group, ethyl group, propyl group, butyl group, pentyl group,
Alkyl groups such as octyl group, hekylidecyl group, methoxyethyl group, chloromethyl group, 1,2-dibromoethyl group, 2-chloroethyl group, benzyl group, phenethyl group,
Alkenyl groups such as allyl group, propenyl group, butenyl group, polyunsaturated hydrocarbon groups such as ethylene, trimethylene, propylene, hexamethylene, 2-chlorotrimethylene, etc., unsaturated hydrocarbon groups such as glyceryl, diglyceryl, pentaerythrityl, dipentaerythrityl Saturated hydrocarbon group, alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, cyclohexenyl group, 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, 1,2-11.3- or 1.
4-phenylene group, 3,5-dimethyl-1,4-phenylene group, 2-t-butyl-1,4-phenylene group, 2-
Examples include arylene groups such as a chloro-1,4-phenylene group and a naphthalene group, and a 1.3.5-trisubstituted benzene group.

R27 further includes, in addition to the above groups, a divalent organic group bonded to any group among the above groups via a 10-1-S-1-8O2- group.

R27 is more preferably 2.4-di-t-butylphenyl group, 2.4-di-t-pentylphenyl group, p-octylphenyl group, p-dodecylphenyl group, 3.5-
Di[-butyl-4-hydroxylphenyl group, 3,5
-di-t-pentyl-4-hydroxylphenyl group.

Preferably, k is an integer of 1 to 4.

Specific compounds represented by the general formula [1 [[] are listed below, but are not limited thereto.

Below margin C5H1t (t) CsH opening (1) C4H
9(t) Va” C4H9(t)
C4H9(t) C4Hg(t) C4H9(t) C4He(t) CsHo(t) 04H9(t) Va -16C3Htt(t) C5Ho(t) C5H11(t) C8I(17 C7H15(See) Va -20CIHy(ri) ■a-21C4H9(t) C<)Te(t)C4
)(9(t) C8HI7(t) C+L(i) ■a-26C4H9(t) CL C1゜C word J
Go+1 04H104H 9(t)C4HCsHo ('lee)C4M9(L)
C9H19(See)C4H9(t)
Cl2H25(See)CaH9(t)
C) (3 04H9 (t) Margin below In the present invention, the alkyl group represented by R11 in the general formula [Vb] has 1 to 12 carbon atoms, and the alkenyl group or alkynyl group has 2 to 4 carbon atoms. and preferred groups represented by R11 include a hydrogen atom,
Alkyl groups (e.g. methyl, ethyl, propyl,
butyl group, chloromethyl group, hydroxymethyl group, benzyl group, etc.), alkenyl group (e.g. vinyl group, allyl group, isopropenyl group, etc.), alkynyl group (e.g. ethynyl group, propynyl group, etc.), or -〇 OR"++ is a group, and R// is, for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group, etc.)
, alkenyl groups (eg, vinyl, allyl, isopropenyl, etc.), alkynyl groups (eg, ethynyl, propynyl, etc.), aryl groups (eg, denyl, tolyl, etc.).

The alkyl groups represented by R+2, R'12 and R''+2 are preferably linear or branched alkyl groups having 1 to 5 carbon atoms, particularly preferably a methyl group.

In R+3 and R+1, the monovalent organic group represented by R″′ is, for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a dodecyl group, an octadecyl group, etc.) ), alkenyl groups (e.g., vinyl groups, etc.), alkynyl groups (e.g., ethynyl groups, etc.), aryl N (e.g., phenyl groups, naphthyl groups, etc.), alkylamino groups (e.g., ethylamino Ji1, etc.), arylamino groups (e.g., anilino groups). ), etc.

Examples of the heterocyclic group formed jointly by R+3 and RI4 include (R28 is a hydrogen atom, an alkyl group, a cycloalkyl group, or a phenyl group).

In the present invention, compounds represented by the general formula [vb] are preferably those represented by the following general formula [Vb'].

General formula [Vb'] R29 is an alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, pendel group, benzyl group, etc.), alkenyl group (e.g., vinyl group, allyl group, isopropenyl group, etc.), alkynyl groups (e.g., ethynyl group, propynyl group, etc.), acyl groups (e.g., formyl group, acetyl group, propionyl group, butyryl group, acryloyl group, propioloyl group, methicryloyl group, ethinoyl group, etc.)
represents.

More preferred groups for R29 are a methyl group, an ethyl group, a vinyl group, an allyl group, a propynyl group, a benzyl group, an acetyl group, a propionyl group, an acryloyl group, a methacryloyl group, and a RI01-noyl group.

Specific compounds represented by the general formula [Vbl] are listed below in the margins, but are not limited thereto.

b-1 V-shi - 2 V-ray-3 H3 V-ray 4 Shih3 V-ray H3 V-shi - 8 V-shi9 4
A two-voice finish on A-shishi - 16 L-ray 17 / To 18 Eng 1 E-b-21 V-Do 22 ~ Shibu
1 V rake 6 V - 27 V rake 8 General formula [Vc] Odor T:,, R+5, R16
Examples of the halogen atom represented by y include a chlorine atom, a bromine atom, and the like, with elementary atoms being preferred.

The alkyl group and xy group represented by , R16 and R17 preferably have 1 to 20 carbon atoms, and the alkenyl group preferably has 2 to 20 carbon atoms, and these may be linear or branched.

Further, these alkyl groups, alkenyl groups, and alkyl groups may be substituted. Substituents include, for example, aryl,
Those substituted via a carbonyl group such as cyano, halogenated terocycle, cycloalkyl, cycloalkenybiro compound residue, bridged hydrocarbon compound residue, acyl, carboxy, carbamoyloxycarbonyl, and further substituted via an atom (specifically those substituted via an oxygen atom such as caltrop, alkoxy, aryloxy, heterocy, siloxy, acyloxy, carbamoyl, nitro, amino (including dialkylamino, etc.), sulfamoylamine) , alkoxycarbonylaminomino, sulfonamide, imide, ureido etc. substituted via nitrogen atom, alkylthio, arylthio, heterocyclic thio,
Examples include those substituted via a sulfur atom such as sulfonyl, sulfinyl, and sulfamoyl, and those substituted via a phosphorus atom such as phosphonyl.

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, sec-butyl group, n-butyl group,
n-amyl group, SeC-amyl group, -amyl group, α.
α-dimethylbenzyl group, octyloxycarbonylethyl group, methoxy group, ethoxy group, octyloxy group,
Examples include allyl group.

an aryl group represented by R15, R+6 and R17,
As the aryloxy group, for example, a phenyl group or a phenyloxy group is particularly preferable, and one having a substituent (for example, an alkyl group, an alkoxy group, etc.) may be used. Specifically, for example, phenyl group, 4-t-butylphenyl group, 2,
Examples include 4-di-t-amylphenyl group.

Among the groups represented by R+6 and RI7, hydrogen atoms,
Alkyl groups, alkoxy groups and aryl groups are preferred, and hydrogen atoms, alkyl groups and alkoxy groups are particularly preferred.

Among the groups represented by R+s, hydrogen atoms, halogen atoms, alkyl groups, and alkoxy groups are particularly preferred.

Specific compounds represented by the general formula [VH1] are listed below in the margins, but are not limited thereto.

c-1 c-2 CH.

c -3 c -4 0 each C4H9 (t) c -5 c -6 C4Hcjt) c -7 c -8 Vc -9 Vc-1°Vc-11 Vc-12 Vc-13 Vc-14 Vc, -16 (,:12ki25(tJ Vc-17 Vc-18 Below margin) When the compounds represented by the above general formulas [Va], [Vb] and [VC] are contained in the silver halide emulsion layer, the general formula according to the present invention [I] J3 and/or [
It is preferable to use 5 to 200 parts by weight, more preferably 10 to 100 parts by weight, per 100 parts by weight of the cyan coupler represented by I[].

In the silver halide photographic light-sensitive material according to the present invention, for the purpose of rapid processing, the following general formulas [Vlal to [VId
A dye image can be formed in the presence of a compound represented by l.

General formula [Vlal i''R4 (wherein, R1, R2, R3 and R4 each represent an alkyl group, and R1 and R2 and/or R3 and R4 combine with each other to form a nitrogen-containing heterocycle with a nitrogen atom. R5 represents a halogen atom, an alkyl group, or an alkoxy group, and nl represents an integer of O to 4.n
When l is an integer of 2 to 4, R5 may be the same or different. ) in the general formula [VIa], Rj, R
The alkyl group represented by 2, R3 and R4 may be linear or branched, and is preferably an alkyl group having 1 to 4 carbon atoms, and this alkyl group also includes those having a substituent. For example, hydroxy group, alkoxy! ! (for example, methoxy group, ethoxy group, etc.), sulfonamide group (for example, alkylsulfonamide group such as methanesulfonamide group, arylsulfonamide group such as benzenesulfonamide group, etc.), aryl group (for example, phenyl group, etc.), etc. It will be done. Examples of the alkyl group represented by R1, R2, R3 and R4 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group,
Examples include 5ec-butyl group, hydroxymethyl group, β-hydroxymethyl group, β-methoxyethyl group, methanesulfonamidoethyl group, and the like. The nitrogen-containing heterocyclic nucleus formed by R1 and R2 and/or R3 and R4 includes
Furthermore, it may contain an oxygen atom, a nitrogen atom, a sulfur atom, etc., such as a pyrrolidine nucleus, a piperidine nucleus, a morpholine nucleus, and the like.

Examples of the halogen atom represented by R5 in the general formula [11] include a bromine atom, a chlorine atom, etc., examples of the alkyl group include a methyl group, an ethyl group, etc., and examples of the alkoxy group include a methoxy group, Examples include ethoxy group. The alkyl group and alkoxy group represented by R5 include those having a substituent.

Specific examples of the compound represented by the general formula [VIa] used in the present invention are shown below, but the present invention is not limited thereto.

Below margin VIa--I V-12i
t -3''VI9-4 a3 CH3 W (L-7';) Addition 78 Shil'i3shi1'i3 These compounds, except for some, are known (for example, in JP-A No. Those skilled in the art can easily synthesize these compounds.
Bend, Desroches, Facets, James, Laby, Sterner, Pittam, Pieceburger Historical Society of American Society, (B
ent, Desslocl+.

Fassott, James, Ruby, 5t
erner, Vittum.

Weissberger: J, Am, Che
m, Soc, )] Yu, 3100 (1951
), [Pen 1~, Brown, Gressmanes, Harnisch: Photo Reproduction Engineering, (B e
nt, 8 rovn.

G lesmaness, t1arnis
h; Phot, Sci.

Eno, ) 8. 125 (19゛64) etc. can be referred to.

General formula [VIb] (In the formula, R6 and R7 each represent a hydrogen atom or an alkyl group, and NR6 and R7 may be combined with each other to form a nitrogen-containing heterocycle. R8 is a halogen atom, an alkyl group, or an alkyl group. group, and 2 represents an integer of O to 4. When R2 is an integer of 2 to 4, R8 may be the same or different.) In the general formula [VIb], an alkyl group represented by R6 and R7 may be linear or branched, and is preferably an alkyl group having 1 to 6 carbon atoms, and these alkyl groups include those having substituents, such as hydroxy groups, alkoxy groups (e.g. methoxy basis,
ethoxy group, etc.), 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 R6 and R7 include methyl group, ethyl group, butyl group, hexyl group, hydroxymethyl group, β-hydroxyethyl group, methoxymethyl group, β-methanesulfonamidoethyl group, etc. . The nitrogen-containing heterocyclic nucleus formed by R6 and R7 may further contain an oxygen atom, a nitrogen atom, a sulfur atom, etc., such as a pyrrolidine nucleus, a piperidine nucleus,
Examples include piperazine nucleus and morpholine nucleus.

Examples of the halogen atom represented by R8 include a bromine atom and a chlorine atom, examples of the alkyl group include a methyl group and an ethyl group, and examples of the alkoxy group include a methoxy group and an ethoxy group. It will be done.

The alkyl group and alkoxy group represented by R8 include those having a substituent.

When R2 is 2 to 4, R8 may be the same or different.

Specific examples of compounds represented by the general formula [VIbl used in the present invention are shown below, but the present invention is not limited thereto.

Below margin ■b-I Vlfb-2
”VIb-3mb-4 b-5Vi Millet 60 (
Jl-1vI'b-15Vnl-16 VI:b-17VZb-18 These compounds are, for example, US Pat. ! T No. 2,286,6
No. 78, No. 2,483,374, No. 2.77G,
No. 313, No. 3.060,225, British Patent No. 9
No. 28.671, Berichte der Deutschen Chemischen Gesellschaft, Volume 16, Page 724 (B ericl+teder Deutscben
Chen+1schen Ge5ellschaf
t) Volume 34 of the same magazine, page 2,125, Volume 92 of the same magazine, page 3,223 (Qhemiscl+e
3erichte), Photographic Science and Engineering Vol. 12, p. 41 (P.
photography science and
Engineering) and Journal of the Chemical Society Volume 1947, Volume 182
page (Journal of the Che
It can be synthesized according to the method described in MicalSociety, etc.

General formula [VIC] (wherein, X represents a hydrogen atom or a hydrolyzable group, R9 represents an aryl group, R4°, R11% R12
and RI3 each represent a hydrogen atom, an alkyl group or an aryl group. ) In the general formula [VIc], 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 R9 in the general formula [VIc] 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 group, ethyl group, propyl group, etc.), halogen atoms (chlorine atom, bromine atom, etc.), alkoxy groups (methoxy group, etc.) ethoxy group, etc.), a sulfonyl group, and an amide group (methylamide group, ethylamide group, etc.).

The alkyl group represented by Rhos R++, R+2, and R+3 in the general formula [VIc] preferably includes an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, butyl group, etc.).

This alkyl group includes those having a substituent, and examples of the substituent include a hydroxyl group, an amimu-L acyloxy group, and the like. Also Rho, R++, R+2 and R+
Examples of the aryl group of 3 include phenyl group and naphthyl group. This aryl group includes those having substituents, such as alkyl groups (methyl group,
Ethyl group 1. (propyl group, etc.), halogen atoms (chlorine atom, bromine atom, etc.), alkoxy groups (methoxy group, ethoxy group, etc.), and hydroxyl groups.

Typical specific examples of the compound represented by the general formula [VIC] used in the present invention are shown below, but the compound of the present invention is not limited thereto.

Below margin CHs Cu3
VEc-15 H ■c-19AL 20 Hirec 21 Mz 22W (
23"l=:, 24 H3 VfJ, -25wo-26 1c-27Mc 28 ■(, -29VI, 30 W, 31 'vLQ-33 VLt, -35 ■Otsu-32 VLc 34 %-36 vxc-37 VIc, -39 ■c-38 Compounds represented by the general formula [VIC] are commercially available, but include U.S. Patent No. 2,688,024, U.S. Pat. and JP-A-57-211147.

In the general formula [VIdl (wherein, A and B each represent a secondary amino group bonded to the carbon atom of the mother nucleus through a nitrogen atom, and Y represents a sulfur atom or an oxygen atom), 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 may be the same or different from each other. good.

Specifically, the above A and B are -N H-R+4 and -
Each can be represented by N H-R15, where R
n and R+5 are each an aliphatic or aromatic group, and R+4 and R+s are preferably electron-donating groups. Specific examples of the groups represented by R14 and R45 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 N (eg, methoxy group, ethoxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, etc.), and the like. R14 and R+s are, for example, methyl group, ethyl group, propyl group, butyl group, methoxymethyl group, β-methoxyethyl group, β
-ethoxyethyl group, thioethyl group, ethylthiomethyl group, allyl group, phenyl group, methoxyphenyl group,
Examples include ethoxyphenyl group, methylthiophenyl group, and ethylthiophenyl group.

Specific examples of the compound represented by the general formula [VId] used in the present invention are shown below, but the present invention is not limited thereto.

Vld-12,5-bis(methylamino)-1,3,4
-thiadiazole Vld-22-methylamino-5-ethylamino-1,
'3,4-thiadiazoleVld-32,5-bis(ethylamino)-1,3,4
-Thiadiazole Vld-42,5-bis(n-7ti)Lt7mi/)-
1,3,4-thiadiazole Vld-52-allylamino-5-methylamino-1,
3,4-thiadiazole VId-62-(2-ethoxyethylamino)=5-methylamino-1,3,4-diazoazoleVTd-72,5-bis(phenylamino)-1,3,
4-thiadiazole Vld-82,5-bis(2-methoxyethylamino)
-1,3,4-diazoazole VId-92-(2-ethoxyethylamino)-5-(
Vld-112-(2-methoxyethylamino)- 5-
Phenylamino-1,3゜4-deadiazoleVld-122-(p-Metho*CeniJLt7mino)-5-(2-methoxyethylamino)-1,3,4-deadiazoleVld-132-(3- Methylbuoprobylamino)-
5-(2-methoxyethylamino)-1,3,4-diazoazoleVld-142,5-bis(methylamino)-1,3,
4-Oxadiazole Vld-152,5-bis(ethylamino)-1,3,
4-Oxadiazole An example of the method for producing the diazole compound represented by the above general formula [VId] is described in JP-A-53-61334, Mei IB [B. C., Guha, Journal of the American Chemical Society, (P. ,C.

Quha, Journal or Ameri
Can Ch13111iCa13ociety)]
, Jou, p. 1036 (1928), and [Journal of Medical Chemistry, (Jou
rnal of Medical Chemistry
try, vol.

15, No. 3, p. 315 (1972)
It is described in etc.

In the present invention, the general formula [VIal, [VIb],
Color development may be carried out in the presence of a compound represented by [VTc] or [VTdl, but the presence here means that it is present at the time of color development; It may be allowed to stand, or it may be developed in advance and included in the developer. Furthermore, it may be included in advance in both the silver halide photographic light-sensitive material and the color developing solution.

When a compound represented by the general formula [VIal, [VIb], [VIc] or [VId] is added to a silver halide color light-sensitive material, the addition m may vary over a wide range depending on the halogen composition of the silver halide emulsion, the amount of silver, etc. The amount varies, but it is approximately 0,001 mol to 1 mol, preferably 0.002 mol to 0.2 mol, per mol of silver halide. In addition, when the photosensitive silver halide emulsion layer has a density of 2Ji or more, generally 2X 10-5 mol to 2X
10-3 mol, preferably 5X10-5 mol to 5X1
It can be contained within the range of 0-3 moles.

General formula [VIal, [VIb], [VIC]! 'ril
;t[VIdl is a compound represented by each photosensitive emulsion layer,
It may be added to any layer constituting a silver halide color photographic light-sensitive material, such as an undercoat layer, an intermediate layer, and a protective layer. It is preferable to add it to the layer closest to the support) or to the bottom layer (the emulsion layer closest to the support) of each photosensitive emulsion layer.

General formulas [VIa ], [VIb ], [VIC
] or [VId] can be added to a predetermined photographic constituent layer of a silver halide color photographic light-sensitive material by directly dispersing it in a hydrophilic colloid solution forming the photographic constituent layer, or by dispersing it, for example, in methanol. , ethanol, isopropanol, acetone, methyl ethyl ketone, dimethyl formamide, dioxane, ethyl acetate, etc., or a mixture of two or more thereof, and then added to the hydrophilic colloid solution. Also, for example, dibutyl phthalate, dioctyl phthalate, dimethyl phthalate,
After being dissolved in one or a mixed solvent of two or more high boiling point organic solvents such as tri-cresyl phosphate and trioctyl phosphate, it may be emulsified and dispersed in a hydrophilic colloid 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.

General formulas [VIal, [VIb], [VIcl] of the present invention
The compound represented by [VId] or [VId] can be added to the coating solution at any time after the preparation of the light-sensitive silver halide emulsion. good. 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. Furthermore, general formulas [VIa ], [VIb
], [VIc ] or [VId ] 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, the general formulas [VIal, [VIb] used in the present invention
], [VIc] or [VId], the amount added is 1 to 500 mg per 12 of the color developer, more preferably 10
~300 mg.

[VIa, [VIb], [VI
In order to add the compound represented by [C] or [VId] to a color developer, it is dissolved in one or a mixture of two or more suitable solvents such as methanol, ethanol, isopropanol, acetone, dimethylformamide, etc. After that, it can be added to the color developer.

Each structural unit forming a dye image in the present invention is
It consists of a single-hole emulsion layer or a multilayer emulsion layer that is 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 magenta dye image-forming unit; a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer with a magenta coupler forming a dye image; at least one blue-sensitive silver halide having a yellow coupler forming a yellow dye image; It consists of a support supporting a yellow dye image-forming structural unit consisting of an emulsion layer.

Examples of the yellow coupler preferably used in the present invention include those represented by the following general formula (E).

General formula (E) In the formula, R1 represents an alkyl group or an aryl group, and R
2 represents an aryl group, and X represents a hydrogen atom or a group that is eliminated during the color development reaction.

R1 is a straight chain or branched alkyl group (e.g. butyl group) or aryl group (e.g. phenyl group), preferably an alkyl group (especially t-butyl group), and R2 is an aryl group (preferably phenyl group). basis)
The alkyl group and aryl group represented by R1 and R2 include those having an @ substituent, and the aryl group of R2 is preferably substituted with a halogen atom, an alkyl group, or the like. X is the following general formula (F) or (G
) are preferable, and of general formula (F), groups represented by general formula (E') are particularly preferable.

General Formula (F) In the formula, zl represents a group of nonmetallic atoms that can form a 4- to 7-membered ring.

General formula (G) -O-Rh In the formula, Ru represents an aryl group, a heterocyclic group or an acyl group, and an aryl group is preferable.

General formula (E') Represents a group of nonmetallic atoms that can be formed.

A preferred yellow coupler according to the present invention in the general formula (E) is represented by the following general formula (E').

In the formula, R14 represents a hydrogen atom, a halogen atom, or an alkoxy group, and a halogen atom is preferred.

R+5, R16 and R17 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a carboxy group, an alkoxycarbonyl group, a carbamyl group, a sulfone group, a sulfamyl group, an alkylsulfonamide group, an acylamide group, represents a ureido group or an amine group, R+s and R16 are each a hydrogen atom, and R17 is an alkoxycarbonyl group,
An acylamido group or an alkylsulfonamide group is preferred. In addition, X represents a group having the same meaning as that shown in the general formula (E), preferably the general formula (F) or (
Among G) and (F), a group represented by the above general formula (E') is more preferred.

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.

Margin below (Y-1) (Y-2) (Y-3) H3 (Y-7) (Y-8) (Y-υ) (Y-10) (Y-13) (Y-14) t- These couplers are manufactured by British Patent No. 1,077.874, Japanese Patent Publication No. 45-40757, Japanese Patent Publication No. 47-1031, Japanese Patent Publication No. 47-26133, Japanese Patent Publication No. 48-94432, Japanese Patent Publication No. 48-94432.
No. 0-87650, No. 51-3631, No. 52-1
No. 15219, No. 54-99433, No. 54-133
No. 329, No. 56-30127, U.S. Patent No. 2,87
No. 5,057, No. 3,253,924, No. 3.265
．． No. 506, No. 3.408.194, No. 3,551,
No. 155, No. 3,551,156, No. 3,664.8
No. 41, 3,725,072@, 3.730.72
No. 2, No. 3.891,445, No. 3,900,48
No. 3, No. 3,929,484, No. 3,933,50
No. 0, 3,973,968@, 3,990,896
No. 4,012,259, No. 4,022,620, No. 4,029.508, No. 4,057,432, No. 4,106,942, No. 4,133,958
No. 4,269,936, No. 4,286,05
No. 3, No. 4,304,845, No. 4.314.023
No. 4,336,327, No. 4,356,258, No. 4,386.155, No. 4,401.752, etc.

In the silver halide photographic light-sensitive material of the present invention, the magenta dye image-forming coupler has the following general formula [a
] and [aI] can be preferably used.

General formula [a] Ar [wherein Ar represents an aryl group, Ra1 represents a hydrogen atom or a substituent, and Ra2 represents a substituent. Y represents a hydrogen atom or a substituent that can be removed by reaction with an oxidized product of a color developing agent, and W represents -NH-1-NHCO-(Nl
jj is bonded to the carbon atom of the pyrazolone nucleus) or -N
HCON H- is represented, and ■ is an integer of 1 or 2. ] In the magenta coupler represented by m 4 Ct Ct general formula [aI] below, specific examples in the blank space [a], Za represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle; The ring formed may have a substituent.

X represents a hydrogen atom or a substituent capable of eliminating 111t by reaction with an oxidized product of a color developing agent.

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, an aryl group, a heterocyclic group, Acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclicoxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group,
Sulf7moylamino group, alkoxycarbonylamino L
Examples include L aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group.

The following margins are general formulas [a] and [aI] used in the present invention.
] For example, the magenta coupler shown in U.S. Patent No. 2
, 600,788, 3,061,432, 3.062.653, 3.127.269, 3,311.476, 3.152.896 ,
Same No. 3,419,391, No. 3,519,429, No. 3,555.3113, No. 3,684.51
No. 4, No. 3.888.680, No. 3,907,5
No. 71, No. 3,928,044, No. 3,930,
No. 861, No. 3,930, No. 866, No. 3,933
, 500, etc., JP-A-49-29639, JP-A-49-111631, JP-A-49-129538, JP-A-50-13041, JP-A-52-58922, JP-A-55-
No. 62454, No. 55-118034, No. 56-36
No. 043, No. 57-35858, No. 6 (1-2385)
5, British Patent No. 1.247.493, Belgian Patent No. 769,116, Belgian Patent No. 192.525,
West German Patent No. 2.156.111, Japanese Patent Publication No. 46-60479, Japanese Patent Publication No. 59-125732, Japanese Patent Publication No. 59-228252, Japanese Patent Publication No. 59-162548,
No. 59-171956, No. 6G-33552, No. 60
-43659 publications, West German patent 1,070,030
No. 1 and U.S. 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 used in the range of 2.times.10@-3 mole to 1 mole, preferably 1.times.10@-2 mole to 8.times.10@-1 mole per mole of silver in the emulsion layer.

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 one for monochrome use or one 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 it has a structure in which layers are laminated on a support in an appropriate number and order, the number and order of layers may be changed as appropriate depending on the important performance and the 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. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to
It may be produced by controlling H and DAQ and adding them sequentially or simultaneously. Conversion methods may be used to change the silver halide composition of the grains after growth.

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 prepared in the process of forming and/or growing the grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt. Metal ions can be added to the inside of the particles and/or on the surface of the particles by adding iron salts or complex salts, and can be reduced inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Can provide sensitizing nuclei.

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. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may consist of a uniform layer inside and on the surface, or
It 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 the [10G] plane to the [111] plane can be used.

Further, 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. That is, compounds containing sulfur that can react with silver ions,
A sulfur sensitization method using activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver pentahalide emulsion of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. 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 includes steps for producing light-sensitive materials,
For the purpose of preventing fog during storage or photographic processing and/or keeping photographic performance stable, silver halide emulsions are used during and/or at the end of chemical ripening, and/or after the end of chemical ripening. Compounds known in the photographic industry as antifoggants or stabilizers can be added prior to coating.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer 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 are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. Ru. It is desirable that the hardening agent be added to the processing solution to the extent that it can harden the photosensitive material, 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 emulsion dispersion method can be applied to a method of dispersing a hydrophobic compound such as a coupler. Usually, a low boiling point and/or water-soluble organic solvent is added to a high boiling point organic solvent with a boiling point of 150°C or higher as necessary. Combined with a hydrophilic binder such as an aqueous gelatin solution, a surfactant is used to dissolve the gelatin in a stirrer, homogenizer,
After emulsification is carried out using a dispersing means such as a colloid mill, a flow jet mixer, or an ultrasonic device, 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 point oils include phenol derivatives that do not react with the oxidized form of the developing agent, phthalates, phosphates, citric esters, benzoates, alkylamides,
Boiling point of fatty acid ester, trimesic acid ester, etc. 150
An organic solvent having a temperature of ℃ or higher 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 layers with the same color sensitivity and/or between layers with different color sensitivities), the oxidized product of the developing agent or the electron transfer agent may migrate, causing color turbidity or sharpness. A color anti-capri agent is used to prevent deterioration of properties and noticeable graininess.

The eye color antifoggant may be used in the emulsion layer itself, or may be used 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 first layer and intermediate layer of the photosensitive material of the present invention 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. May contain.

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 the silver halide photosensitive material using the silver halide emulsion of the present invention reduces the gloss of the photosensitive material, increases the writeability, and sticks the photosensitive materials together. A matting agent can be added for prevention purposes.

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 the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Various surfactants are used for the purposes of preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, hardening, and sensitization).

The light-sensitive material using the silver halide emulsion of the present invention includes a photographic emulsion layer, other layers are a baryta layer or an α-olefin polymer, etc., a flexible reflective support such as paper or synthetic paper laminated with cellulose acetate, cellulose acetate, It can be applied to films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, boreethylene 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 applied 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 electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, or the like.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures 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 for the treatment step.
Any processing step can be used. Examples of treatment steps preferably used in the present invention are listed below.

1. Color development - bleach fixing - washing with water 2. Color development - bleach fixing - stabilization 3. Color development - constant bleaching, washing with water 4. Color development - constant bleaching - stabilization Note that the water washing step, which may be performed between each treatment bath, was 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 more stable than the free state and are therefore generally in salt form, such as hydrochloride or! iI! ! Used in acid salt form. These compounds are also generally used at a concentration of about 0.1 g to about 30 degrees per color developer 12, preferably from about 1 g to about 15 degrees per color developer 11.

For rapid development, the amount is more preferably 4 g or more, particularly preferably 6 g to 15 g.

Particularly useful primary aromatic amino color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and 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, N,
N'-dimethyl-p-phenylenediamine hydrochloride, 2
-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-
Ethyl-N-β-hydroxyedylaminoaniline, 4
-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate.

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 developing solution is usually 7 or more, and generally in the range of 10 to 13. For quick development, p
H10.5 or higher is preferable.

Color development temperature is usually 15°C or higher, generally 20°C.
It is in the range of °C to 50 °C. For rapid 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. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the metal complex salt 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. It has a structure in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred RflJ used to form such metal complexes of various acids include 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 The bleaching agent used in the sodium acetate salt contains a metal complex salt of an ionic 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.

Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
Buffers, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid It may contain one or more pH buffers consisting of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. Further, a bleaching accelerator may be included.

When carrying out the process of the present invention while 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-fix 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 a suitable oxidizing agent, For example, hydrogen peroxide, bromate, persulfate, etc. can be used as appropriate.

The temperatures of bleaching, fixing and bleach-fixing baths are also usually 15°C or higher, generally in the range of 20°C to 50°C, but preferably 30°C or higher 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-piping agent, an ammonium compound, a chelating agent, etc. For these specific conditions, reference may be made to JP-A-58-134636, etc., but the treatment temperature is preferably 20°C to 45°C.

The water used in the washing step may be either so-called "reserved water" or "running water", but efficient upstream water is preferable. Furthermore, it is also possible to use the method for reducing the amount of washing water and the multistage countercurrent treatment method described in JP-A-57-8543 and JP-A-58-134,636.

- [Example] The present invention will be described 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 1 Coating m: n+g/1ooC1' 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 high boiling point organic solvent 3011 and ethyl acetate 1001Q shown in the table, and this solution is dissolved in a 5% aqueous gelatin solution containing sodium dodecylbenzenesulfonate. After adding the mixture to 300 d, it was emulsified and dispersed using an ultrasonic homogenizer, and the resulting dispersion was mixed with 500 g of a photosensitive silver chlorobromide emulsion, and the mixture was coated on polyethylene-coated paper and dried to prepare Layer 1.

Layer 2 was also created in accordance with the method shown for layer 1 above.

However, the amount of coupler applied in layer 1 is 6.0 mg/100 (
It was set as t2.

These samples F1.1 to F25 were exposed to red light using a photosensitive needle (Model 11KS-7, manufactured by Konishiroku Photo Industry Co., Ltd.), and then subjected to the following treatments.

Standard treatment process (treatment temperature and treatment time) [1] Color development yA & 38℃ 3 minutes 30 seconds [2]
Bleach constant @ 33℃ 1 minute 30 seconds [3] Washing process
25-30℃ 3 minutes [4] Drying 75-80℃
Approximately 2 minutes However, for color development, use the following color developer [
A] and [B] were used.

Processing solution composition (color developer [A1 composition) Benzyl alcohol 151g ethylene glycol 151Q potassium sulfite 2.0g potassium bromide
0.7g sodium chloride
0.2g potassium carbonate
30.0 (J hydroxylamine 51! II salt
3゜0g polyphosphoric acid (TPPS)
2.503-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbenzsulfone R derivative) 1. Add OQ potassium hydroxide 2.0g water to bring the total volume to 11, and adjust to 1lH10.20.

Color developer [B] Composition Color developer [A] except that it does not contain benzyl alcohol
] The composition was the same as that of

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 (1 ethylenediaminetetraacetate Fli 3 (1f
Oh Fa M! 7: / Monium (70% solution)
1001Q ammonium sulfite (40% solution)
pl-I with 27.5d potassium carbonate or glacial acetic acid 7.
Adjust to 1 and add water to make the total volume 12.

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 of the following test relative to the initial density [)o-1,0 before the test. In other words, it was expressed as .

(Bright fading test conditions) 85° C. 60% RH 12 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.

(Comparative cyan coupler) t Comparative high boiling point organic solvent DOP: Dioctyl phthalate (Example IVa-11) T
OP trioctyl diphosphate (example rVb-7) DIR
: Dibutyl phthalate (Example ■a-9) From the results in Margin Table 2 below, first of all, Comparative Samples 1 to 3 have poor bright fading properties, Comparative Samples 3 and 8 have significantly low bright fading properties, and Comparative Samples No. 10 was insufficient in both light fading and light fading properties. In other words, it is clear that these comparative samples cannot simultaneously satisfy both the light fading property and the light fading property.

Furthermore, if a color developing solution containing no benzyl alcohol is used, it is undesirable because it deteriorates.

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 photobleachability without deteriorating the photobleaching property, or improves the photobleaching property without deteriorating the photobleaching property. It is clear that the bright color fading property has been improved, and some have even improved both at the same time, producing effects that could not even be expected 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 halogenated limited photographic material, which was used as Comparative Sample 1.

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

(tJV-1) (UV-2) Sample 2 to 11 was created.

Regarding the obtained sample, the color developing solution [
Exposure, processing, and image storage test were carried out in the same manner as in Example 1, except that 81 was changed to the following color developer [C] and the development time was changed to 1 minute. The obtained results are also shown in Table 4.

Color developer [C] Composition Ethylene glycol 15v1 Potassium sulfite 2.0 (Potassium monobromide 0.7g Sodium chloride
0.2 (J potassium carbonate
50g Human O-xylamine sulfate
3.0g polyphosphoric acid (TPPS>
2.5! +3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 8 g Optical brightener (4,4'-diaminostilbenesulfonic acid derivative) i, o g Potassium hydroxide 2.0 g of auxiliary developer (Vlc-6>100 mg water was added to bring the total amount to 12, and the pH was adjusted to 11.0.

The results of Table 4 below show that compared to Comparative Sample 1, the improved effects of the present invention are even more amplified in samples 2 to 11 when the multilayer silver halide photographic photosensitive month r1 and J3 are used. It was an acceptable result.

Furthermore, a rapid processing LIv using a color developing solution [C] was applied to J: ℃
Test r1 according to the present invention showed no deterioration and was good<r
It is clear that there are results.

<Example 3> Color developer [Δ1 and [C
] in 3-methyl-4-amino-N-1 pool-N-(
β-methanesulfonamide edyl)-1 niline sulfate instead of 3-meb-ru 4-ami2-N-edilu-N
-Human L1 xyethylaniline sulfate M salt, 3-methyl-
4-amino-N-edyl-N-(2-methoxyedyl)
-Aniline-pt~Color developer [DI, [E] with the same composition except that luenesulfonate was used in equimolar amounts.
It was created.

Examples except that the above color developing solutions [0] and [E] were used.
2 Tested in the same manner as in Example 2, almost the same results as 19Is Patent applicant Konishi Roku Photo Industry Co., Ltd. (Method) % Formula % 2. Name of the invention Silver halide photographic photosensitive @r1 3. Relationship with the case of the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Representative Director of Roku Konishi Photo Industry Co., Ltd.
Benko Keioi 8 Agent 102 Address 1-1, Kudankita 4-chome, Chiyoda-ku, Tokyo (n Posted on April 220 6, 1985, subject to amendment)

Claims (1)

[Scope of Claims] 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 [I] and/or [ A silver halide photographic material comprising a cyan dye image-forming coupler represented by [II] and a compound represented by the following general formula [III] as oil droplets. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc.▼ Represents an 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.) General formula [II] ▲ Formula , chemical formulas, tables, etc.▼ (In the formula, R_4 represents an alkyl group, and R_5 represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
It represents an alkylthio group, an arylthio group, an alkylsulfonyl group, or an 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 [III] ▲ Numerical formula, chemical formula, table, etc.▼ (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. )