JPH05241283A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent fade and yellow staining under high temperature and high humidity and to restrain deterioration even in the case of using a processing solution replenished in a small rate. CONSTITUTION:The silver halide photographic sensitive material containing a magenta coupler having an amine type stabilizing agent in the molecule is exposed and processed with the color developing solution replenished in an amount of 20-100ml per m<2> of the photosensitive material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of processing a silver halide photographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material), and more specifically, image storability and image quality of a formed dye image after running processing. The present invention relates to a method for processing a silver halide photographic light-sensitive material excellent in heat resistance.

[0002]

BACKGROUND OF THE INVENTION In a silver halide photographic light-sensitive material which is directly used for viewing, a combination of a yellow coupler, a magenta coupler and a cyan coupler is usually used as a color forming agent for forming a dye image. These couplers are required to have basic properties such as color reproducibility, color developability and image storability in a dye image to be obtained. It is desired that the color does not fade even when stored underneath, the uncolored part does not yellow (hereinafter referred to as Y stain), and the image quality does not change.

Heretofore, 5-pyrazolone compounds have been often used as magenta couplers. However, 5
-Dyes formed from pyrazolone compounds have side absorption that is unfavorable for color reproduction, and improvement thereof is desired. U.S. Pat. Nos. 3,725,067, 3,758,309,
No. 3,810,761 discloses pyrazoloazole-based couplers. The dye formed from the pyrazoloazole-based coupler has no unfavorable side absorption in color reproduction, but has extremely low fastness to light and significantly impairs the photographic performance of the photographic light-sensitive material.

Further, JP-A-59-125732, JP-A-61-282845, JP-A-61-292639, and JP-A-6-262945.
No. 1-279855 discloses a technique in which a pyrazoloazole coupler is used in combination with a phenol compound or a phenyl ether compound.
208048, 62-157031, 63-1
No. 63351 discloses a technique of using an amine compound in combination.

However, in the above technique, the fastness of the dye image to light is insufficient, and when the above compound is used in combination with the pyrazoloazole type coupler, the absorption of the formed dye becomes broad and color reproduction is achieved. It turned out to be unfavorable. Further, it was found that in the method of continuously processing the light-sensitive material (running processing), the characteristics of the finished print were largely changed due to the change of the processing component concentration, and the stability particularly when the dye image was stored was significantly deteriorated. .. In order to prevent this, the running process is generally performed while replenishing the replenisher with the process solution.

In this case, however, a large amount of overflow liquid is generated as the replenishment liquid is replenished, which is a serious problem in terms of the environment. Therefore, reduction of the replenishment liquid of the color developing solution (low replenishment) is strong. Is desired. However, when the replenishment of the processing solution is reduced, the Y-stain and the adhesiveness of the surface of the photosensitive material are increased by using the above-mentioned piazoloazole-based compound and a phenol-based, phenyl ether-based, or amine-based compound in combination, resulting in a finished print. It has been revealed that various problems occur in handling and storage.

[0007]

The first object of the present invention is to prevent the deterioration of the image such as fading and the generation of Y stain even when exposed to light after the running process and stored under high temperature and high humidity, and adhere. Another object of the present invention is to provide a processing method of a silver halide photographic light-sensitive material in which deterioration of image quality due to the above is suppressed.

A second object of the present invention is to consider environmental issues,
After performing a very low replenishment running process and a running process that reduces the overflow liquid, the deterioration of the image such as fading and Y stain is suppressed even when exposed to light or stored under high temperature and high humidity. Another object of the present invention is to provide a processing method of a silver halide photographic light-sensitive material, which is capable of suppressing deterioration of image quality due to adhesion and the like.

[0009]

The above object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material containing a magenta coupler having an amine-based image stabilizer in the molecule on a support. The replenishment amount of color developer is
It was achieved by a method of processing a silver halide photographic light-sensitive material characterized by processing with a color developing solution which is 20 to 100 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material.

Further, the above-mentioned object of the present invention is represented by the following general formula [I
A], general formula [IB], general formula [IC], general formula [I
D], general formula [IE], general formula [IF-1], general formula [IF-2], general formula [IF-3], and general formula [I
F-4], when a magenta coupler represented by
More preferably achieved.

[0011]

[Chemical 11]

[Wherein A represents a residue obtained by removing R ₂ or R ₃ from a pyrazolotriazole magenta coupler represented by the following general formula [II] or general formula [III], and L represents a divalent linkage. Represents a group. Y represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle with a nitrogen atom, and R ₁ represents a substituent. n represents an integer of 0 to 4.

[0013]

[Chemical 12]

In the formula, R ₂ and R ₃ represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. More preferably, the magenta coupler represented by the general formula [IA] described in (1) above is represented by the following general formula [IA-1] or general formula [IA-2]. Photosensitive material.

[0015]

[Chemical 13]

[In the formula, L ¹ represents a divalent linking group having a main chain having a chain length of 5 or less, and R ₁ and R ₂ represent a substituent.
Y represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle with a nitrogen atom, and n represents an integer of 0 to 4. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. Most preferably, the magenta coupler represented by the general formula [IA] described in (1) above is represented by the following general formula [IA-3] or general formula [IA-4].
Is a silver halide color photographic light-sensitive material.

[0017]

[Chemical 14]

[Wherein R ₁ , R ₂ and R ₄ represent a substituent, Y represents a group of non-metal atoms necessary for forming a 5-membered or 6-membered heterocycle with a nitrogen atom, and n represents 0 to 4
Represents the integer. m represents 1 or 2. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ] A silver halide color photographic light-sensitive material comprising at least one magenta coupler represented by the general formula [IB].

[0019]

[Chemical 15]

[Wherein A represents a residue obtained by removing R ₂ or R ₃ from the pyrazolotriazole magenta coupler represented by the general formula [II] or the general formula [III], and R _B
Represents an alkylene group, L _B represents a divalent linking group or a simple bond, R _B represents an alkylene group, and Y represents a non-membered group necessary for forming a 5- or 6-membered heterocycle with a nitrogen atom. Represents a group of metal atoms. ] A silver halide color photographic light-sensitive material containing at least one magenta coupler represented by the general formula [IC]

[0021]

[Chemical 16]

[Wherein A represents a residue obtained by removing R ₂ or R ₃ from the pyrazolotriazole magenta coupler represented by the general formula [II] or the general formula [III], and L _C
Represents a divalent linking group or a simple bond, and E represents -CO
-, - SO -, - SO 2 -, - N (R 16) -SO 2 -,
Represents —N (R ₁₆ ) —CO—, —O—CO—, R ₁₆ represents a hydrogen atom or a substituent, and Y represents a non-member necessary for forming a 5- or 6-membered heterocycle with a nitrogen atom. Represents a group of metal atoms. ] A silver halide color photographic light-sensitive material characterized by containing at least one magenta coupler represented by the general formula [ID].

[0023]

[Chemical 17]

[Wherein A represents a residue obtained by removing R ₂ or R ₃ from the pyrazolotriazole magenta coupler represented by the general formula [II] or the general formula [III], and L _D represents a divalent linkage. Represents a group or a simple bond, and B is -O-,-
_{S -, - SO 2 -,} - N (R 16) -, - N (R 16) 2 -
And R _D represents a hydrogen atom or a substituent, R _a ,
R _b , R _c and R _d represent an alkyl group, Y _D represents a group of non-metal atoms necessary to form a 5-membered or 6-membered group,
One atom in the group of non-metal atoms represents a bond with B, and R ₁₆ represents a hydrogen atom or a substituent. ] Further, at least one magenta coupler represented by the general formula [IE] is used.
Silver halide color photographic light-sensitive material characterized by containing two

[0025]

[Chemical 18]

[Wherein A represents a residue obtained by removing R ₂ or R ₃ from the pyrazolotriazole magenta coupler represented by the general formula [II] or the general formula [III], and L _E represents a divalent linkage. represents a group, R _E1 and R _E2 is a hydrogen atom or a substituent, R _E1 and R _E2 may be the same or different, may form a 5- to 7-membered ring fused together , K
Represents 0 or 1, and Z _E represents —O—, —S— or —N (R
₁₆ )-, and R ₁₆ represents a hydrogen atom or a substituent. ] A silver halide color photographic light-sensitive material containing at least one magenta coupler represented by any one of formulas [IF-1] to [IF-4].

[0027]

[Chemical 19]

[Wherein, L _a and L _b represent a divalent linking group or a simple bond, R _F represents an alkylene group or an arylene group, and Y is necessary for forming a 5- to 6-membered ring. A non-metal atom group, n _f represents 0 or 1, R _a1 ,
R _b1 , R _c1 , R _d1 and R _e1 represent a hydrogen atom or a substituent, and at least one of R _{a1 to} R _d1 is a hydroxyl group, an alkoxy group, an aryloxy group or

[0029]

[Chemical 20]

And X _f is --S--, --SO ₂ --or-
N (R ₁₆ ) _2- , R ₁₆ represents a hydrogen atom or a substituent, and two R ₁₆ may be the same or different;
Represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]

The present invention will be described in more detail below. The present inventors drastically reduced the developer replenisher during the running process, and after performing the running process with the color developer whose replenishing amount of the color developer is 20 to 100 ml per 1 m ² of the light-sensitive material. , We are keenly aware of the processing method of silver halide photographic light-sensitive material, which suppresses the generation of fading and Y-stain even when it is exposed to light and is stored under high temperature and high humidity and which suppresses image deterioration due to adhesion. As a result of research, surprisingly, by using a magenta coupler having the above amine-based image stabilizer in the molecule in a light-sensitive material, the replenishment amount of the color developing solution was 1 m ^{2 of the} silver halide photographic light-sensitive material. An image of fading or Y stain generation even after being exposed to light or stored under high temperature and high humidity after running processing with a color developing solution of 20 to 100 ml per The present inventors have found a method for processing a silver halide photographic light-sensitive material in which deterioration of the image quality is suppressed and deterioration of image quality due to adhesion or the like is suppressed.

Further, surprisingly, the processing for virtually eliminating the overflow of the color developing solution, specifically, the running processing with the color developing solution of 20 to 60 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material is carried out. Even after performing the running process, deterioration of the image due to discoloration or Y stain generation and deterioration of image quality due to adhesion etc. is minimal even if exposed to light or stored under high temperature and high humidity after the running process. It turns out that it can be suppressed to the limit.

The magenta coupler having an amine image stabilizer in the molecule will be described below. The above general formulas [IA], [II], [III], [IA-1],
[IA-2], [IA-3], [IA-4], [I
B], [IC], [ID], [IE], [IF-1],
In [IF-2], [IF-3] and [IF-4], R ₁ , R ₂ R ₃ , R ₄ , R _D , R _E1 , R _E2 , R _a1 ,
The substituents represented by R _b1 , R _c1 , R _d1 and R _e1 include
There is no particular limitation, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl groups, but in addition to these, halogen atoms and cycloalkenyl, alkynyl, heterocycles, and the like. Ring, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy,
Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, and other groups, spiro compound residues, and bridged hydrocarbon compounds Residues and the like are also included.

R ₁ , R ₂ R ₃ , R ₄ , R _D , R _E1 ,
Of the substituents represented by R _E2 , R _a1 , R _b1 , R _c1 , R _d1 and R _e1 , the alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched. As an aryl group,
Phenyl is preferred. Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group. The alkyl component and the aryl component in the alkylthio group and the arylthio group are the above R ₁ , R ₂ R ₃ , R ₄ and
_Examples thereof include an alkyl group and an aryl group represented by R _D , R _E1 , R _E2 , R _a1 , R _b1 , R _c1 , R _d1 and R _e1 . The alkenyl group preferably has 2 to 32 carbon atoms and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferable. Examples of the sulfonyl group include an alkylsulfonyl group and an arylsulfonyl group. Examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group. Examples of the phosphonyl group include an alkylsulfonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, and an arylphosphonyl group. Examples of the acyl group include an alkylcarbonyl group and an arylcarbonyl group.

Examples of the carbamoyl group include an alkylcarbamoyl group and an arylcarbamoyl group. Examples of the sulfamoyl group include an alkylsulfamoyl group and an arylsulfamoyl group. Examples of the acyloxy group include an alkylcarbonyloxy group and an arylcarbonyloxy group.

Examples of the carbamoyloxy group include an alkylcarbamoyloxy group and an arylcarbamoyloxy group. Examples of the ureido group include an alkylureido group and an arylureido group. As the sulfamoylamino group, an alkylsulfamoylamino group,
Examples thereof include an arylsulfamoylamino group.

The heterocyclic group is preferably a 5- to 7-membered one, and specific examples thereof include a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group and a 2-benzothiazolyl group. The heterocyclic oxy group is preferably one having a 5- to 7-membered heterocycle, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-
5-oxy group etc. are mentioned.

The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,
3,5-triazole-6-thio group and the like can be mentioned. Examples of the siloxy group include a trimethylsiloxy group, a triethylsiloxy group and a dimethylbutylsiloxy group.
Examples of the imide group include a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, and a glutarimide group.

As the spiro compound residue, spiro [3,
3] Heptan-1-yl and the like can be mentioned. As a bridged hydrocarbon compound residue, bicyclo [2,2,1] heptane-
1-yl, tricyclo [3,3,1,1 ³⁷ ] decane-1
-Yl, 7,7-dimethyl-bicyclo [2,2,1] heptan-1-yl and the like. These R ₁ , R ₂ R
₃ , R ₄ , R _D , R _E1 , R _E2 , R _a1 , R _b1 , R _c1 , R _d1
And each group represented by R _e1 further includes those having a substituent.

Examples of the group represented by X which can be removed by the reaction with the oxidation product of the color developing agent include halogen atom (chlorine atom, bromine atom, fluorine atom and the like) and alkoxy, aryloxy, heterocyclic oxy, acyloxy and sulfonyl. Oxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by N atom,
Examples include groups such as alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl.
Preferred is a halogen atom, especially a chlorine atom.

When n is 2 or more, a plurality of R _1's may be the same or different, and a plurality of R ₁ 's may form a condensed ring. Also included in the present invention are polymer couplers and polymer couplers such as dimer couplers containing a pyrazolotriazole ring in R ₂ , R ₃ or X. Further, the present invention also includes a group represented by A in the general formula [IA] having a group obtained by removing A from the compound represented by the general formula [IA].

The above general formulas [IA], [IB], [I]
C], [ID], [IE], [IF-1], [IF-
2], [IF-3] and [IF-4], L, L
Examples of the divalent linking group represented by ¹ , L _B , L _C , L _D , L _E , L _a and L _b include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl. , Cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, alkoxy, aryloxy, heterocycleoxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxy A divalent group derived from each group of carbonialamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, etc. and a divalent group which can be formed by combining these divalent groups. Represents Mashiku is represented by the following general formula [X].

[0045]

[Chemical 21]

In the formula, the R ₁₃ side is bonded to the pyrazoloazole ring. R ₁₃ , R ₁₄ and R ₁₅ in the general formula [X] each independently represent an alkylene group having 1 to 12 carbon atoms, an arylene group, an alkylenearylene group or an aralkylene group. The alkylene group, which may be linear or branched, is, for example, a methylene group, a methylmethylene group, a dimethylene group, a decamethylene group, etc., and the arylene group is, for example, a phenylene group, a naphthylene group, etc., and an aralkylene group. As the alkylenearylene group,

[0047]

[Chemical formula 22]

And the like. The above R ₁₃ , R ₁₄ and R ₁₅
The alkylene group, arylene group, alkylenearylene group or aralkylene group represented by can have a substituent, and as the substituent, the above R ₁ , R ₂ , R ₃ and R _{4 can be used.}
Each substituent represented by Further, L, L ₂ and L ₃ in the general formula [X] are

[0049]

[Chemical formula 23]

Represents However, R ₁₆ represents a hydrogen atom, an alkyl group or an aryl group, and when two R ₁₆ are present,
Each R ₁₆ may be the same or different. p, q, r, s, t
And u represents an integer of 0 or 1.

[0051] -L _B -R _B in the general formula [IB] -,
-L _C in the general formula [IC] -, -L _D in the general formula [ID] -, -L _E in the general formula [IE] -, -L _a in the general formula [IF-1] - [IF-4] - and -L _b - chain length of the main chain of the divalent linking group is preferably atom having 15 or less represented by the case 10 or less but more preferably, there are cyclic moiety in the linking group wherein the The number of atoms in the portion is counted along the path with the smallest number of atoms, such as 3 for m-phenylene and 2 for o-phenylene.

R _B in the general formula [IB] has 1 to 32 carbon atoms.
The alkylene group may be linear or branched, and examples thereof include a methylene group, a methylmethylene group, a dimethylene group, and a decamethylene group. R _F in the general formulas [IF-1] to [IF-4] has 1 to 3 carbon atoms.
It represents two alkylene and arylene groups, and the alkylene group may be linear or branched and is, for example, a methylene, methylmethylene, dimethylene, decamethylene group or the like, and the arylene group is a phenylene or naphthylene group or the like.

The nonmetal atom group represented by Y _D in the general formula [ID] is preferably saturated hydrocarbon or saturated hydrocarbon containing oxygen atom, nitrogen atom and / or sulfur atom. The alkyl group represented by R _a , R _b , R _c and R _d in the general formula [ID] preferably has 1 to 32 carbon atoms, and may be linear or branched, or cyclic. It may be saturated or unsaturated, and examples thereof include a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, and a vinyl group. Of these, a linear alkyl group is particularly preferable. The following groups in the general formulas [IF-1] to [IF-4] are

[0054]

[Chemical formula 24]

It represents a phenol-based image stabilizer residue represented by, and more preferably, it is represented by the general formula [FA] or the general formula [FB].

[0056]

[Chemical 25]

In the general formula [FA], R ₁₂₂ ,
R ₁₂₃ , R ₁₂₅ and R ₁₂₆ are each a hydrogen atom, a halogen atom,
Hydroxyl group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or acylamino group, of which alkyl group, an alkenyl group, an alkyl group described for the R ₁ for an aryl group, an alkenyl group,
The same as the aryl group can be mentioned. Further, examples of the halogen atom include fluorine, chlorine, bromine and the like.

Further, specific examples of the alkoxy group include a methoxy group, an ethoxy group, a benzyloxy group and the like. Further, the acylamino group is R ₁₂₇ —CO
NH-, wherein R ₁₂₇ is an alkyl group (eg, methyl, ethyl, n-propyl, n-butyl,
n-octyl, tert-octyl, benzyl etc.), alkenyl group (eg allyl, octenyl, oleyl group), aryl group (eg phenyl, methoxyphenyl, naphthyl etc.) or heterocyclic group ( For example, each group of pyridinyl and pyrimidyl) can be represented.

In the general formula [FA], R ₁₂₄
Represents an alkyl group, a hydroxyl group, an aryl group, an alkoxy group, an alkenyloxy group or an aryloxy group. Of these, the alkyl group and the aryl group are the same as those represented by R ₁ above. It can be specifically mentioned. The alkoxy group for R ₁₂₄ may be the same as the alkoxy group described for R ₁₂₂ , R ₁₂₃ , R ₁₂₅ and R ₁₂₆ .

R ₁₂₂ and R ₁₂₃ may be ring-closed to each other to form a 5-membered or 6-membered heterocyclic ring, and R ₁₂₃ and R ₁₂₄ may be ring-closed to form a 5-membered or 6-membered ring. These rings may include those in which another ring is spiro-bonded. Typical examples of the phenolic image stabilizer residue represented by the general formula [A] are shown below, but the invention is not limited thereto.

[0061]

[Chemical formula 26]

[0062]

[Chemical 27]

[0063]

[Chemical 28]

[0064]

[Chemical 29]

[0065]

[Chemical 30]

In the general formula [B], R ₁₃₁ represents a secondary or tertiary alkyl group, a secondary or tertiary alkenyl group, a cycloalkyl group or an aryl group, and R ₁₃₂ represents a halogen atom, an alkyl group or an alkenyl group. , A cycloalkyl group or an aryl group, and n ² represents an integer of 0 to 3. When two or more R ₁₃₁ and R ₁₃₂ are present in the compound, each R ₁₃₁ and R ₁₃₂ may be the same or different. Y _B1 represents S, SO, SO ₂ or an alkylene group.

The secondary or tertiary alkyl group or secondary or tertiary alkenyl group represented by R ₁₃₁ is preferably one having 3 to 32 carbon atoms, particularly one having 4 to 12 carbon atoms. Include groups such as t-butyl, s-butyl, t-amyl, s-amyl, t-octyl, i-propyl, i-propenyl, and 2-hexenyl.

The alkyl group represented by R ₁₃₂ is preferably one having 1 to 32 carbon atoms, and the alkenyl group is preferably one having 2 to 32 carbon atoms, and may be linear or branched. Specifically, groups such as methyl, ethyl, t-butyl, pentadecyl, 1-hexynonyl, 2-chlorobutyl, benzyl, 2,4-di-t-amylphenoxymethyl, 1-ethoxytridecyl, allyl and isopropenyl are Can be mentioned.

The cycloalkyl group represented by R ₁₃₁ and R ₁₃₂ preferably has 3 to 12 carbon atoms, and examples thereof include cyclohexyl, 1-methylcyclohexyl and cyclopentyl groups. The aryl group represented by R ₁₃₁ and R ₁₃₂ is preferably a phenyl group or a naphthyl group, specifically, phenyl, 4-nitrophenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 3 −
Hexadecyloxyphenyl, α-naphthyl and the like can be mentioned.

The alkylene group represented by Y _B1 is preferably one having 1 to 12 carbon atoms, specifically, methylene,
Mention may be made of groups such as ethylene, propylene, butylidene, hexamethylene and the like. These R ₁₃₁ , R ₁₃₂ ,
Each group represented by Y _B1 may have a substituent. R
_{Examples of} the substituent which ₁₃₁ , R ₁₃₂ and Y _B1 may have are:
For example, halogen atom and nitro, cyano, amide,
Examples include groups such as sulfonamide, alkoxy, aryloxy, alkylthio, arylthio and acyl. Typical examples of the general formula [FB] are shown below, but the present invention is not limited thereto.

[0071]

[Chemical 31]

[0072]

[Chemical 32]

[0073]

[Chemical 33]

The above general formula [IA] and general formula [IA-
1], general formula [IA-2], general formula [IA-3], general formula [IA-4], general formula [IB], general formula [IC], general formula [IF-1], general formula [1]. IF-2], general formula [I
F-3] and the general formula [IF-4], the non-metal atom group represented by Y is

[0075]

[Chemical 34]

It is preferable to contain R ₁₇ and R ₁₈ each independently represent a hydrogen atom, an alkyl group or an aryl group, and n ¹ represents an integer of 0-2. The general formula [IA], the general formula [IA-1], the general formula [IA-2],
General formula [IA-3], general formula [IA-4], general formula [I
B], general formula [IC], general formula [IF-1], general formula [IF-2], general formula [IF-3], and general formula [I
F-4]

[0077]

[Chemical 35]

The 5- or 6-membered heterocyclic ring represented by the formula (6) may be saturated or unsaturated, but a saturated ring is preferable. Further, these heterocycles have R ₁ , R ₂ R ₃ , R ₄ , R _D ,
It may have a substituent represented by R _E1 , R _E2 , R _a1 , R _b1 , R _c1 , R _d1 and R _e1 .

General formula [IA-1] and general formula [IA-
2], L ¹ represents a divalent linking group having a main chain with a chain length of 5 or less. When a ring structure moiety is present in the linking group, the number of atoms in the moiety is, for example, m. -The phenylene is counted along the path with the smallest number of atoms such as 3, and the o-phenylene is counted as 2. The linking group represented by L ¹ is represented by, for example, the following general formula [X ₁ ].

General formula [X ₁ ] * ₁ -A ₁ -A ₂ -A ₃ -A ₄ -A _5- * ₂ [In the formula, A _{1 to} A ₅ are atoms each having a valence of 2 or more or It represents a mere bond, each atom may be further substituted with a hydrogen atom or a substituent, * ₁ represents a position bonded to the pyrazolotriazole ring, and * ₂ represents a position bonded to the phenoxy group. ]

[0081] A ₁ to A 2 or more valences of atoms that may have a valence _{of 5} represents the Periodic Table _{II A, III A, IV A} , V A,
An atom of Group VI _A , preferably a non-metal atom,
More preferred are carbon, nitrogen, oxygen, silicon, phosphorus, sulfur and selenium, and most preferred are carbon, nitrogen, oxygen, sulfur and phosphorus.

In the general formulas [IF-1] to [IF-4], when R _F represents an arylene group and n _f represents 1, the linking group La also has a main chain length similar to L ^1. Most preferably, it represents a divalent linking group having 5 or less atoms, and in that case L
a is the same as L ¹ . Examples of preferable L ¹ are shown below, but L ¹ is not limited thereto.

[0083]

[Chemical 36]

[0084]

[Chemical 37]

[0085]

[Chemical 38]

[0086]

[Chemical Formula 39]

[0087]

[Chemical 40]

[Wherein R ₁₀ , R ₁ , * ₁ , * ₂ , n, n
¹ is as described above, n ₁ represents 1 or 2, and n ₂
Is 1, 2 or 3, n ₃ is 0, 1, 2 or 3, n ₄
Represents an integer of 1 to 4, n ₅ represents an integer of 1 to 5, n ₆ represents 0 or 1, and n ₇ represents 0, 1 or 2. Typical examples of the magenta coupler according to the present invention are shown below, but the present invention is not limited thereto.

[0089]

[Chemical 41]

[0090]

[Chemical 42]

[0091]

[Chemical 43]

[0092]

[Chemical 44]

[0093]

[Chemical 45]

[0094]

[Chemical 46]

[0095]

[Chemical 47]

[0096]

[Chemical 48]

[0097]

[Chemical 49]

[0098]

[Chemical 50]

[0099]

[Chemical 51]

[0100]

[Chemical 52]

[0101]

[Chemical 53]

[0102]

[Chemical 54]

[0103]

[Chemical 55]

[0104]

[Chemical 56]

[0105]

[Chemical 57]

[0106]

[Chemical 58]

[0107]

[Chemical 59]

[0108]

[Chemical 60]

[0109]

[Chemical formula 61]

[0110]

[Chemical formula 62]

[0111]

[Chemical 63]

The pyrazolotriazole-based magenta coupler according to the present invention is a journal of the chemical
Society (Journal of the Che
medical Society), Perkin (Perki)
n); I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, 58-42045, 59-162548, 59.
-171956, 60-33552, 60-4
No. 3659, No. 60-172892, No. 60-190.
No. 779, No. 61-189539, No. 61-2417.
54, 63-163351, 62-15703.
It can be easily synthesized by those skilled in the art with reference to No. 1.

Next, typical synthesis examples of the pyrazolotriazole type magenta coupler according to the present invention will be shown below. Synthesis Example 1 Synthesis of Exemplified Compound MA-1 The synthetic route is shown below.

[0114]

[Chemical 64]

Compound (I) 10.0 g, potassium carbonate 9.2 g and α-bromolauric acid ethyl (II) 1
After adding 7.6 g to 250 cc of acetonitrile and heating under reflux for 10 hours, precipitated potassium bromide was filtered off by hot filtration. The filtrate was evaporated under reduced pressure, and the residue was washed with ethyl acetate 20
Extracted at 0 cc. After washing with water, it was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The pale yellow residue was recrystallized from acetonitrile to give 15.2 g of compound (II
I) was obtained.

After dissolving 9.1 g of the above compound (III) in 45 cc of ethyl alcohol, sodium hydroxide 1.
A solution prepared by dissolving 6 g in 50 cc of water was added, and the mixture was heated under reflux for 3 hours. After the reaction, the alkali was neutralized with diluted hydrochloric acid, ethyl alcohol was distilled off under reduced pressure, the mixture was extracted with ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The obtained oily substance was recrystallized from 300 cc of acetonitrile to obtain 7.2 g of white crystalline compound (IV).

Next, 1.4 g of p-nitrophenol and 20 cc of dioxane were added to 4.3 g of compound (IV), and after dissolution, dicyclohexylcarbodiimide (DCC) .2.
3 g was added, and the mixture was stirred at room temperature for 2 hours. After filtering the precipitate, the solvent was distilled off under reduced pressure, 50 cc of ethyl acetate was further added, and the solution was mixed with 50 cc of a 5% aqueous sodium carbonate solution to 3 cc.
After washing twice, it was dried over anhydrous magnesium sulfate.

The solvent was distilled off under reduced pressure to obtain 5.1 g of orange oily compound (V). Dimethylacetamide (60 cc) was added thereto, and compound (VI) (2.2 g) was further added and dissolved by heating. Then, 150 cc of acetonitrile and 0.5 g of imidazole were added, and the mixture was heated under reflux for 4 hours. After distilling off the solvent acetonitrile under reduced pressure, ethyl acetate 300c
c and 200 cc of water were added for liquid separation. 5% more organic phase
It was washed with 100 cc of an aqueous sodium carbonate solution three times and then dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography to obtain 5.0 g of white amorphous Exemplified Compound (MA-1). (The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.)

[0119]

[Chemical 65]

[0120]

[Chemical 66]

[0121]

[Chemical 67]

[0122]

[Chemical 68]

[0123]

[Chemical 69]

[0124]

[Chemical 70]

[0125]

[Chemical 71]

[0126]

[Chemical 72]

[0127]

[Chemical formula 73]

[0128]

[Chemical 74]

[0129]

[Chemical 75]

[0130]

[Chemical 76]

The pyrazolotriazole-based magenta coupler according to the present invention is a journal of the chemical
Society (Journal of the Che
medical Society), Perkin (Perki)
n); I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, 59-171956, 60-43659, 60.
It can be easily synthesized by those skilled in the art with reference to Nos. 172892 and 60-190779.

Next, typical synthesis examples of the pyrazolotriazole type magenta coupler according to the present invention will be shown below. Synthesis Example 2 Synthesis of Exemplified Compound MB-1 Synthetic Route

[0133]

[Chemical 77] Synthesis of Intermediate B-3 To 30.7 g of Intermediate B-1 was added 150 ml of N, N-dimethylacetamide, 20 ml of morpholine was added, and the mixture was heated with stirring at 100 ° C. for 4 hours under a nitrogen stream. After cooling the reaction solution to room temperature, water (300 ml) and ethyl acetate (300 ml) were added for extraction, and the mixture was washed twice with 0.5N hydrochloric acid (50 ml),
The organic layer was dried and the solvent was distilled off under reduced pressure. The oily substance obtained was purified by silica gel column chromatography (yield 1
8.8 g), the product was dissolved in 50 ml of ethanol, 150 ml of 2N aqueous sodium hydroxide solution was added, and the mixture was heated with stirring at 60 ° C. for 3 hours.

The reaction solution was cooled at room temperature and neutralized with concentrated hydrochloric acid to precipitate white crystals. This was collected by filtration and washed with water to obtain 12.2 g of white crystalline intermediate B-3. (The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.)

Synthesis of Exemplified Compound MB-1 5.7 g of Intermediate B-3 and 4.8 g of Intermediate B-4 were added as D.
It was dissolved in 30 ml of MF, 4.6 g of dicyclohexylcarbodiimide (DCC) was added, and the mixture was stirred at room temperature for 5 hours.
After filtering off the deposited precipitate, 150 m of water was added to the reaction solution.
1 and 250 ml of ethyl acetate were added for extraction. After drying the organic layer, the solvent was distilled off under reduced pressure, and the obtained product was purified by silica gel column chromatography to obtain 6.3 g of white amorphous MB-1. (The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.)

Synthesis Example 3 Synthesis of Exemplified Compound MB-25 Synthetic Route

[0137]

[Chemical 78]

10 ml of acetic acid and 0.73 g of morpholine were added to 0.75 ml of 40% formalin aqueous solution, and the mixture was stirred at room temperature for 1 hour, then 4.6 g of Intermediate B-5 was added, and the mixture was heated and stirred for 3 hours. 100 ml of ethyl acetate and 1 part of water in the reaction solution
After extraction with 100 ml of water and washing with 100 ml of a 3% aqueous sodium hydrogencarbonate solution twice, the organic phase was dried and the solvent was distilled off under reduced pressure. The obtained product was purified by silica gel column chromatography to obtain 2.2 g of pale yellow amorphous MB-25. (The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.)

[0139]

[Chemical 79]

[0140]

[Chemical 80]

[0141]

[Chemical 81]

[0142]

[Chemical formula 82]

[0143]

[Chemical 83]

[0144]

[Chemical 84]

[0145]

[Chemical 85]

The pyrazolotriazole-based magenta coupler according to the present invention is a journal of the chemical compound.
Society (Journal of the Che
medical Society), Perkin (Perki)
n); I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, 59-171956, 60-43659, 60.
It can be easily synthesized by those skilled in the art with reference to Nos. 172892 and 60-190779. Next, a typical synthesis example of the pyrazolotriazole-based magenta coupler according to the present invention is shown below.

Synthesis Example 4 Synthesis of Exemplified Compound MC-7 The synthetic route is shown below.

[0148]

[Chemical formula 86]

C-1 (4.8 g) was dissolved by heating in 20 ml of N, N-dimethylacetamide, and then acetonitrile 100 was added.
ml and C-2 (7.7 g) were added, and the mixture was heated under reflux for 5 hours. After distilling off the acetonitrile under reduced pressure, the reaction solution was diluted with 200
It was poured into ml of water and the precipitated crystals were collected by filtration. The product was purified by silica gel column chromatography to obtain 4.4 g of white amorphous C-3. (The structure was confirmed by ¹ HNMR, FD mass spectrum, and IR spectrum.) Further, 4.2 g of C-3 and 1.4 g of C-4 were dissolved in 50 ml of 1,4-dioxane, and 1.7 g of dicyclohexylcarbodiimide (DCC). Was added and the mixture was stirred at room temperature for 2 hours.

After removing the insoluble matter by filtration, 200 ml of ethyl acetate was added for extraction, and the mixture was washed with 50 ml of 0.5N hydrochloric acid and then with 50 ml of 2% aqueous sodium hydrogen carbonate solution. After drying the organic layer, the solvent was distilled off under reduced pressure, and the obtained product was recrystallized from acetonitrile to give white crystals of MC-7.
4.7 g was obtained. (The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.)

[0151]

[Chemical 87]

[0152]

[Chemical 88]

[0153]

[Chemical 89]

[0154]

[Chemical 90]

[0155]

[Chemical Formula 91]

[0156]

[Chemical Formula 92]

[0157]

[Chemical formula 93]

The pyrazolotriazole type magenta coupler according to the present invention is a journal of the chemical
Society (Journal of the Che
medical Society), Perkin (Perki)
n); I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, 59-171956, 60-43659, 60.
-172892, 60-190779, Synthesis, 1984, 894 pages, 1984, 122 pages, 1984, 40 pages, 1981, JP-A-49-53574, British Patent No. 1,410,846, etc. It can be easily synthesized by those skilled in the art.

Next, typical synthesis examples of the pyrazolotriazole type magenta coupler according to the present invention will be shown below.

Synthesis Example 5 Synthesis of Exemplified Compound MD-1 A synthetic route is shown below.

[0161]

[Chemical 94]

D-1 (4.8 g) was dissolved by heating in 20 ml of N, N-dimethylacetamide, and then acetonitrile 100 was added.
ml and D-7.7g were added, and it heated and refluxed for 5 hours. After distilling off the acetonitrile under reduced pressure, the reaction solution was diluted with 200
It was poured into ml of water and the precipitated crystals were collected by filtration. The product was purified by silica gel column chromatography to obtain 4.5 g of white amorphous D-3. (The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.)

Furthermore, 4.2 g of D-3 and 1.2 g of D-4
100 ml of toluene and 3.0 of p-toluenesulfonic acid
g was added and the mixture was heated under reflux for 6 hours. The reaction solution was cooled at room temperature, washed with water, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 3.1 g of white amorphous MD-1. (The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.)

[0164]

[Chemical 95]

[0165]

[Chemical 96]

[0166]

[Chemical 97]

[0167]

[Chemical 98]

[0168]

[Chemical 99]

[0169]

[Chemical 100]

[0170]

[Chemical 101]

[0171]

[Chemical 102]

[0172]

[Chemical 103]

The pyrazolotriazole-based magenta coupler according to the present invention is a journal of the chemical
Society (Journal of the Che
medical Society), Perkin (Perki)
n); I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, 59-171956, 60-43659, 60.
-172892, 60-190779, New Experimental Chemistry Course, Vol. 14-III, pp. 1585-1594 (197).
7) Maruzen, Vol. 14-III, pp. 1576-1584 (1977) Maruzen, Helv. Chem. Acta. ，
36, 75 (1953), J. Am. Chem. So
c. 72, 2762 (1950), Drg. Syn
th. It can be easily synthesized by those skilled in the art with reference to Volume II, page 395 (1943) and the like.

Next, typical synthesis examples of the pyrazolotriazole type magenta coupler according to the present invention will be shown below.

Synthesis Example 6 Synthesis of Exemplified Compound ME-2 The synthetic route is shown below.

[0176]

[Chemical 104] E-1 4.8 g was added to N, N-dimethylacetamide 20.
After heating and dissolving in ml, 100 ml of acetonitrile and 2.0 g of succinic anhydride were added, and the mixture was heated under reflux for 5 hours. After acetonitrile was distilled off under reduced pressure, the reaction solution was poured into 200 ml of water, and the precipitated crystals were collected by filtration. The product was purified by silica gel column chromatography to obtain 4.6 g of white amorphous E-2. (The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.)

Furthermore, 4.5 g of E-2 and 3.6 g of E-3
Was dissolved in 50 ml of 1,4-dioxane, 3.1 g of dicyclohexylcarbodiimide (DCC) was added, and the mixture was stirred at room temperature for 4 hours. After separating insoluble matter by filtration, ethyl acetate 200
ml, 100 ml of water was added for extraction, and after washing with water,
The organic layer was dried and the solvent was distilled off under reduced pressure. The obtained product was purified by silica gel column chromatography to obtain 25.8 g of pale yellow amorphous ME-25.8. (The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.)

[0178]

[Chemical 105]

[0179]

[Chemical formula 106]

[0180]

[Chemical formula 107]

[0181]

[Chemical 108]

[0182]

[Chemical 109]

[0183]

[Chemical 110]

[0184]

[Chemical 111]

[0185]

[Chemical 112]

[0186]

[Chemical 113]

[0187]

[Chemical 114]

[0188]

[Chemical 115]

The pyrazolotriazole-based magenta coupler according to the present invention is a product of Journal of the Chemical
Society (Journal of the Che
medical Society), Perkin (Perki)
n); I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, 58-42045, 59-162548, 59.
-171956, 60-33552, 60-4
No. 3659, No. 60-172892, No. 60-190.
No. 779, No. 61-189539, No. 61-2417.
54, 63-163351, 62-15703.
No. 1, Synthesys, 1984, p. 894, ibid.
122 pages, 984, 40 pages, 1981, JP-A-49-
53574, British Patent No. 1,410,846, New Experimental Chemistry Course 14-III, pp. 1585-1594 (1
977) Maruzen, Vol. 14-III, 1576-1584.
Page (1977) Maruzen, Helv. Chem. Act
a. 36, 75 (1953), J. Am. Che
m. Soc. 72, 2762 (1950), Dr.
g. Synth. It can be easily synthesized by those skilled in the art with reference to Volume II, page 395 (1943) and the like.

Next, typical synthetic examples of the pyrazolotriazole type magenta coupler according to the present invention will be shown below.

Synthesis Example 7 Synthesis of Exemplified Compound MF-1 The synthetic route is shown below.

[0192]

[Chemical formula 116]

[0193]

[Chemical 117]

Synthesis of Intermediate F-4 33.3 g of Intermediate F-1 was added with 1000 cc of ethyl acetate,
Sodium acetate (9.8 g) and water (200 cc) were added, and the mixture was ice-cooled to 5 ° C. Intermediate F was added to the reaction solution that was vigorously stirred.
-2 32.7 g of ethyl acetate solution was added dropwise over about 2 hours and then stirred at room temperature for 2 hours. The reaction solution was separated and further washed twice with 500 cc of 5% aqueous sodium hydrogen carbonate solution, and then the organic phase was dried and concentrated to dryness.

The obtained product was recrystallized from ethanol to obtain 51.8 g of intermediate F-3. Furthermore, the intermediate F-
3 51.5g with 2000cc of toluene and 15.0g
Phosphorus oxychloride was added and heated under reflux for 5 hours. The reaction solution was cooled to room temperature, washed with 500 cc of water three times, and toluene was distilled off under reduced pressure. The obtained brown oily substance was recrystallized from acetonitrile to obtain 42.6 g of Intermediate F-4. (The structure was identified by ¹ HNMR, FD mass spectrum and IR spectrum.)

Synthesis of Intermediate F-7 42.5 g of Intermediate F-4 was added to 250 cc of acetic acid and 45 c of water.
c and sulfuric acid (45 cc) were added, and the mixture was heated under reflux for 4 hours. The reaction solution was ice-cooled, 300 g of ice and 500 cc of ethyl acetate were added for extraction, the organic phase was washed 5 times with 500 cc of 5% aqueous sodium hydrogen carbonate solution, dried and then concentrated to dryness.
The product obtained is recrystallized from acetonitrile, 30.9
g of intermediate F-5 was obtained. Add this to ethanol 300
After dissolving in cc, 24.6 g of Intermediate F-6 and 8.6 g of potassium carbonate were added, and the mixture was heated under reflux for 4 hours.

The precipitated inorganic salt was filtered off, ethanol was distilled off under reduced pressure, the product was dissolved in 500 cc of ethyl acetate, and this was washed 3 times with 400 cc of water. After drying the organic phase,
The solvent was distilled off under reduced pressure. The product was purified by column chromatography and further recrystallized with a mixed solvent of ethyl acetate and hexane to obtain 14.0 g of Intermediate F-7. (The structure was identified by ¹ HNMR, FD mass spectrum and IR spectrum.)

Synthesis of Exemplified Compound MF-1 14.0 g of Intermediate F-7 was dissolved in 300 cc of methanol, 2.0 g of palladium-carbon (support rate: 5%) was added, and contacted under hydrogen gas atmosphere for 4 hours. The reduction was performed.
After removing palladium-carbon as a catalyst by filtration, the solvent methanol was distilled off under reduced pressure to obtain 13.5 g of Intermediate F-8.

Further, this was dissolved in 150 ml of n-butanol, 2.26 g of divinyl sulfone was added, and the mixture was heated under reflux for 3 hours. After concentrating the solvent n-butanol, it was purified by silica gel column chromatography, and further recrystallized with a mixed solvent of ethyl acetate-hexane to obtain 1
1.5 g of intermediate F-9 was obtained.

Next, 11.5 g of Intermediate F-9 was dissolved in 100 ml of chloroform, and cooled to 5 ° C. with ice, and 1.81 g of N-chlorosuccinimide was added little by little over about 2 hours. The reaction solution was washed with water and dried, then the solvent was distilled off under reduced pressure, and the obtained product was recrystallized from acetonitrile to obtain 10.8 g of white crystals of MF-1.
(The structure was identified by ¹ HNMR, FD mass spectrum, and IR spectrum.) Magenta couplers having an amine-based image stabilizer in the molecule were photographed by solid dispersion method latex dispersion method, oil-in-water emulsion dispersion method, etc. It can be added to the light-sensitive material using various methods known in the industrial field.

The layer to which the magenta coupler having an amine-based image stabilizer in the molecule is added may be any layer in the light-sensitive material, but a silver halide photographic emulsion layer is preferred.
The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is characterized by containing silver chloride in an amount of 95 to 99.9 mol%, but is substantially free of silver iodide. Silver is preferred. The content rate of silver chloride is 97 to 99.9.
Mol% is more preferred. In the case of developing in a shorter time or reducing the replenishment amount of the color developing solution, 99.5-9
It is more preferably 9.9 mol%.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. US Pat. Nos. 4,183,756 and 4,225,66.
6, JP-A-55-26589, JP-B-55-427.
No. 37, The Journal of Photographic Science (J. Photogr. Sci.) 21,
39 (1973) and other methods,
Particles having a shape such as an octahedron, a tetradecahedron, and a dodecahedron can be prepared and used. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes. The grain size of the silver halide grains according to the present invention is not particularly limited, but it is preferably 0.
1 to 0.2 μm, more preferably 0.2 to 1.0 μm
The range is.

The above particle size can be measured by various methods commonly used in the art. A typical method is Loveland's “Particle Size Analysis Method” (ASMTM Symposium on Light.
Microcopy, pp. 94-122, 1955) or
The method described in "Theory of Photographic Process, 3rd Edition" (Co-authored by Mies and James, Chapter 2, published by Macmillan, 1966) can be mentioned.

This particle size can be measured using a projected area of the particle or an approximate diameter value. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area. The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse. Preferably, the coefficient of variation is 0.
The number of monodispersed silver halide grains is 22 or less, more preferably 0.15 or less. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation. Coefficient of variation = S / R (where S is the standard deviation of the particle size distribution, and R is the average particle size.)

The grain size referred to here is the diameter of a spherical silver halide grain, and the diameter of a cubic image or a shape other than a spherical grain when the projected image is converted into a circular image of the same area. Represents. As a device and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method of making seed particles and the method of growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a double mixing method, and a combination thereof, but those obtained by the double mixing method. Is preferred. Further, the pAg controlled double jet method described in JP-A-54-48521 may be used as one form of the simultaneous mixing method.

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

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

A known method can be used for reduction sensitizing the silver halide emulsion according to the present invention. For example,
It is also possible to use a method of adding various reducing agents,
A method of aging under conditions of high silver ion concentration or a method of aging under conditions of high pH can be used.

As a reducing agent used for reduction sensitization of the silver halide emulsion according to the present invention, stannous chloride of stannous chloride,
Examples thereof include boranes such as tri-t-butylamine borane, sodium sulfite, sulfites such as potassium sulfite, reductones such as ascorbic acid, and thiourea dioxide. Among these, thiourea dioxide, ascorbic acid and its derivatives, and sulfite can be preferably used. Compared with the case where reduction sensitization is performed by controlling the silver ion concentration and pH during ripening, the method using a reducing agent as described above is excellent in reproducibility and is preferable.

These reducing agents are dissolved in a solvent such as water or alcohol and added to the silver halide emulsion for ripening, or they are added during the formation of silver halide grains to reduce and increase them simultaneously with grain formation. You may feel. The amount of these reducing agents to be added needs to be adjusted according to the pH of the silver halide emulsion, the silver ion concentration, etc., but generally 10 ^-7 to 10 ^-2 mol per mol of the silver halide emulsion. Is preferred.

After the reduction sensitization, a small amount of an oxidizing agent may be used for modifying the reduction sensitizing nucleus or deactivating the remaining reducing agent. Examples of compounds used for such purposes include:
Examples thereof include potassium hexacyanoferrate (III), bromosuccinimide, p-quinone, potassium perchlorate, and hydrogen peroxide solution.

The silver halide emulsion according to the present invention can be reduction-sensitized and can be used in combination with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer. As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and the sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like.

As the gold sensitizer applied to the silver halide emulsion according to the present invention, various gold complexes other than chloroauric acid, gold sulfide, gold thiosulfate and the like can be added. Examples of the ligand compound used include dimethylrhodnin, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used varies depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc.
It is preferably 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol. More preferably 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸
It is a mole.

The silver halide emulsion according to the present invention has the purpose of preventing fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuations during storage, and preventing fog that occurs during development. Known antifoggants and stabilizers can be used.

Examples of the compound which can be used for such purpose include the compounds represented by the general formula (II) described in JP-A-2-146036, page 7, lower column. The compounds include (IIa-1) to (IIa-8) and (IIb-) described on page 8 of the publication.
1)-(IIb-7) compounds, 1- (3-methoxyphenyl) -5-mercaptotetrazole and the like can be mentioned.

These compounds can be added in the steps of preparing silver halide emulsion grains, chemical sensitization step, completion of chemical sensitization step, coating solution preparation step and the like depending on the purpose. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 × 10 ⁵ mol per mol of silver halide.
It is preferably used in an amount of about ^-4 mol.

[0220] When added to the end of the chemical sensitization, the amount of 1 × 10 ^-6 mol to 5 × 10 ^-2 mol per mol of silver halide is preferred, 1 × 10 ^-5 mol to 5 × 10 ^{- 3} mol is more preferred. When it is added to the silver halide emulsion layer in the coating solution preparation step, the amount is 1 per mol of silver halide.
The amount is preferably in the range of × 10 ^-6 mol to 1 × 10 ^-1 mol.
It is more preferably x10 ^-5 mol to 1 x 10 ^-2 mol. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating solution coating is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol.

When the silver halide photographic light-sensitive material of the present invention is used as a color photographic light-sensitive material, it is combined with a yellow coupler, a magenta coupler and a cyan coupler, and spectrally sensitized in a specific region of a wavelength range of 400 to 900 nm. A layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

Any known compound can be used as the spectral sensitizing dye used in the silver halide emulsion according to the present invention, and as the blue-sensitive sensitizing dye, Japanese Patent Application No. 2-5 can be used.
BS-1 to 108 described in No. 1124, pages 108 to 109
8 can be preferably used alone or in combination. As the green sensitizing dye, GS-1 to 5 described on page 110 of the same specification are preferably used. Examples of the red sensitizing dye include RS-described on pages 111 to 112 of the same specification.
1-8 are preferably used.

When the silver halide photographic light-sensitive material of the present invention is exposed by a printer using a semiconductor laser, it is necessary to use a sensitizing dye having infrared sensitivity, which is an infrared-sensitive sensitizing dye. As for Japanese Patent Application No. 3-7361
The dyes of IRS-1 to 11 described in No. 9 specification, pages 12 to 14 are preferably used. Further, it is preferable to use the supersensitizers SS-1 to SS-9 described on pages 14 to 15 of the same specification in combination with these dyes.

In the silver halide photographic light-sensitive material of the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. Any known compound can be used for this purpose. As a coupler used in the silver halide photographic light-sensitive material according to the present invention, any coupler capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. Compounds can also be used, but as a typical example, a yellow coupler having a spectral absorption maximum wavelength in the wavelength range of 350 to 500 nm, a wavelength range of 500 to 600 nm.
A typical one is a magenta coupler having a spectral absorption maximum wavelength and a known cyan coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.

Examples of yellow couplers which can be preferably used in the silver halide photographic light-sensitive material of the present invention include pivaloyl type yellow couplers. As a cyan coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention, Japanese Patent Application No. 2-23 can be used.
Examples thereof include couplers represented by the general formula [CI] and general formula [C-II] described on page 17 of the specification of No. 4208. Specific compounds are described in CC in pages 18 to 21 of the specification.
Examples thereof include those described as -1 to CC-9.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher. If necessary, a low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. Examples of the high boiling point organic solvent that can be used for dissolving and dispersing the coupler include phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but it is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 mol per mol of silver halide. It is used in a range of × 10 ^-2 to 1 mol.
In the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin are used. Hydrophilic colloids such as sugar derivatives, cellulose derivatives, and synthetic hydrophilic substances such as homopolymers or copolymers can also be used.

The total amount of gelatin used as the binder is preferably 7.5 g / m ² or less so that the effects of the present invention can be more realized. The lower limit is not particularly limited, but generally 3 from the viewpoint of physical properties or photographic performance.
It is preferably g / m ² or more. As the reflective support according to the present invention, any material may be used, and a polypropylene containing a white pigment, a polyethylene terephthalate support or the like may be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used in the reflective support of the present invention, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used.
For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, alumina hydrate, oxidation Examples thereof include titanium, zinc oxide, talc and clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water resistant resin layer on the surface of the reflective support according to the present invention is preferably 10% by weight or more as the content in the water resistant resin layer. Is preferably 13% by weight or more, and more preferably 15% by weight or more. The degree of dispersion of the white pigment in the water resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and more preferably 0.10 or less as the coefficient of variation described in the above publication. Is more preferable.

The silver halide photographic light-sensitive material according to the present invention is directly or undercoated (adhesiveness of the surface of the support, after the surface of the support is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary. It may be applied via one or more undercoat layers) to improve antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties. When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability.

As a coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful. In the development processing of the silver halide photographic light-sensitive material according to the present invention, aminophenol and p-phenylenediamine compounds widely used in various color photographic processes are used as the color developing agent used in the color developing solution. Be done. Particularly, aromatic primary amine type color developing agents are preferably used.

Aromatic primary amine color developing agents include (1) N, N-dimethyl-p-phenylenediamine hydrochloride (2) N-methyl-p-phenylenediamine hydrochloride (3) 2-amino -5- (N-ethyl-N-dodecylamino) toluene (4) N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate (5) N-ethyl-N -(Β-Hydroxyethyl) -3
-Methyl-4-aminoaniline sulfate (6) 4-amino-3-methyl-N, N-diethylaniline (7) 4-amino-N- (β-methoxyethyl) -N-
Ethyl-3-methylaniline p-toluenesulfonate (8) 4-Amino-N-ethyl-N- (γ-hydroxypropyl) -3-methylaniline p-toluenesulfonate

These color developing agents are preferably used in the range of 1 × 10 ^-3 to 2 × 10 ^-1 mol per liter of the developing solution, and preferably in the range of 5 × 10 ^-3 to 2 × 10 ^-1 mol. Is more preferably used. To the color developing solution, a known developer component compound can be added in addition to the color developing agent. Usually, an alkaline agent having a pH buffering action, a development inhibitor such as chloride ion or benzotriazole, a preservative, a chelating agent and the like are used. As the alkaline agent used in the color developing solution for the silver halide photographic light-sensitive material according to the present invention, potassium carbonate, potassium borate, trisodium phosphate, etc. are used, and sodium hydroxide is mainly used for the purpose of pH adjustment and the like. Potassium hydroxide or the like is used. The color developer generally has a pH of 9 to 12, and preferably has a pH of 9.5 to 11.

Halide salt ions are often used for the purpose of suppressing development, but in the processing method according to the present invention, chloride ions are mainly used because development must be completed in a very short time. And potassium chloride, sodium chloride and the like are used. The amount of chloride ion is about 3.0 × 10 ^-2 mol or more, preferably 4.0 × 10 ^{-2 to} 5.0 × 10 ^-1 mol per liter of the color developing solution.

Bromide ions can be used within a range that does not impair the effects of the present invention, but they have a great effect of suppressing development, and are approximately 1.
It is preferably 0 × 10 ⁻³ or less, preferably 5.0 × 10 ⁻⁴ or less. As preservatives, hydroxyamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazide aminoketones, sugars,
Monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines and the like are particularly effective preservatives. Particularly, dialkyl-substituted hydroxylamines such as diethylhydroxyamine and alkanolamines such as triethanolamine can be preferably used.

As the chelating agent used in the color developing solution according to the present invention, compounds such as aminopolycarbanoic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid are used. Especially ethylenediaminetetraacetic acid,
Nitriloacetic acid, diethylenetriaminepentaacetic acid and 1-hydroxyethylidene-1,1-diphosphonic acid are preferably used.

The color developing temperature is usually 15 ° C. or higher and generally 20 to 50 ° C. Further, for rapid treatment, it is preferable to carry out at 30 ° C. or higher. The color development processing time is generally 10 seconds to 4 minutes, but for the purpose of speeding up, it is preferably carried out in the range of 10 seconds to 1 minute, and when further speeding up is required. It is preferably carried out in the range of 10 to 30 seconds. In the processing method of the present invention, when the color development processing time is short, such as 10 to 30 seconds, the effect is remarkable.

In the present invention, the replenishing amount of the color developing solution during the running process while continuously replenishing the color developing solution is ^{20 to} 100 m / m ² of the photographic light-sensitive material.
Although it is 1, it is preferable that the overflow does not substantially occur during running, considering the recent environmental pollution caused by the developer waste liquid. Specifically, the replenishment amount of the developer is preferably 20 to 60 ml per 1 m ² of the photographic light-sensitive material.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development processing. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Also, as an alternative to water washing
You may perform a stabilization process. As a development processing apparatus used for the development processing of the silver halide photographic light-sensitive material of the present invention, even if it is a roller transport type that conveys the light-sensitive material by sandwiching it between rollers arranged in a processing tank, The endless belt method of fixing and conveying may be used, but particularly, the method of forming the processing tank in a slit shape and supplying the processing liquid to the processing tank and conveying the photosensitive material may also be used.

[0241]

EXAMPLES Examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

Example 1 (Preparation of silver halide emulsion) Three types of silver halide emulsions shown below were prepared by the neutral method and the simultaneous mixing method.

[0243]

[Table 1]

Each silver halide emulsion was prepared by using STB-1 as an emulsion stabilizer after the completion of chemical sensitization.
2 × 10 ⁻⁴ mol was added per mol.

(Preparation of Color Light-Sensitive Material) Each layer having the following constitution was coated on a support having polyethylene laminated on one side of a paper support and polyethylene containing titanium oxide on the other side of the first layer. Then, a multilayer silver halide color photographic light-sensitive material 101 was produced.

First layer coating liquid: 26.7 g of yellow coupler (Y-1), 0.67 g of stain inhibitor (HQ-1), dye image stabilizer (ST-
1) 10.0 ml, the same (ST-2) 6.7 g and high boiling point organic solvent (DNP) 6.7 g were dissolved by adding 60 ml of ethyl acetate, and this solution was dissolved in 10% sodium alkylnaphthalene sulfonate (SU-1). ) A yellow coupler dispersion was prepared by emulsifying and dispersing in 200 ml of 10% gelatin aqueous solution containing 10 ml using a homogenizer. This dispersion was mixed with a blue-sensitive silver chlorobromide emulsion (10 g of Em-1 converted to silver) and a gelatin solution for coating to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, as a hardening agent, (H-1) was added to the second and fourth layers, and (H-2) was added to the seventh layer. As the coating aid, (SU-1) and (SU-2) and the surfactant shown in Table 3 were added to adjust the surface tension.

[0248]

[Table 2]

[0249]

[Table 3]

The compounds used in Table 2 are shown below.

[0251]

[Chemical 118]

[0252]

[Chemical 119]

[0253]

[Chemical 120]

[0254]

[Chemical 121]

Samples 102 to 124 were prepared by adding 1 mmol / m ^{2 of the} magenta coupler shown in Table 4 to the third layer. The comparison compound of the said additive is shown.

[0256]

[Chemical formula 122]

The obtained sample was subjected to wedge exposure using green light with a sensitometer KS-7 (manufactured by Konica Corporation), and the tank capacity of the color developer was set to 3 according to the following processing steps A and B. After continuous processing was performed until a double amount of color developing replenisher was replenished, the following evaluations were performed.

Processing step A Temperature Time Replenishment amount Color development 35.0 ± 0.3 ° C. 45 seconds 80 ml Bleach fixing 35.0 ± 0.3 ° C. 45 seconds 51 ml Stability 30-34 ° C. 90 seconds 250 ml (3 tanks Cascade) Dry 60-80 ℃ 30 seconds

Processing step B Temperature Time Replenishment amount Color development 39.0 ± 0.3 ° C. 45 seconds 40 ml Bleach fixing 35.0 ± 0.3 ° C. 45 seconds 51 ml Stability 30-34 ° C. 90 seconds 250 ml (3 tanks Cascade) Dry 60-80 ℃ 60 seconds

The composition of the treatment liquid is shown below. The replenishment amount is an amount per 1 m ² of the light-sensitive material. Stabilization is stable tank 3 → 1
It was replenished by the countercurrent method.

[Color Developing Solution] (Processing Step A) (1) Tank Solution Pure Water 800 mL Triethanolamine 10 g N, N-Diethylhydroxylamine 5 g Potassium Chloride 2 g 1-Hydroxyethylidene-1,1-diphosphonic Acid 1. 0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4 g potassium carbonate 27 g Water was added to make 1 liter, and the pH was adjusted to 10.10 with potassium hydroxide or sulfuric acid. adjust.

(2) Replenisher Liquid Pure water 800 ml Triethanolamine 18 g N, N-diethylhydroxylamine 9 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g N-ethyl-N-β-methanesulfonamidoethyl -3-Methyl-4-aminoaniline sulfate 8.2 g Potassium carbonate 27 g Water is added to make 1 liter, and the pH is adjusted to 10.60 with potassium hydroxide or sulfuric acid.

[Color Developing Solution] (Processing Step B) (1) Tank Solution Pure Water 800 ml Triethanolamine 10 g N, N-Diethylhydroxylamine 3.6 g Potassium Chloride 4.5 g Diethylenetriamine 5 Acetic Acid 5.0 g Sulfurous Acid Potassium 0.4 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 6.0 g Potassium carbonate 25 g Water was added to make 1 liter, and the pH was adjusted to 10 with potassium hydroxide or sulfuric acid. Adjust to 10.

(2) Replenisher liquid Pure water 800 ml Triethanolamine 14 g N, N-diethylhydroxylamine 5 g Potassium sulfite 0.6 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline Sulfate 12 g Potassium carbonate 35 g Water is added to make 1 liter, and the pH is adjusted to 11.50 with potassium hydroxide or sulfuric acid.

[Bleach-fixing tank solution and replenisher] Ethylenediaminetetraacetic acid ferric ammonium salt 53 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70%) solution 123 g Ammonium sulfite (40%) solution 51 g pH with ammonia or glacial acetic acid 5. Adjust to 4 and add water to bring the total volume to 1 liter.

[Stable tank solution and replenisher] o-Phenylphenol 0.1 g Ubitex (manufactured by Ciba-Geigy) 1.0 g Zinc sulfate-7-hydrate 0.1 g Ammonium sulfite (40% solution) 5.0 ml 1- Hydroxyethylidene-1,1-diphosphonic acid 3.0 g Ethylenediaminetetraacetic acid 1.5 g Adjust the pH to 7.8 with aqueous ammonia or glacial acetic acid, add water, and add water to obtain a total volume of 1 liter.

(Evaluation method) To evaluate the fastness to light, the above nuclear-treated sample was stored in sunlight (exposure table) for 10 weeks,
The residual ratio of the dye image at a density of 0.8 was used. In addition, the adhesiveness was evaluated by subjecting the obtained sample to humidity control under conditions of 23 ° C. and 80% RH for 10 hours, overlapping the surfaces of the samples with each other, and measuring 50 g.
Add a weight so that it becomes / cm ² , and again at 23 ℃, 80%
The adhesive area when the humidity was controlled for 10 hours under RH conditions was visually evaluated.

◎ No "adhesion" is observed. * Almost no "adhesion" is seen. △ Some "adhesion" can be seen, but it is acceptable as a product. × "Adhesion" is visible and not acceptable as a product. XX "Adhesion" is quite visible and completely impossible as a product.

[0269]

[Table 4]

As is clear from Table 4, when the running process (processing step A) in which the replenishment amount of the developing agent is reduced is carried out, the amine-based image stabilizer of the present invention is contained in the molecule. When no magenta coupler is used (Sample 101
It is understood that the light resistance is remarkably inferior.
However, it can be seen that when the magenta coupler having the amine-based image stabilizer of the present invention in the molecule is used, the light resistance is very good.

When the magenta coupler having the amine-based image stabilizer of the present invention in the molecule is not used, the replenishment amount of the developing agent is remarkably reduced, and the overflow solution of the developing agent is practically eliminated. Treatment step B)
Even in the case of carrying out the above, it can be seen that when the magenta coupler having the amine-based image stabilizer of the present invention in the molecule is used, deterioration of light resistance is not observed.

Regarding the adhesiveness, when the magenta coupler having the amine-based image stabilizer of the present invention in the molecule is used, the occurrence of adhesion is suppressed and the overflow liquid of the developing agent is practically eliminated. It can be seen that even when the running process (process B) is performed, the occurrence of adhesion is suppressed to the minimum.

Comparison between magenta couplers having the amine-based image stabilizer of the present invention in the molecule shows that the light resistance is improved as the linking group connecting the amine-based image stabilizer is shortened. I understand. (Samples 105-1
09) From this, it is suggested that the physical distance between the mother nucleus of the coupler and the image stabilizer affects the light resistance.

Example 2 Samples 201 to 224 were prepared by adding the magenta couplers shown in Table 5 in the same manner as in Example 1 as in Example 1. In addition to the above-mentioned processing steps A and B, the following processing step C was also performed.

Processing step C Temperature Time Replenishment amount Color development 39.0 ± 0.3 ° C. 20 seconds 60 ml Bleach-fixing 35.0 ± 0.3 ° C. 40 seconds 50 ml Stability 30-34 ° C. 90 seconds 250 ml (3 tanks Cascade) Dry 60-80 ℃ 30 seconds

The composition of the processing liquid is shown below. The replenishment amount is an amount per 1 m ² of the light-sensitive material. Stabilization is stable tank 3 → 1
It was replenished by the countercurrent method.

[Color Developing Solution] (Processing Step C) (1) Tank Solution Pure Water 800 mL Triethanolamine 10 g N, N-Diethylhydroxylamine 5 g Potassium Chloride 2 g 1-Hydroxyethylidene-1,1-diphosphonic Acid 1. 0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4 g potassium carbonate 27 g Water was added to make 1 liter, and the pH was adjusted to 10.10 with potassium hydroxide or sulfuric acid. adjust.

(2) Replenisher Liquid Pure water 800 ml Triethanolamine 18 g N, N-diethylhydroxylamine 15 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g N-ethyl-N-β-methanesulfonamidoethyl -3-Methyl-4-aminoaniline sulfate 8.2 g Potassium carbonate 27 g Water is added to make 1 liter, and the pH is adjusted to 11.0 with potassium hydroxide or sulfuric acid.

[Bleach-fixing tank liquid and replenisher] Ethylenediaminetetraacetic acid ferric ammonium salt 53 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70%) solution 123 g Ammonium sulfite (40%) solution 51 g pH with ammonia or glacial acetic acid 5. Adjust to 4 and add water to bring the total volume to 1 liter.

[Stable tank solution and replenisher] o-Phenylphenol 0.1 g Ubitex (manufactured by Ciba Geigy) 1.0 g Zinc sulfate-7-hydrate 0.1 g Ammonium sulfite (40% solution) 5.0 ml 1- Hydroxyethylidene-1,1-diphosphonic acid 3.0 g Ethylenediaminetetraacetic acid 1.5 g Adjust the pH to 7.8 with aqueous ammonia or glacial acetic acid, add water, and add water to obtain a total volume of 1 liter.

The fastness to light was evaluated by storing the above-mentioned nuclear-treated sample in the sun (exposure table) for 12 weeks and determining the residual ratio of the dye image at a density of 1.5. Further, the adhesiveness was evaluated by superposing the surfaces of the samples obtained by controlling the humidity of the obtained sample for 10 hours at 25 ° C. and 75% RH at 50 g / c.
Add weight to m ² again at 25 ℃, 70% RH
The adhesive area when the humidity was controlled under the conditions for 10 hours was visually evaluated in the same manner as in Example 1.

[0282]

[Table 5]

As is apparent from Table 5, even when the treatment (treatment step C) in which the treatment time was remarkably shortened was carried out, the amine-based image stabilizer of the present invention of the present invention was contained in the molecule. When using magenta coupler, the improvement of light resistance is seen,
Also, it can be seen that adhesion hardly occurs.

Similar processing and evaluation are carried out by MA-12, M
A-11, MA-32, MA-36, MA-23, MA
-87, MB-28, MB-3, MB-39, MC-
5, MC-10, MC-20, MD-1, MD-2, M
D-20, MD-21, MD-15, ME-3, ME-
6, ME-18, ME-23, ME-37, MF-1,
MF-2, MF-5, MF-18, MF-28, MF-
No. 36 was performed, but the effect of the present invention was obtained.

Example 3 In the same manner as in Example 1, the magenta couplers shown in Tables 6, 7 and 8 were added in the same manner as in Example 1, and Table 6,
The color image stabilizers shown in Tables 7 and 8 were added to the third layer in an amount of 1 mmol / m ² to prepare samples 301 to 350.
In addition, the obtained sample was processed in the processing steps A and B of Example 1.
Then, the treatment was performed according to the treatment step C of Example 2.

The fastness to light was evaluated by storing the above nuclear-treated sample in the sun (exposure table) for 10 weeks and determining the residual ratio of the dye image at a density of 1.0. The stain was evaluated by storing the obtained sample under conditions of 85 ° C. and 60% RH for 10 days, and measuring the increase in the blue reflection density of the unexposed area immediately after the treatment and evaluating it.

Further, the adhesiveness was evaluated by measuring the obtained sample with 2
After conditioning the humidity for 12 hours at 0 ° C. and 80% RH, overlay the surfaces of the conditioned samples on top of each other, add a weight to 75 g / cm ² , and again for 10 hours at 20 ° C. and 80% RH. The adhesive area when the humidity was adjusted was visually evaluated in the same manner as in Example 1.

[0288]

[Chemical 123]

[0289]

[Table 6]

[0290]

[Table 7]

[0291]

[Table 8]

As is clear from Tables 6, 7, and 8, when the magenta coupler having the amine-based image stabilizer of the present invention in the molecule is not used (Samples 301 to 30)
4) It can be seen that the light resistance is remarkably inferior. Also, a sample (Sample 305-using a magenta coupler having an amine-based image stabilizer in the molecule and an amine-based and phenol-based color image stabilizer commonly used in a photographic system together
In 320), there are some cases in which the light resistance is improved, but it is not sufficient. Further, the replenishment amount of the developing agent is remarkably reduced, and the processing (processing step B) and the developing time in which the overflow solution of the developing agent is practically eliminated. It can be seen that in the treatment which is remarkably shortened (treatment step C), a large amount of adhesiveness and stain are observed.

However, in the case of using the magenta coupler having the amine-based image stabilizer of the present invention in the molecule, in any of the processing steps A, B and C,
It can be seen that the light resistance is improved and the occurrence of adhesion or stain is minimized.

Further, similar samples were prepared, and the same treatments and evaluations were carried out, using MA-71, MA-72, MA-2, MA-4,
MA-98, MA-12, MA-11, MA-32, M
A-36, MA-23, MA-87, MB-28, MB
-3, MB-39, MC-2, MC-5, MC-10,
MC-20, MD-1, MD-2, MD-20, MD-
21, MD-15, ME-3, ME-18, ME-2
3, ME-37, MF-1, MF-2, MF-5, MF
-18, MF-28, MF-33, and MF-36 were performed, but the effect of the present invention was obtained.

[0295]

EFFECTS OF THE INVENTION According to the present invention, after a very low replenishment running process and a running process in which the overflow liquid is reduced, even when exposed to light or stored under high temperature and high humidity, fading or Y It has become possible to provide a method of processing a silver halide photographic light-sensitive material in which deterioration of an image such as stain is suppressed and deterioration of image quality due to adhesion is suppressed.

Claims (9)

[Claims] 1. A method of processing a silver halide photographic light-sensitive material containing a magenta coupler having an amine-based image stabilizer in the molecule on a support, wherein the silver halide photographic light-sensitive material is replenished with a color developer. The method for processing a silver halide photographic light-sensitive material is characterized in that it is processed with a color developing solution in an amount of 20 to 100 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material. 2. A method for processing a silver halide photographic light-sensitive material, wherein the magenta coupler according to claim 1 is a magenta coupler represented by the general formula [IA]. [Chemical 1] (Wherein, A represents the general formula (II) or the general formula R ₂ from pyrazolotriazole magenta couplers represented by (III)
Alternatively, it represents a residue obtained by removing R ₃ , and L represents a divalent linking group. Y represents a non-metal atom group necessary for forming a 5- or 6-membered heterocycle with a nitrogen atom, and R ₁ represents a substituent. n represents an integer of 0 to 4. [Chemical 2] (In the formula, R ₂ and R ₃ represent a hydrogen atom or a substituent,
X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ) 3. A silver halide photographic light-sensitive material, wherein the magenta coupler represented by the general formula [IA] according to claim 2 is the general formula [IA-1] or the general formula [IA-2]. Processing method. [Chemical 3] (In the formula, L ¹ represents a divalent linking group having a main chain of 5 or less atoms, R ₁ and R ₂ represent a substituent. Y represents a 5-membered or 6-membered heterocyclic ring together with a nitrogen atom. Represents a non-metal atom group necessary for forming, and n represents an integer of 0 to 4. X
Represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ) 4. A silver halide photographic light-sensitive material, wherein the magenta coupler represented by the general formula [IA] according to claim 2 is the general formula [IA-3] or the general formula [IA-4]. Processing method. [Chemical 4] (In the formula, R ₁ , R ₂ and R ₄ represent a substituent, Y represents a group of non-metal atoms necessary for forming a 5-membered or 6-membered heterocycle with a nitrogen atom, and n represents 0 to 4 Represents an integer of 1, and m represents 1 or 2. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidation product of a color developing agent.) 5. A method for processing a silver halide photographic light-sensitive material, wherein the magenta coupler according to claim 1 is a magenta coupler represented by the general formula [IB]. [Chemical 5] (In the formula, A represents a residue obtained by removing R ₂ or R ₃ from the pyrazolotriazole magenta coupler represented by the general formula [II] or the general formula [III] according to claim 2, and R _B is an alkylene group. And L _B represents a divalent linking group or a simple bond, and Y represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle with a nitrogen atom.) 6. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the magenta coupler according to claim 1 is a magenta coupler represented by the following general formula [IC]. [Chemical 6] (In the formula, A represents a residue obtained by removing R ₂ or R ₃ from the pyrazolotriazole magenta coupler represented by the general formula [II] or the general formula [III] of claim 2, and L _c is a divalent group. Represents a linking group or a simple bond, and E is -CO
-, - SO -, - SO 2 -, - N (R 16) -SO 2 -,
—N (R ₁₆ ) —CO—, represents a linking group represented by —O—CO—, R ₁₆ represents a hydrogen atom or a substituent, and Y forms a 5-membered or 6-membered heterocycle with a nitrogen atom. Represents a group of non-metal atoms required to do so. ) 7. A method for processing a silver halide photographic light-sensitive material, wherein the magenta coupler according to claim 1 is a magenta coupler represented by the general formula [ID]. [Chemical 7] (In the formula, A represents a residue obtained by removing R ₂ or R ₃ from the pyrazolotriazole magenta coupler represented by the general formula [II] or the general formula [III] of claim 2, and L _D is a divalent group. Represents a linking group or a simple bond, and B is -O-,-
_{S -, - SO 2 -,} - N (R 16) -, - C (R 16) 2 -
Represents a linking group represented by, R _D represents a hydrogen atom or a substituent, R _a , R _b , R _c and R _d represent an alkyl group, and Y _D represents a 5- or 6-membered heterocyclic ring together with a nitrogen atom. Represents a group of non-metal atoms necessary to form a group, one atom in the group of non-metal atoms represents a bond with B, R
₁₆ represents a hydrogen atom or a substituent. ) 8. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the magenta coupler according to claim 1 is a magenta coupler represented by the general formula [IE]. [Chemical 8] (In the formula, A represents a residue obtained by removing R ₂ or R ₃ from the pyrazolotriazole magenta coupler represented by the general formula [II] or the general formula [III] according to claim 2, and L _E is a divalent group. R _E1 and R _E2 each represent a hydrogen atom or a substituent, and R _E1 and R _E2 may be the same or different and are bonded to each other to form a 5- to 7-membered ring. Is also good.
k represents 0 or 1, Z _E represents -O-, -S-, -N
(R ₁₆ )-represents a linking group, and R ₁₆ represents a hydrogen atom or a substituent. ) 9. A method of processing a silver halide photographic light-sensitive material, wherein the magenta coupler according to claim 1 is a magenta coupler represented by any of general formulas [IF-1] to [IF-4]. [Chemical 9] (In the formula, L _a and L _b represent a divalent linking group or a simple bond, R _F represents an alkylene group or an arylene group,
Y represents a non-metallic atomic group necessary to form a 5- or 6-membered ring, n _f is 0 or _{1, R a1, R b1,} R c1, R d1 and R _e1 is a hydrogen atom or a substituent _Represents R _a1 , R _b1 ,
At least one of R _c1 , R _d1 and R _e1 represents a hydroxyl group, an alkoxy group, an aryloxy group or a linking group represented by the general formula [F1], and X _F represents —S—, —SO ₂ —, —C.
(R _{16) 2} - R ₁₆ represents a linking group represented by represents a hydrogen atom or a substituent. Two R _{16 s} may be the same or different, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent. ) [Chemical 10]