JPH05100387A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance processing stability, to reduce variation among printers, and to improve preservation stability with the lapse of time by incorporating 2 kinds of specified magenta couplers and a specified compound in a silver halide emulsion layer. CONSTITUTION:The silver halide emulsion layer contains each one of the magenta couplers represented by formulae I and II and the compound capable of releasing a development inhibitor or its precursor. In formulae I-III, each of R1-R4 is H or alkyl or the like; J is methylene or the like; each of X1 and X2 is H or a group to be released by coupling with the oxidation product of a color developing agent; each of Z1 and Z2 is a nonmetallic atomic group necessary to form an N-containing hetero ring; R<1> is alkyl; R<2> is alkyl or aryl; R<3> is oxycarbonyl or the like; and X is a group releasing the development inhibitor or its precursor when the compound couples with the oxidation product of a color developing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having excellent processing stability, small printer-to-printer variation and good raw storage stability.

[0002]

BACKGROUND OF THE INVENTION Silver halide color photographic light-sensitive materials include
Usually, a yellow coupler, a magenta coupler and a cyan coupler are used in combination. Among these, a 5-pyrazolone-based magenta coupler is widely used as the magenta coupler. The 5-pyrazolone-based magenta coupler has various problems in color reproducibility because the dye formed by the development process has a secondary absorption at around 430 nm. Novel magenta couplers have been studied to solve this problem, and are disclosed in, for example, US Pat. No. 3,725,065,
No. 3,810,761 and No. 3,758,3
The pyrazolotriazole couplers described in No. 09 and No. 3,728,067 have been developed.

These couplers have many advantages in that they have little side absorption, are advantageous in color reproducibility, are excellent in color developability, and are also excellent in storage stability in the presence of formalin.

However, these pyrazoloazole-based magenta couplers, for example, in a color negative film, when printing on a color negative paper, the hue of the finished color paper may deviate due to the difference in the printing equipment (hereinafter referred to as printer) used. Was found (hereinafter referred to as printer-to-printer variation).

This phenomenon is also observed in other conventional couplers, but the degree thereof is extremely small and it was not a problem. However, it has been found that when a pyrazoloazole-based magenta coupler is used, the hue shift of the finished color paper due to the difference in printer becomes a level that cannot be ignored.

This phenomenon is thought to be mainly due to the following reasons. That is, when printing on a color paper from a color negative film using a printer, the printer first (1) measures the blue density, green density, and red density of the color negative film, respectively, and (2) then measures these measured values. Convert to the exposure of color paper,
(3) The color paper is exposed with this exposure amount. Various printers are commercially available in the market, and the spectral sensitivity of the detector used for photometry in (1) may differ depending on the model of these printers. Also, due to the spectral absorption characteristics of the coloring dyes in the color negative film, For example, the half value width may be too small, or the spectral absorption characteristics may vary depending on the density, so that a hue shift may occur.

Some of the above-mentioned pyrazoloazole-based magenta couplers have large fluctuations in spectral absorption characteristics depending on the concentration, and this is considered to be one of the reasons why the variation between printers becomes large when the pyrazoloazole-based magenta coupler is used in a color negative film. Be done. Therefore, in silver halide color photographic light-sensitive materials containing a pyrazoloazole-based magenta coupler, there has been a demand for development of a technique for reducing printer fluctuation.

To solve this problem, the present inventors have proposed Japanese Patent Application No.
It was found that the combination of two kinds of pyrazoloazole-based magenta couplers as described in JP-A-147908 was effective, but the effect was still insufficient.

Further, it has been revealed that silver halide color photographic light-sensitive materials containing these pyrazolotriazole couplers have a problem that their photographic performance is apt to change during long-term storage after production. In recent years, the industry is increasingly demanding to improve the photographic performance of silver halide color photographic light-sensitive materials, and there is a strong demand for what has so-called homogeneity, with little difference in sensitivity over time and between lots. As the silver halide color photographic light-sensitive materials become more silver-saving and thinner, the change in photographic performance during storage over time increases, so there is little change in photographic performance during storage over time, that is, raw storage stability is good. Development of a silver halide color photographic light-sensitive material has been desired.

Further, these pyrazolotriazole type magenta couplers are used in the development process, especially in the pH of the color developing solution.
It has been found that there is a drawback that the change in color density is large with respect to fluctuations, and even when processed with color developing solutions of different pH, the change in color density is small, that is, silver halide color with good processing stability. Development of a photographic light-sensitive material is desired.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material which is excellent in processing stability, has little variation between printers, and has good raw storage stability.

[0012]

The above object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, and the silver halide emulsion layer having the following general formula [M- I], at least one magenta coupler represented by the following general formula [M-II], and at least one magenta coupler represented by the following general formula [M-II]
-I], a silver halide color photographic light-sensitive material containing at least one compound capable of releasing a development inhibitor or a precursor of a development inhibitor by reacting with an oxidized product of a color developing agent. Achieved by

[0013]

[Chemical 3] [In the formula, R ₁ represents a hydrogen atom, an alkyl group or an aryl group. R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group or an aryl group. Further, R ₂ , R ₃ and R ₄ may be ones in which R ₂ , R ₃ or R ₄ are bonded to each other to form a saturated or unsaturated ring. At least two of R ₂ , R ₃ and R ₄ are not hydrogen atoms. J represents a methylene group, an oxygen atom, or a sulfur atom. X ₁ and X ₂ represent a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent.
Z ₁ and Z ₂ represent a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z ₁ and Z ₂ may have a substituent. ]

[0014]

[Chemical 4][In the formula, R¹ Represents an alkyl group, R² Is an alkyl group or
Represents an aryl group, R³ Is an oxycarbonyl group, sulfo
Amide group, carbamoyl group, acylamino group, urei
Group, oxycarbonylamino group, sulfonyloxy
Represents a group, a carbonyloxy group or a sulfamoyl group.
R^Four Represents a substituent, and n represents 0, 1, 2, or 3. X is
When coupled with the oxidant of the color developing agent and released,
Forms ortho-quinone methide or para-quinone methide
Represents a group that releases a development inhibitor or its precursor. ]
Magenta coupler represented by the general formula [MI] of the present invention
Will be described in detail.

In the general formula [MI], R ₁ represents a hydrogen atom, an alkyl group or an aryl group.

The alkyl group represented by R ₁ preferably has ₁ to 32 carbon atoms and may be linear or branched.

The aryl group represented by R ₁ is preferably a phenyl group.

In the general formula [MI], J represents a methylene group, an oxygen atom or a sulfur atom.

Examples of the group capable of splitting off upon reaction with the oxidation product of the color developing agent represented by X ₁ include, for example, a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, Sulfonyloxy, 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.

Examples of the nitrogen-containing heterocycle formed by Z ₁ include a pyrazole ring, an imidazole ring, a triazole ring and a tetrazole ring.

More specifically, the compound represented by the general formula [M-I] is, for example, the following general formulas [M-Ia] to [M-If].
Represented by

[0022]

[Chemical 5] In the general formulas [M-Ia] to [M-If], R ₁
And X ₁ are respectively synonymous with R ₁ and X ₁ in the general formula [MI], and R _{11 to} R ₁₇ represent a hydrogen atom or a substituent.

The substituent represented by R _{11 to} R ₁₇ is not particularly limited, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl groups. In addition to these, halogen atom and cycloalkenyl, alkynyl, heterocycle, 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 groups, and spiro compound residues, Examples include bridged hydrocarbon compound residues.

The alkyl group represented by R _{11 to} R ₁₇ preferably has 1 to 32 carbon atoms and may be linear or branched.

The aryl group represented by R _{11 to} R ₁₇ is preferably a phenyl group.

Examples of the acylamino group represented by R _{11 to} R ₁₇ include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R _{11 to} R ₁₇ include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkylthio group represented by R ₁₁ to R _17, the alkyl moiety in the arylthio group, the aryl component is an alkyl group represented by R ₁₁ to R _17, an aryl group.

The alkenyl group represented by R _{11 to} R ₁₇ is preferably one having 2 to 32 carbon atoms, and the cycloalkyl group is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. It may be chained or branched.

The cycloalkenyl group represented by R _{11 to} R ₁₇ is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

The sulfonyl group represented by R _{11 to} R ₁₇ includes an alkylsulfonyl group, an arylsulfonyl group and the like;
As the sulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, etc .; as the phosphonyl group, an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; as an acyl group, an alkylcarbonyl group, Arylcarbonyl group, etc .; carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, etc .; Sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, etc .; Acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc. Groups etc .; as carbamoyloxy groups, alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc .; as ureido groups, alkylureido groups, arylureido groups, etc .; sulfamoylamido The group is an alkylsulfamoylamino group, an arylsulfamoylamino group, or the like; the heterocyclic group is preferably a 5- to 7-membered one, specifically, a 2-furyl group, a 2-thienyl group, a 2- A pyrimidinyl group,
2-benzothiazolyl group and the like; as the heterocyclic oxy group,
Those having a 5- to 7-membered heterocycle are preferable, for example, 3,
4,5,6-tetrahydropyranyl-2-oxy group, 1
-Phenyltetrazole-5-oxy group and the like; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, 2-pyridylthio group, 2-benzothiazolylthio group,
2,4-diphenoxy-1,3,5-triazole-6
-Thio group, etc .; siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group, succinimide group, 3-heptadecyl succinimide group, phthalimide group, glutarimide group, etc. The spiro compound residue includes spiro [3.
3] heptan-1-yl, etc .; as the bridged hydrocarbon compound residue, bicyclo [2.2.1] heptan-1-yl,
Tricyclo [3.3.1.1 ^3,7 ] decan-1-yl,
7,7-Dimethyl-bicyclo [2.2.1] heptane-
1-yl and the like can be mentioned.

The above general formula [M-Ia] to general formula [M-I]
Among the magenta couplers represented by f], the magenta couplers represented by the general formulas [M-Ia] to [M-Ib] are particularly preferable.

The most preferred substituents R _{11 to} R ₁₇ on the heterocycle are those represented by the following general formula [M-Ig]. Formula _{[M-Ig] R 18 -CH} 2 - wherein, R ₁₈ is synonymous with the R ₁₁ to R _17. R ₁₈ is preferably a hydrogen atom or an alkyl group.

Typical examples of the magenta coupler represented by the general formula [MI] according to the present invention will be given below.
The present invention is not limited to this.

[0035]

[Chemical 6]

[0036]

[Chemical 7]

[0037]

[Chemical 8]

[0038]

[Chemical 9]

[0039]

[Chemical 10]

[0040]

[Chemical 11]

[0041]

[Chemical 12]

[0042]

[Chemical 13]

[0043]

[Chemical 14]

[0044]

[Chemical 15] Next, the magenta coupler represented by formula [M-II] of the present invention will be described in detail.

In the formula [M-II], R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group or an aryl group. Two or three of R ₂ , R ₃ and R ₄ may be bonded to each other to form a saturated or unsaturated ring. At least two of R ₂ , R ₃ and R ₄ are not hydrogen atoms.

The alkyl group represented by R ₂ , R ₃ and R ₄ preferably has 1 to 32 carbon atoms and may be linear or branched. The aryl group represented by R ₂ , R ₃ and R ₄ is preferably a phenyl group.

The saturated or unsaturated ring formed by combining two or three members out of R ₂ , R ₃ and R ₄ is cycloalkane, cycloalkene, heterocyclic ring, benzene ring or bridged hydrocarbon ring. Is mentioned.

In the general formula [M-II], X ₂ and Z ₂ are
It is synonymous with X < ₁ >, Z < ₁ > of the said general formula [MI].

More specifically, the compounds represented by the general formula [M-II] are, for example, the following general formulas [M-IIa] to [M-IIf].
Represented by

[0050]

[Chemical 16] In the general formulas [M-IIa] to [M-IIf], R ₂₁
To R ₂₇ have the same meanings as the above R _{11 to} R ₁₇ .

Typical examples of the magenta coupler represented by the general formula [M-II] according to the present invention will be given below.
The present invention is not limited to this.

[0052]

[Chemical 17]

[0053]

[Chemical 18]

[0054]

[Chemical 19]

[0055]

[Chemical 20]

[0056]

[Chemical 21]

[0057]

[Chemical formula 22]

[0058]

[Chemical formula 23] A magenta coupler represented by the general formula [MI] (hereinafter,
Magenta coupler [MI]) and general formula [MI]
The magenta coupler represented by [I] (hereinafter referred to as magenta coupler [M-1I]) is referred to as the Journal of the Chemical Societ.
y), Perkin I (1977), 2047-
2052, US Pat. No. 3,725,067, JP-A-59
-99437, 58-42045, 59-16
2548, 59-171956, 60-335.
No. 52, No. 60-43659, No. 60-172982
No. 60-190779, No. 62-209457, No. 63-307453, etc. can be referred to for synthesis.

In the present invention, the magenta coupler [M-
I] is usually 1 × 10 ⁻³ mol to 1 mol of silver halide.
It can be used in an amount of 1 mol, preferably 1 × 10 ⁻² mol to 8 × 10 ⁻¹ mol.

The magenta coupler [M-II] is used in the range of 1 × 10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1 mol, per mol of silver halide. You can

In the present invention, the magenta coupler [M-I] and the magenta coupler [M-II] are used together, but the molar ratio of the magenta coupler [M-I] and the magenta coupler [M-II] is 10: 1 to 1: 1. : 5 is preferable, and 5: 1 to 1: 3 is more preferable. The couplers of this invention can be used with other types of magenta couplers.

In the present invention, the magenta coupler [M-
I] and the magenta coupler [M-II] are contained in at least one of the green-sensitive silver halide emulsion layers.

Next, a compound capable of releasing a development inhibitor or a precursor of the development inhibitor by the reaction with the oxidant of the color developing agent represented by the general formula [DI] of the present invention (hereinafter referred to as the present invention (Hereinafter referred to as "DIR coupler") will be described in more detail.

[0064]

[Chemical formula 24][In the formula, R¹ Represents an alkyl group, R² Is an alkyl group or
Represents an aryl group, R³ Is an oxycarbonyl group, sulfo
Amide group, carbamoyl group, acylamino group, urei
Group, oxycarbonylamino group, sulfonyloxy
Represents a group, a carbonyloxy group or a sulfamoyl group.
R^Four Represents a substituent, and n represents 0, 1, 2, or 3. X is
When coupled with the oxidant of the color developing agent and released,
Forms ortho-quinone methide or para-quinone methide
Represents a group that releases a development inhibitor or its precursor. ]
In the general formula [D-I], R¹ An alkyl group represented by
May be linear, branched or cyclic.
Examples of the kill group include methyl group, ethyl group and dodecyl group.
Examples of the branched alkyl group include a group and the like.
Examples include isopropyl group, t-butyl group and t-octyl group.
Examples of the cyclic alkyl group include cyclopro
Pill group, cyclohexyl group, adamantyl group, etc.
Be done. These R¹ The alkyl group represented by
And a substituent having, for example, a halogen atom.
Atom, aryl group, alkoxy group, aryloxy
Group, alkylsulfonyl group, acylamino group, hydroxy group
Examples thereof include a sil group. R¹ As a branched or cyclic
Alkyl groups are preferred, especially branched alkyl groups such as
Most preferred is the t-butyl group.

In the general formula [D-I], R² Represented by
Examples of the alkyl group include¹ Similar groups to
It These R² The alkyl group represented by is R¹ Similar to
Those having a substituent are also included. R² Alkyl represented by
Preferred as the group is a linear or branched alkyl group
Is.

In the general formula [D-I], R² Table
Examples of the aryl group include phenyl group and naphthyl group.
And the like. These R² An aryl group represented by
May further have a substituent, and examples of the substituent include
Is a halogen atom, an alkyl group, an aryl group, an alkoxy group.
Si group, aryloxy group, nitro group, cyano group and acyl group
Examples thereof include a ruamino group. R² An aryl group represented by
Is preferably a substituted or unsubstituted phenyl group.
R² Is particularly preferably a linear alkyl group,
Most preferred is a ru radical.

In the above general formula [D-I], R³ Haso
An oxycarbonyl group which may have a substituent and a sulfur
Honamide group, carbamoyl group, acylamino group, urea
Id group, oxycarbonylamino group, sulfonyloxy
A group, a carbonyloxy group or a sulfamoyl group,
Preferably, the groups represented by the following general formulas A to H and J to L are used.
is there.

[0068]

[Chemical 25]R in the general formulas A to H and J to L¹¹ Is an alkyl group,
Represents an alkyl group or an aryl group, R¹² And R¹³ Are mutual
Independently hydrogen atom, alkyl group, cycloalkyl group
Alternatively, it represents an aryl group.

R¹¹ , R¹² And R¹³ An alkyl group represented by
Examples of the cycloalkyl group and the cycloalkyl group include 1 to 1 carbon atoms.
30 linear or branched alkyl groups and cycloalkyls
Groups (eg methyl group, n-butyl group, cyclohexyl
Group, 2-ethylhexyl group, n-dodecyl group and n-hexyl group
Xadecyl group). Also, R¹¹ , R¹² And R¹³
The aryl group represented by, for example, has from 6 to 6 carbon atoms.
22 aryl groups (eg phenyl and 1-naphthyl)
Group).

These R¹¹ , R¹² And R¹³ Represented by
Further substituted by alkyl group, cycloalkyl group and aryl group
Those having a group are also included, and as this substituent,
For example, halogen atoms (eg chlorine atom and bromine source)
Child), hydroxyl group, aryl group (eg phenyl group)
And 4-t-butylphenyl group), an aryloxy group
(For example, phenoxy group, p-methylphenoxy group and
2,4-di-t-amylphenoxy group), alkoxy group
(For example, methoxy group, ethoxy group, i-propoxy group and
And n-dodecyloxy group), cycloalkyloxy group
(Eg cyclohexyloxy group), alkylthio group
(Eg methylthio group), alkylsulfonylamino group
(For example, a methanesulfonylamino group and n-butanesul
(Fonylamino group) and alkylcarbonylamino groups (eg
For example, an acetylamino group and 3- (2,4-di-t-amido)
Ruphenoxy) butanoylamino group) and the like.

Also, R¹¹ , R¹² And R¹³ Ally represented by
In addition to the above substituents,
Those that have are also included.

In the above general formulas E and K, J represents a divalent organic connecting group selected from an alkylene group and an arylene group, and this alkylene group is, for example, a straight chain or branched chain having 1 to 10 carbon atoms. Alkylene group (for example, a methylene group, an ethylene group, a methylethylene group, a propylene group, a dimethylmethylene group, a butylene group and a hexylene group), and examples of the arylene group include an arylene group having 6 to 14 carbon atoms ( For example, 1,2-
A phenylene group, a 1,4-phenylene group and a 1,4-naphthylene group).

In the general formula [D-I], R^Four Represented by
The substituent is any group that can be substituted on the benzene ring.
Well, for example, halogen atom, alkyl group, alkoxy
Group, aryloxy group, acyloxy group, imide group,
Sylamino group, sulfonamide group, oxycarbonyl
Group, carbamoyl group, sulfamoyl group, carbonylo
Xy, oxycarbonylamino, ureido and sulfur
Examples include a sulfonyl group.

In the general formula [D-I], n is 0,
1, 2, or 3, but when n represents 2 or 3,
Each R^Four May be the same or different. Preferred
Ku n is 0 or 1.

In the general formula [D-I], the group represented by X forms an ortho-quinone methide or para-quinone methide upon coupling with an oxidized product of a color developing agent and is released, and a development inhibitor or It is a group that releases the precursor, and preferably includes groups represented by the general formulas [D-II] and [D-III].

[0076]

[Chemical formula 26]In the general formulas [D-II] and [D-III], R^{twenty one} Is
Represents a group capable of substituting on a benzene ring, for example, a halogen atom,
Alkyl group, alkenyl group, aralkyl group, alkoxy
Group, alkoxycarbonyl group, anilino group, acylami
Group, ureido group, cyano group, nitro group, sulfone amine
Group, sulfamoyl group, carbamoyl group, aryl
Group, carboxyl group, sulfo group, cycloalkyl group,
Lucansulfonyl group, arylsulfonyl group or acyl
Groups.

R^{twenty one} As a nitro group, acylamino
Group, sulfonamide group, sulfamoyl group, cyano group,
An alkoxycarbonyl group and the like are preferable.

K represents an integer of 0 to 4, preferably
Represents 0, 1, 2. Particularly preferred k is 1.

In the general formulas [D-II] and [D-III],
And R^{twenty two} And R^{twenty three} The groups represented by are each independently a hydrogen atom,
It represents an alkyl group or an aryl group. R^{twenty two} And R^{twenty three} Represented by
Examples of the alkyl group include methyl group, ethyl group, i
-Propyl group, trifluoromethyl group, cyclohexyl
Group and dodecyl group. R^{twenty two} And R^{twenty three} Represented by
Examples of the aryl group include phenyl group and p-tolyl
Group, p-octylphenyl group, naphthyl group
It

In the general formulas [D-II] and [D-III], T represents a linking group. As the linking group represented by T,
For example, US Pat. Nos. 4,146,396 and 4,65.
Group utilizing the cleavage reaction of hemiacetal described in 2,516 or 4,698,297, and cleavage reaction utilizing the intramolecular nucleophilic reaction described in US Pat. No. 4,248,962. Timing groups to be awakened, the timing groups described in US Pat. No. 4,409,323 or US Pat. No. 4,421,845, US Pat.
A group described in No. 3 which causes a cleavage reaction by utilizing hydrolysis of imino ketal or West German Published Patent 2,626,26
Examples of the group described in No. 317 are those capable of causing a cleavage reaction by utilizing ester hydrolysis.

In the general formulas [D-II] and [D-III], m represents 0 or 1.

In the general formulas [D-II] and [D-III], DI represents a group which becomes a development inhibitor by cleaving, and a preferable development inhibitor is, for example, a 5-mercaptotetrazole compound (for example, 1 -Phenyl-5-mercaptotetrazole, 1- (4-hydroxyphenyl) -5-
Mercaptotetrazole, 1- (2-methoxycarbonylphenyl) -5-mercaptotetrazole, 1-ethyl-5-mercaptotetrazole and 1-propyloxycarbonylmethyl-5-mercaptotetrazole),
Benzotriazole compounds (eg 5- (or 6
-) Nitrobenzotriazole, 5- (or 6-)
Phenoxycarbonylbenzotriazole), 1,3
4-thiadiazole-based compound (for example, 5-methyl-2-
Mercapto-1,3,4-thiadiazole, 5- (2-
Methoxycarbonylethylthio) -2-mercapto-
1,3,4-thiadiazole), 1,3,4-oxadiazole-based compound (for example, 5-methyl-2-mercapto-1,3,4-oxadiazole), benzothiazole-based compound (for example, 2-mercapto) Benzothiazole),
Benzimidazole compounds (eg 2-mercaptobenzimidazole), benzoxazole compounds (eg 2-mercaptobenzoxazole), 1,2,4
-Triazole compounds (for example, 3- (2-furyl)-
5-hexylthio-1,2,4-triazole). DI is preferably a group forming a 1,3,4-oxadiazole compound or a 5-mercaptotetrazole compound.

The development inhibitor is preferably a compound having a substituent containing a bond (for example, an ester bond, a urethane bond, a sulfonic acid ester bond and a carbonic acid ester bond) capable of causing a cleavage reaction during the development processing.

Typical examples of the DIR coupler of the present invention will be given below, but the present invention is not limited thereto.

[0085]

[Chemical 27]

[0086]

[Chemical 28]

[0087]

[Chemical 29]

[0088]

[Chemical 30]

[0089]

[Chemical 31]

[0090]

[Chemical 32] The amount of these DIR couplers of the present invention to be used is not particularly limited, but it is preferable to use 0.0001 to 0.1 mol, and particularly 0.001 to 0.05 mol, per mol of silver halide.
It is preferable to use mol.

In the present invention, the magenta coupler [M-
I], magenta coupler [M-II] and DIR of the present invention
In order to incorporate the coupler into the silver halide emulsion layer, a conventionally known method, for example, a known high boiling solvent such as dibutyl phthalate and tricresyl phosphate, and a low boiling solvent such as butyl acetate and ethyl acetate are mixed. Liquid magenta coupler [MI], magenta coupler [MI]
I] and the DIR coupler of the present invention, either alone or in combination, and dissolved, and then mixed with an aqueous gelatin solution containing a surfactant, and then emulsified by using a high-speed rotary mixer or a colloid mill or an ultrasonic disperser. After dispersion, a method of directly adding to the emulsion can be adopted. Further, after the above emulsified dispersion is set, it may be shredded, washed with water, and then added to the emulsion.

In the present invention, the magenta coupler [MI] according to the present invention, the magenta coupler [M-II] and the DIR coupler according to the present invention are separately dispersed by the above dispersion method and added to the silver halide emulsion. But you can
A method in which these compounds are simultaneously dissolved, dispersed and added to the emulsion is preferred.

As the silver halide emulsion used in the light-sensitive material of the present invention, any ordinary silver halide emulsion can be used. The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder of the emulsion.

The emulsion layer and other hydrophilic colloid layers may be hardened and may contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer. A coupler is used in the emulsion layer of the color photographic light-sensitive material.

Further, the development accelerator, the bleaching accelerator, the developer, the silver halide solvent, the toning agent, the hardener and the hardener can be obtained by coupling the colored coupler, the competing coupler and the oxidized product of the developing agent, which have the effect of color correction. Compounds that release photographically useful fragments such as film agents, fog agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or emulsion layers,
Dyes may be included which are bleached or bleached from the light-sensitive material during the development process. For the light-sensitive material, formalin scavenger, fluorescent whitening agent, matting agent, lubricant, image stabilizer, surfactant, color fog inhibitor, development accelerator,
Development retarders and bleaching accelerators can be added.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

In order to obtain a dye image using the light-sensitive material of the present invention, a color photographic process generally known can be carried out after exposure.

[0100]

EXAMPLES Specific examples of the present invention will be described below.
Embodiments of the invention are not limited to these. Example 1 In Example, the addition amount in the silver halide photographic light-sensitive material
Is 1m unless otherwise specified² The hit one is shown. Also, halo
Silver genide is shown in terms of silver, sensitizing dyes and couplers
It is shown per mol of silver in the same layer.

Multilayer color photographic light-sensitive material samples 101 to 115 were prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support. First layer: antihalation layer (HC) A gelatin layer containing black colloidal silver.

Dry film thickness 3 μm Second layer; Intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Dry film thickness 1.0 μm Third layer; low-sensitivity red-sensitive silver halide emulsion layer (RL) Monodisperse emulsion consisting of AgBrI containing 0.3 μm average grain size and 3 mol% AgI (Emulsion I: wide distribution) 12%) 1.8 g Sensitizing dye I 6.0 × 10 ⁻⁴ mol Sensitizing dye II 1.0 × 10 ⁻⁴ mol Cyan coupler (C-1) 0.06 mol Colored cyan coupler (CC-1) 0.003 mol DIR compound (DD-1) 0.0015 mol DIR compound (DD-2) 0.002 mol dioctyl phthalate 0.6 g dry film thickness 3.5 μm fourth layer; high-sensitivity red-sensitive silver halide emulsion layer (RH) Monodisperse emulsion consisting of AgBrI containing 0.5 μm average particle size and 3 mol% AgI (emulsion II: 12% wide distribution) 1.3 g Sensitizing dye I 3.0 × 10 ⁻⁴ mol Sensitizing dye II 1.0 × 10 ^-4 mol Uncoupler (C-1) 0.02 mol Colored cyan coupler (CC-1) 0.0015 mol DIR compound (DD-2) 0.001 mol Dioctyl phthalate 0.2 g Dry film thickness 2.5 μm Fifth layer; Intermediate Layer (IL) The same gelatin layer as the second layer.

Dry film thickness 1.0 μm Sixth layer; low-sensitivity green-sensitive silver halide emulsion layer (GL) Emulsion I 1.2 g Sensitizing dye III 2.5 × 10 ⁻⁴ mol Sensitizing dye IV 1.2 × 10 ^-4 mol Magenta coupler (described in Table 1 and Table 2) Colored magenta coupler (CM-1) 0.009 mol DIR compound (described in Table 1 and Table 2) Tricresyl phosphate 0.5 g Dry film thickness 3 .5 μm 7th layer; high-sensitivity green-sensitive silver halide emulsion layer (GH) Emulsion II 1.3 g Sensitizing dye III 1.5 × 10 ⁻⁴ mol Sensitizing dye IV 1.0 × 10 ⁻⁴ mol Magenta coupler ( Listed in Table 1 and Table 2) Colored magenta coupler (CM-1) 0.002 mol DIR compound (listed in Table 1 and Table 2) Tricresyl phosphate 0.3 g Dry film thickness 2.5 μm Eighth layer; Yellow Filter layer (YC) Gelatin layer containing emulsified dispersion of the color colloidal silver and 2,5-di -t- octylhydroquinone.

Dry film thickness 1.2 μm 9th layer; low-sensitivity blue-sensitive silver halide emulsion layer (BL) Monodispersed emulsion consisting of AgBrI containing 0.48 μm average grain size and 3 mol% AgI (Emulsion III: wide distribution) 12%) 0.9 g Sensitizing dye V 1.3 × 10 ⁻⁴ mol Yellow coupler (Y-1) 0.29 mol Tricresyl phosphate 0.5 g Dry film thickness 3.5 μm 10th layer; high sensitivity Blue-sensitive silver halide emulsion layer (BH) Monodisperse emulsion consisting of AgBrI with average grain size 0.8 μm and AgI 3 mol% (Emulsion IV: 12% wide distribution) 0.5 g Sensitizing dye V 1.0 × 10 ^-4 mol Yellow coupler (Y-1) 0.08 mol DIR compound (DD-2) 0.0015 mol tricresyl phosphate 0.10 g Dry film thickness 2.5 μm 11th layer; 1st protective layer (PRO -1) Odor Silver oxide emulsion (AgI 2 mol%, average particle size 0.07 μm) 0.5 g A gelatin layer containing ultraviolet absorbers (UV-1) and (UV-2). Dry film thickness 2.0 μm 12th layer; Second protective layer (PRO-2) Polymethylmethacrylate particles (diameter 1.5 μm) and formalin scavenger (HS-1), (HS-2)
A gelatin layer containing.

Dry film thickness 1.5 μm In addition to the above composition, a gelatin hardening agent (H-
1), (H-2) and a surfactant were added. Sensitizing Dye I Anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing Dye II Anhydro-9-ethyl-3,3'- The-
(3-Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III Anhydro-5,5'-diphenyl-9-
Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxide Sensitizing dye IV Anhydro-9-ethyl-3,3'-di-
(3-Sulfopropyl) -5,6,5 ', 6'-dibenzooxacarbocyanine hydroxide Sensitizing dye V Anhydro-3,3'-di- (3-sulfopropyl) -4,5-benzo-5 ′ -Methoxythiacyanine hydroxide

[0107]

[Chemical 33]

[0108]

[Chemical 34]

[0109]

[Chemical 35]

[0110]

[Table 1]

[0111]

[Table 2] The photographic material prepared as described above was subjected to wedge exposure by a usual method, and then developed by the processing steps shown in Table 3 below.

[0112]

[Table 3] The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used. Color developer Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl -N-Ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to 1 liter and potassium hydroxide or 20% was added.
Adjust to pH 10.06 with sulfuric acid. Color development replenisher water 800 ml potassium carbonate 35 g sodium hydrogen carbonate 3 g potassium sulfite 5 g sodium bromide 0.4 g hydroxylamine sulfate 3.1 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline Sulfate 6.3g Potassium hydroxide 2g Diethylenetriaminepentaacetic acid 3.0g Water to make 1 liter, potassium hydroxide or 20%
Adjust to pH 10.18 with sulfuric acid. Bleaching solution Water 700 ml 1,3-Diaminopropanetetraacetic acid ferric ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Water is added to make 1 liter, and pH is 4.4 using ammonia water or glacial acetic acid. Adjust to. Bleaching replenisher Water 700 ml 1,3-Diaminopropanetetraacetic acid Ferric ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting the pH to 4.0 using ammonia water or glacial acetic acid, add water. Set to 1 liter. Fixing solution Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using glacial acetic acid or ammonia water, add water to make 1 liter. Fixing replenisher Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using glacial acetic acid or ammonia water, add water to make 1 liter. Stabilizer and stabilizing replenisher Water 900 ml 36 36 g

[0113]

[Chemical 36] Dimethylol urea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UC-L-77) 0.1 g Ammonia water 0.5 ml After adding water to make 1 liter, Ammonia water or 50
Adjust to pH 8.5 with% sulfuric acid. [Evaluation of raw storability] The prepared samples 101 to 115 were 40
A sample that had been left to stand for 7 days in an atmosphere of ° C and a relative humidity of 80% to be forcibly deteriorated was exposed to light in the same manner as above, and then subjected to the same development processing. The fog and sensitivity of the green photosensitive layer of the obtained sample were measured, and the fog increase amount (ΔFog) with respect to the sample which was not forcibly deteriorated and the after-forced deterioration when the sensitivity of the sample without forcible deterioration was set to 100 The relative sensitivity of the sample was measured. [Evaluation of processing stability] Samples 101 to 115 were exposed to white light through a step wedge for sensitometry in the same manner as described above, and then the pH of the color developing solution was adjusted to 10.4.
The same processing was performed by using the color developing solutions changed to 1 and 10.0, and the variation values of gamma in the linear portion in the characteristic curve of green density were compared.

The fluctuation value of gamma is the rate of change of gamma value B at pH 10.4 with respect to gamma value A at pH 10.0, and was calculated by the following formula.

Gamma fluctuation value = {(B / A) -1} × 100 The smaller the gamma fluctuation value, the smaller the change. [Evaluation of variation between different types of printers] Samples 101 to 115 were exposed to uniform white light, and the same as the above (however, the color developing solution
The pH was brought to 10.18. ) Development processing was performed. Using this developed sample, printing was performed by the printer A so that the reflection density became 0.5, and print samples 101A to 115A were created.

Next, using a printer B having a spectral sensitivity of a detector in a green region different from that of the printer A, printing was performed on each sample under the same printing conditions as the printer A to prepare print samples 101B to 115B. With respect to the obtained print samples 101B to 115B, deviation from gray of each print sample, that is, variation between different printers was visually evaluated by 10 panelists. The above results are also shown in Table 4.

[0117]

[Table 4] As is clear from Table 4, the light-sensitive material 101 other than the present invention.
Causes a large increase in fog and a decrease in sensitivity when it is forcibly deteriorated, has a large gamma fluctuation value when the pH of the color developing solution changes, and also has a large fluctuation between different printers.

Although the photosensitive materials 102 and 103 have small variations between different types of printers, the fog increases and the sensitivity decreases greatly when they are forcibly deteriorated, and the gamma variation value when the pH of the color developing solution changes is also large.

On the other hand, the light-sensitive materials 104 to 1 of the present invention
No. 15 has a small increase in fog and a decrease in sensitivity when it is forcibly deteriorated, and has a good raw storability. In addition, the gamma fluctuation value when the pH of the color developing solution is changed is small, and the fluctuation between different types of printers is also small, resulting in very good performance.

[0120]

According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material which exhibits little fluctuation between printers, has good raw storability, and has good processing stability.

Claims (1)

[Claims] 1. At least one layer of halogen on a support.
For silver halide color photographic light-sensitive material having silver halide emulsion layer
In the silver halide emulsion layer, the following general formula [M-
I], at least one of magenta couplers represented by
A small number of magenta couplers represented by the following general formula [M-II]
Coloring represented by the following general formula [D-I]
A development inhibitor or
At least one compound capable of releasing a precursor of an image suppressing agent
Silver halide color photographic effect characterized by containing
Light material. [Chemical 1][In the formula, R₁Is a hydrogen atom, an alkyl group or an aryl group
Represents R₂, R₃And R_FourIs a hydrogen atom, alkyl group,
Represents a reel group. Also, R₂, R₃And R_FourAre these
R₂, R₃Or R_FourBind to form a saturated or unsaturated ring
It may be one that does. R₂, R₃And R_FourAt least
Two are not hydrogen atoms. J is methylene group, oxygen source
Represents a child and a sulfur atom. X₁, X₂Is hydrogen atom or color development
Represents a group capable of splitting off upon reaction with the oxidant of the main drug.
Z₁, Z₂Is a nonmetallic source necessary to form a nitrogen-containing heterocycle
Represents the child group, and the Z₁, Z₂The ring formed by
You may have. ] [Chemical 2][In the formula, R¹ Represents an alkyl group, R² Is an alkyl group or
Represents an aryl group, R³ Is an oxycarbonyl group, sulfo
Amide group, carbamoyl group, acylamino group, urei
Group, oxycarbonylamino group, sulfonyloxy
Represents a group, a carbonyloxy group or a sulfamoyl group.
R^Four Represents a substituent, and n represents 0, 1, 2, or 3. X is
When coupled with the oxidant of the color developing agent and released,
Forms ortho-quinone methide or para-quinone methide
Represents a group that releases a development inhibitor or its precursor. ]