JPH05100386A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and processing stability 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 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, Z is a nonmetallic atomic group necessary to form an N-containing hetero ring; X in formula I is H or a group to be released by coupling with the oxidation product of a color developing agent; R is H or a substituent; RA is halogen or alkoxy; RB is acylamino or the like; R<1> is alkyl: R<2> is alkyl or aryl: R<3> is oxycarbonyl or the like; R<4> is a substituent: and X in formula III 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 high sensitivity, excellent processing stability and good storage stability over time.

[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 such as little secondary absorption, advantageous color reproducibility, and excellent color developability.

However, it has been found that there is a drawback that the change in color density is large with respect to the change in the developing process, especially the change in the pH of the developing solution.

In order to remedy this drawback, the present inventors have found the methods described in Japanese Patent Application No. 1-299771 and Japanese Unexamined Patent Publication No. 3-126031, but the effect is not sufficient.
Further, these methods have problems such as reduction in sensitivity and deterioration of storage stability over time, and it has been desired to develop a technique of improving development processing fluctuation without deteriorating photographic performance.

Further, it has been revealed that the silver halide color photographic light-sensitive material containing these pyrazolotriazole type couplers has a problem that the 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.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material having high sensitivity, excellent processing stability, and good storage stability over time.

[0008]

SUMMARY OF THE INVENTION An 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 of the magenta couplers represented by the following general formula, at least one of the magenta couplers represented by the following general formula [M-II], and the following general formula [DI]
A silver halide color photographic light-sensitive material characterized by containing at least one compound capable of releasing a development inhibitor or a precursor of a development inhibitor by reacting with an oxidant of a color developing agent represented by It

[0009]

[Chemical 4] [In the formula, Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a substituent which is released by the reaction with the oxidized product of the color developing agent. R represents a hydrogen atom or a substituent. ]

[0010]

[Chemical 5] [In the formula, R _A represents a halogen atom or an alkoxy group, and R _B represents an acylamino group, a sulfonamide group, an imide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an alkoxycarbonylamino group, or an alkoxy group. l represents an integer of 0 to 4. ]

[0011]

[Chemical 6][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. ]
First, the matrix represented by the general formula [MI] according to the present invention is used.
Zenta coupler (hereinafter referred to as magenta coupler [MI]
Say. ) Will be described.

[0012]

[Chemical 7] [In the formula, Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a substituent which is released by the reaction with the oxidized product of the color developing agent. R represents a hydrogen atom or a substituent. The substituent represented by R is not particularly limited, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl groups. 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, a heterocyclic thio group, a spiro compound residue, a bridged hydrocarbon compound residue and the like are also included.

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

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

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

As the sulfonamide group represented by R,
Examples thereof include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R 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. The alkenyl group may be linear or branched. Good.

The cycloalkenyl group represented by R preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

The sulfonyl group represented by R is an alkylsulfonyl group, an arylsulfonyl group, etc .; The sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group, etc .; The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group. , An aryloxyphosphonyl group, an arylphosphonyl group, etc .; as an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .;
As the carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group and the like; as the sulfamoyl group,
An alkylsulfamoyl group, an arylsulfamoyl group, etc .; an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .; a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; an ureido group , An alkylureido group, an arylureido group, etc .; As a sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc .; As a heterocyclic group, a 5- to 7-membered one is preferable. Is a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group, etc .; 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, etc .; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, 2-pyridylthio group, 2-benzo Thiazolylthio group, 2,4-
Diphenoxy-1,3,5-triazole-6-thio group, etc .; Siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; Imido group, succinimide group, 3-heptadecylsuccinic group Acid imide group, phthalimide group, glutarimide group, etc .; Spiro compound residues include spiro [3.3] heptan-1-yl, etc .; Bridged hydrocarbon compound residues include
Bicyclo [2.2.1] heptan-1-yl, tricyclo [3.3.1.1 ^3,7 ] decan-1-yl, 7,7-
Dimethyl-bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

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

[0022]

[Chemical 8] (R ₁ ′ has the same meaning as R above, Z ′ has the same meaning as Z above, and R ₂ ′ and R ₃ ′ each represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group). Can be mentioned,
Preferred is a halogen atom, especially a chlorine atom.

The nitrogen-containing heterocyclic ring formed by Z or Z'includes a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring and the like, and the substituent which the ring may have is the above-mentioned R. Are mentioned.

More specifically, the general formula [MI] is represented by, for example, the following general formulas [MI-1] to [MI-6].

[0025]

[Chemical 9] In the general formulas [M-I-1] to [M-I-6], R is
_{1 to} R ₈ and X have the same meanings as R and X above. Further, among the general formula [MI], the following general formula [M-
I-7].

[0026]

[Chemical 10]R in the formula₁, X and Z ″ Is R in the general formula [M-I],
It is synonymous with X and Z.

The above general formulas [M-I-1] to [M-I-]
Among the magenta couplers represented by [6], the magenta coupler represented by the general formula [MI-1] is particularly preferable.

The most preferable substituents R and R ₁ on the heterocycle are represented by the following general formula [MI-8]. Formula [M-I-8] R 9 -CH 2 - wherein, R ₉ is as defined above R. R ₉ is preferably a hydrogen atom or an alkyl group.

Further, by the Z in the general formula [MI],
Formed ring and Z in the general formula [M-I-7] ″ By
Substituents that the ring formed may have, as well as the general formula
R in [M-I-1] to [M-I-5]₂~ R₈age
Of these, those represented by the following general formula [MI-9] are preferable.
Yes. General formula [MI-9] -R _Ten-SO₂-R ₁₁ Where R _TenIs an alkylene group, R ₁₁Is an alkyl group,
Represents an alkyl group or an aryl group.

R _TenThe alkylene group represented by is preferably
The number of carbon atoms in the straight chain portion is 2 or more, more preferably 3 to 6
And may be linear or branched.

R ₁₁The cycloalkyl group represented by
Those having 5 to 6 members are preferable.

Typical specific examples of the magenta coupler [MI] will be given below, but the present invention is not limited thereto.

[0033]

[Chemical 11]

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

[0038]

[Chemical 16]

[0039]

[Chemical 17]

[0040]

[Chemical 18]

[0041]

[Chemical 19]

[0042]

[Chemical 20]

[0043]

[Chemical 21]

[0044]

[Chemical formula 22]

[0045]

[Chemical formula 23]

[0046]

[Chemical formula 24] In addition to the typical examples of the magenta coupler [MI] described above, specific examples of the magenta coupler [MI] include pages (18) to (32) of JP-A-62-166339.
Among the compounds listed on the page, Nos. 1-4, 6, 8
~ 17, 19-43, 45-59, 61-104, 10
The compound shown by 6-121,123-162,164-223 can be mentioned.

Further, the coupler is a Journal of the Chemical Society.
Society), Perkin I (1977),
2047-2052, U.S. Pat. No. 3,725,067,
JP-A-59-99437, JP-A-58-42045, JP-A-59-162548, JP-A-59-171956 and JP-A-6.
0-33552, 60-43659, 60-1
72982, 60-190779, and 62-20.
It can be synthesized with reference to Nos. 9457 and 63-307453.

Next, the above general formula [M-II] according to the present invention.
The magenta coupler represented by (hereinafter referred to as magenta coupler [M-II]) will be described.

[0049]

[Chemical 25] [In the formula, R _A represents a halogen atom or an alkoxy group, and R _B represents an acylamino group, a sulfonamide group, an imide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an alkoxycarbonylamino group, or an alkoxy group. l represents an integer of 0 to 4. ] General formula [M-
II], the halogen atom represented by R _A is
Examples thereof include chlorine atom, bromine atom and fluorine atom, and examples of the alkoxy group include methoxy group and dodecyloxy group. Preferred as R _A is a chlorine atom.

The acylamino group represented by R _B is
Examples thereof include a 2,4-di-t-pentylphenoxyacetamide group and a 4- (2,4-di-t-pentylphenoxy) butanamide group. Examples of the sulfonamide group include:
For example, a 4-dodecyloxyphenylsulfonamide group can be mentioned, an imide group can be, for example, an octadecenylsuccinimide group, and a carbamoyl group can be, for example.
Examples include 4- (2,4-di-t-pentylphenoxy) butylaminocarbonyl group, examples of the sulfamoyl group include tetradecanesulfamoyl group, and examples of the alkoxycarbonyl group include tetradecaneoxycarbonyl group. Examples of the alkoxycarbonylamino group include a dodecyloxycarbonylamino group, and examples of the alkoxy group include a methoxy group, an ethoxy group, and an octyloxy group. Preferable for R _B is p for R _A
It is an acylamino group substituted at position. Also, l is preferably 1.

Typical specific examples of the magenta coupler [M-II] are shown below, but the present invention is not limited thereto.

[0052]

[Chemical formula 26]

[0053]

[Chemical 27] These magenta couplers [M-II] are 1-phenyl-
General synthetic methods for synthesizing 5-pyrazolone compounds, for example, US Pat. Nos. 2,369,489 and 2,3
76,380, 2,472,581, 2,600,788, 2,93.
No. 3,391, No. 3,615,506, British Patent No. 956,261, No. 1,13.
It can be synthesized by the method described in Japanese Patent No. 4,329 and Japanese Patent Publication No. 45-20636.

A specific synthesis example of the magenta coupler [M-II] is shown below. Synthetic Example (Synthesis of Exemplified Compound II-5) 11.5 g of 1-pentachlorophenyl-3- (2-chloro-5-aminoanilino) -5-pyrazolone was added to 75 ml of ethyl acetate, and 2.7 g of sodium acetate was further dissolved. Add 20 ml of water, 1
Stir for hours. Then 4-dissolved in 25 ml of ethyl acetate
9.2 g of (2,4-di-t-pentylphenoxy) butanoyl chloride was added over 10 minutes. After stirring for 3 hours, the aqueous layer was removed, washed with 50 ml of water, and ethyl acetate was removed by distillation under reduced pressure. The obtained residue was recrystallized from toluene to obtain 12.8 g of the desired product. White crystals, melting point 125-127 ° C. The compound was identified by Mass, NMR and IR spectra, and it was confirmed that the compound was Exemplified compound M-5.

The magenta coupler [MI] is usually used in an amount of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol per mol of silver halide. it can.

The magenta coupler [M-II] is used in an amount of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² 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 added together in one silver halide emulsion layer, the molar ratio of the magenta coupler [MI] and the magenta coupler [M-II] is 1".
0: 1 to 1: 5 are preferable, and 5: 1 to 1: 3 are more preferable. The couplers of this invention can be used with other types of magenta couplers.

The magenta coupler [M-I] and the magenta coupler [M-II] can be separately used in two or more silver halide emulsion layers having the same color sensitivity. For example, a high-sensitivity silver halide emulsion layer and a low-sensitivity silver halide emulsion layer can be used separately.

In the present invention, the magenta coupler [M-
I] and the magenta coupler [M-II] are preferably 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 reacting with an oxidant of a 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.

[0061]

[Chemical 28][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 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.

[0065]

[Chemical 29]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 off with an oxidized product of a color developing agent to form 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].

[0073]

[Chemical 30]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 (eg, ester bond, urethane bond, sulfonic acid ester bond and carbonic acid ester bond) capable of causing a cleavage reaction during development processing.

Typical specific examples of the DIR coupler of the present invention are shown below, but the present invention is not limited thereto.

[0082]

[Chemical 31]

[0083]

[Chemical 32]

[0084]

[Chemical 33]

[0085]

[Chemical 34]

[0086]

[Chemical 35]

[0087]

[Chemical 36] 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 [M-I], the magenta coupler [M-II] and the DIR coupler of 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, by coupling with a colored coupler having a color correcting effect, a competing coupler and an oxidized product of a developing agent, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener and a hardener. 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 anti-irradiation 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 commonly known color photographic process can be carried out after exposure.

[0097]

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 following composition on the triacetyl cellulose film support from the support side. 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 grain 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 Mo Cyan coupler (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) Monodisperse 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

[0104]

[Chemical 37]

[0105]

[Chemical 38]

[0106]

[Chemical Formula 39]

[0107]

[Table 1]

[0108]

[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.

[0109]

[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. Stabilizing solution and stabilizing replenishing solution Water 900 ml 40 40 g

[0110]

[Chemical 40] 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 Sensitivity] After the treatment, the sensitometric characteristics of green light measurement were measured for each of the above samples.

The sensitivity was obtained from the reciprocal of the exposure amount required to give a density of fog +0.3, and the sensitivity of Sample 101 was 10
Table 4 shows the sensitivities of Samples 101 to 115 with relative sensitivity of 0. [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 gamma fluctuation value is the rate of change of the gamma value B at pH 10.4 with respect to the 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.

The above results are also shown in Table 4.

[0115]

[Table 4] As is clear from Table 4, Samples 105 to 1 according to the present invention
No. 15 has a high sensitivity and a small increase in fog and a decrease in sensitivity when forcedly deteriorated, and has a good raw storage property.
It can be seen that the gamma fluctuation is small when the pH value changes.

[0116]

According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material having high sensitivity, good raw storability and 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, Z is a nonmetal necessary for forming a nitrogen-containing heterocycle.
Represents a group of atoms, and the ring formed by Z has a substituent
May be. X is released by the reaction with the oxidant of the color developing agent.
Represents a substituent to be eliminated. R represents a hydrogen atom or a substituent.
You ] [Chemical 2][In the formula, R_ARepresents a halogen atom or an alkoxy group
And R_BIs an acylamino group, sulfonamide group, imide
Groups, carbamoyl groups, sulfamoyl groups, alkoxy groups
Rubonyl group, alkoxycarbonylamino group, alkoxy
Represents a group. l represents an integer of 0 to 4. ] [Chemical 3][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. ]