JPH07209829A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve lightfastness of dye image and to enhance image storage stability and manufacture aptitude by incorporating a specified dye image forming coupler and a polyol in a silver halide emulsion layer. CONSTITUTION:The photographic sensitive material has on a support one of silver halide emulsion layers containing the dye image forming coupler represented by the formula and the polyol in an amount of >=2 times the weight of the coupler in the same layer. In the formula, Z is a nonmetallic atomic group necessary to form an optionally substituted N-containing heterocyclic group; X is H or a group to be released by coupling with the oxidation product of a color developing agent: and R is H car a substituent.

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, more specifically, excellent color reproducibility and
The present invention relates to a silver halide color photographic light-sensitive material excellent in light fastness of a dye image.

[0002]

2. Description of the Related Art Conventionally, a combination of a yellow coupler, a magenta coupler and a cyan coupler is used in a color photographic paper which is directly provided for viewing. Many efforts have been made to date to improve the fastness of color dye images obtained from these couplers and to preserve and continue to utilize them for many years.

However, the storage stability in the light (light resistance) under the condition of being exposed to light is still at an insufficient level, and improvement is desired. In particular, among the three color dyes of yellow, magenta, and cyan, the magenta dye has the weakest light resistance, and efforts have been made to improve it.

Furthermore, the pyrazoloazole-based magenta couplers developed in recent years are basically different from 5-pyrazolone-based magenta couplers which have been conventionally used, in that the coloring dye has no sub-absorption at around 430 nm, so that basically color reproducibility is obtained. However, it is known that the magenta dye obtained from the pyrazoloazole-based magenta coupler is inferior in light resistance to the magenta dye obtained from the 5-pyrazolone-based magenta coupler. However, many improved techniques have been proposed. For example, JP-A-56
-159644, 59-125732, 61-145552, 60-2621
59 and 61-90155, and phenol or phenyl ether compounds described in JP-A-3-39956 and the like.
61-73152, 61-72246, 61-189539, 61-1895
40, 63-95439, etc., amine compounds, JP-A-61-140941, 61-145554, 61-158329, 6
Techniques using the metal complexes described in 2-183459 and the like can be mentioned.

On the other hand, JP-A-61-120146 and 61-120149
No. 61-120150, No. 61-120151, No. 61-120154 and the like, magenta obtained by substituting a secondary or tertiary alkyl group in a nitrogen-containing heterocycle of a pyrazoloazole-based magenta coupler. Techniques for improving the light resistance of dyes have been proposed.

[0006]

However, although these improved techniques are effective in improving the light resistance, they cannot be said to be sufficient, and even when these techniques are used, the light resistance of the magenta dye is not sufficient for the yellow dye and the cyan dye. At present, it is inferior to the light resistance of. Further, JP-A-4-140742 and JP-A-4-147136 disclose a technique for improving the light resistance of a magenta dye by using a high-boiling organic solvent in a weight ratio of 4 or more with respect to a pyrazoloazole-based magenta coupler. However, the degree of improvement in light resistance is not sufficient, and the use of such a large amount of high-boiling-point organic solvent deteriorates the stability of the dispersion containing the coupler over time, and There is a problem of poor manufacturing suitability such as coating failure.

On the other hand, Japanese Patent Application Laid-Open No. 4-265975 discloses a technique for improving the color development activity of a pyrazoloazole type magenta coupler by using a monohydric alcohol as a high boiling point organic solvent. The effect of improving the light resistance of the dye is small.

Therefore, a first object of the present invention is to provide a silver halide photographic light-sensitive material which has improved light resistance of a dye image and excellent image storability.

A second object of the present invention is to provide a silver halide photographic light-sensitive material excellent in color reproducibility.

A third object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in production suitability in the production of a light-sensitive material and which has excellent stability over time of a dispersion containing a coupler.

[0011]

The above object of the present invention can be achieved by any one of the following constitutions (1) to (11).

(1) In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the formula [MI] The dye image-forming coupler represented by the above formula and a polyhydric alcohol, and the polyhydric alcohol is contained in the same silver halide emulsion layer.
-I] A silver halide color photographic light-sensitive material containing 2.0 or more by weight ratio to the dye image-forming coupler.

(2) The polyhydric alcohol is contained in the same silver halide emulsion layer in a weight ratio of 2.0 or more with respect to the dye image-forming coupler represented by the general formula [MI].
The silver halide color photographic light-sensitive material as described in the above item (1), which contains 5.0 or less.

(3) The dye image-forming coupler represented by the general formula [MI] is a dye represented by the general formula [M-II] "Chemical Formula 2" or [M-III] "Chemical Formula 2". The silver halide color photographic light-sensitive material as described in the above item (1) or (2), which is an image forming coupler.

(4) The dye image-forming coupler represented by the general formula [M-I] is represented by the general formula [M-VIII] "Chemical Formula 3".
Alternatively, the silver halide color photographic light-sensitive material described in the above item (1) or (2), which is a dye image-forming coupler represented by [M-IX] "Chemical Formula 4".

(5) R in the general formula [M-VIII]
_The silver halide color photographic light-sensitive material as described in (4) above, wherein ₉ is a secondary or tertiary alkyl group.

(6) The polyhydric alcohol is a compound represented by the general formula [I].
A silver halide color photographic light-sensitive material according to any one of items (1) to (5).

(7) The polyhydric alcohol is a compound represented by the general formula [II] "Chemical formula 5" or [III] "Chemical formula 5", and the above-mentioned items (1) to (5) are provided. A silver halide color photographic light-sensitive material as described in the above item.

(8) The silver halide color photograph described in the above items (1) to (5), wherein the polyhydric alcohol is a compound represented by the general formula [IV] "Chemical formula 6". Photosensitive material.

(9) The silver halide color photograph described in the above items (1) to (5), wherein the polyhydric alcohol is a compound represented by the general formula [V] "Chemical formula 7". Photosensitive material.

(10) The silver halide color photograph as described in the above items (1) to (5), wherein the polyhydric alcohol is a compound represented by the general formula [VI] "Chemical formula 8". Photosensitive material.

(11) The polyhydric alcohol represented by the above general formula [I] is represented by the above general formula [VII] "Chemical formula 9" to "IX""Chemical formula 1".
(6) which is a compound represented by "1"
A silver halide color photographic light-sensitive material as described in the above item.

The present invention will be described in more detail below.

First, the coupler represented by the general formula [MI] will be described.

[0025]

[Chemical 12]

In the general formula [MI], the substituent represented by R is not particularly limited, but is typically alkyl or
Aryl, anilino, acylamino, sulfonamide,
Examples thereof include alkylthio, arylthio, alkenyl, and cycloalkyl groups, but in addition to these, halogen atoms 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, heterocyclicthio groups, and spiro A compound residue, a bridged hydrocarbon compound residue, etc. are also mentioned.

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 has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 3 carbon atoms.
12, particularly 5 to 7, are preferable, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R is preferably one having 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 aryloxy group. Phosphonyl group, arylphosphonyl group, etc .; Acyl group, alkylcarbonyl group, arylcarbonyl group, etc .; Carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, etc .; Sulfamoyl group, alkylsulfamoyl group, aryl group, aryl Sulfamoyl group etc .; Acyloxy group as alkylcarbonyloxy group, arylcarbonyloxy group etc .; Carbamoyloxy group as alkylcarbamoyloxy group, arylcarbamoyloxy group Group or the like; ureido group alkylureido group, an arylureido group or the like; sulfamethoxazole The sulfamoylamino group alkylsulfamoyl group, an aryl sulfamoylamino group or the like; 5 is a heterocyclic group
7-membered ones are preferable, and specifically, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazole group and the like;
The heterocyclic group oxy group is preferably one having a 5- to 7-membered heterocyclic group, 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-benzothiazolylthio group, 2, 4-diphenoxyl-1,3,5-triazole-6-thio group, etc .; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group as succinimide group, 3-heptadecylsuccinic group Acid imide group, phthalimide group, glutarimide group, etc .; Spiro [3.3] heptan-1-yl etc. as spiro compound residue;
The bridged hydrocarbon compound residue bicyclo [2.2.1] heptane-1-yl, tricyclo [3.1.1 ^{3.1 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,

[0036]

[Chemical 13]

(R ₁ ′ has the same meaning as R above, Z ′ has the same meaning as Z above, and R ₂ ′ and R ₃ ′ represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group), etc. Each group is mentioned, but a halogen atom, particularly a chlorine atom is preferable.

The nitrogen-containing heterocycle 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 represented by the above R. The ones mentioned are mentioned.

What is represented by the general formula [MI] is more specifically represented by, for example, the following general formulas [M-II] to [M-VII].

[0040]

[Chemical 14]

In the formulas [M-II] to [M-VII], R _{1 to} R ₈ and X have the same meanings as R and X.

Among the couplers represented by the above formulas [M-II] to [M-VII], the couplers represented by the above formulas [M-II] and [M-III] are preferable. More preferably, the following general formulas [M-VIII] and [M-IX]
It is represented by.

[0043]

[Chemical 15]

In the above general formula [M-VIII], R ₉ and R ₁₀ represent an alkyl group. X is the above general formula [MI]
It is synonymous with X in. The alkyl group represented by R ₉ and R ₁₀ preferably has 1 to 32 carbon atoms, may be linear or branched, and may have a substituent. R ₉
And as a substituent for substituting the alkyl group represented by R ₁₀ ,
Examples of the substituent represented by R in the general formula [MI] are given. Further, R ₉ is preferably a secondary or tertiary alkyl group.

[0045]

[Chemical 16]

In the general formula [M-IX], R ₁₁ and X have the same meanings as R and X in the general formula [M-I]. R ₁₂ represents a hydrogen atom or a substituent. R ₁₃ and R ₁₄ represent a substituent. n represents an integer of 0 to 3. Examples of the substituent represented by R ₁₂ , R ₁₃ and R ₁₄ include the substituent represented by R in the above formula [MI], preferably an alkyl group, an alkoxy group, an acylamino group, a sulfonamide group, and a ureido group. , A sulfonyl group, an imide group or a halogen atom.

Specific examples of the coupler represented by the general formula [MI] are shown below.

[0048]

[Chemical 17]

[0049]

[Chemical 18]

[0050]

[Chemical 19]

[0051]

[Chemical 20]

In addition to the above specific examples, the couplers of the present invention include compounds represented by Exemplified Compounds 1 to 64 described on pages 5 to 9 of JP-A-63-253946 and JP-A 2-100048. Compounds represented by Exemplified Compounds M-1 to M-29 described on pages 5 to 6 of JP-A No. 62-215272, pages 106 to 114 of JP-A No. 62-215272.
Exemplary Compounds M-16 to M-34, M-37 to M-3
9, compounds represented by M-41 to M-47, compounds represented by M-1 to M-15 described on pages 12 to 14 of JP-A-2-96133, JP-A-61-292143 1 to 7 on page 6 of the above, and compounds 1 to 11, 15 to 16, 18 to 28, 30 to 41 of exemplary compounds described on pages 19 to 32 of JP-A-3-125143. Compounds, compounds represented by Exemplified Compounds 1 to 24 on pages 3 to 5 of JP-A-4-128744, JP-A-4-42222
Examples thereof include compounds represented by Exemplified Compounds 1 to 22 described on pages 5 to 7 of JP-A-49.

These couplers are usually silver halide 1
It can be used in a range of 1 × 10 ^{−3 to} 2 mol, preferably 1 × 10 ^{−2 to} 7 × 10 ⁻¹ mol per mol.

Next, the polyhydric alcohol used in the present invention will be described. In the present invention, the polyhydric alcohol means a compound having two or more alcoholic hydroxyl groups in the molecule, and is a carbon atom in an aliphatic compound, an alicyclic compound, or a heterocyclic compound having no aromaticity. It is a compound having two or more hydroxyl groups substituted in the molecule.

The polyhydric alcohol of the present invention preferably has a total carbon number of 6 or more.

The polyhydric alcohol of the present invention preferably has a molecular weight of 5000 or less, and is preferably liquid at room temperature.

The polyhydric alcohol of the present invention preferably has a hydroxyl value of 50 or more.

The polyhydric alcohol of the present invention is preferably log
The P value is 3 or more.

The polyhydric alcohol of the present invention is preferably a compound represented by the following general formulas [I] to [VI].

General formula [I] R _A1 —O—R _A2 [wherein R _A1 represents an alkyl group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group, and R _A2 represents an alkyl group, an alkenyl group or a cycloalkyl group. , A cycloalkenyl group,-(O =) C-R _A3 , -SO ₂ -R _A4 ,-(O =) P <(-O-R
_A5 ) (− O−R _A6 ), − (O =) P <(R _A7 ) (R _A8 ), −CON <(R _A9 ).
Represents (R _A10 ) or —SO ₂ N <(R _A11 ) (R _A12 ).

Here, R _{A3 to} R _A9 and R _A11 each represent an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group or an aryl group, and R _A10 and R _A12 represent a hydrogen atom or an alkyl group, an alkenyl group, It represents a cycloalkyl group, a cycloalkenyl group or an aryl group.

However, the alkyl group, alkenyl group, cycloalkyl group, and cycloalkenyl group represented by R _A1 and / or the alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, and / or R _{A3 to} R _A12 represented by R _A2. The alkyl group, the alkenyl group, the cycloalkyl group and the cycloalkenyl group represented by are substituted with at least one position on the carbon atom, and the total number of alcoholic hydroxyl groups in the molecule is 2 or more. Further, R _A1 and R _A2 are not condensed with each other to form a ring. ]

[0063]

[Chemical 21]

[In general formula [II] and general formula [III], R _A21 , R _A22 , R _A23 and R _A24 are each a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, It represents an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, or a sulfamoyl group.

However, at least two of R _A21 , R _A22 , R _A23 and R _A24 are hydrogen atoms, and not all are hydrogen atoms. ]

[0066]

[Chemical formula 22]

[Wherein, R _A41 , R _A42 and R _A43 each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or a carbamoyl group, and L represents an alkylene group or an arylene group. Represent, Y
_A is a hydrogen atom or a carbamoyl group, a sulfamoyl group,
It represents an acyl group, and m represents 0 or 1. ]

[0068]

[Chemical formula 23]

[Wherein R ₅₁ represents a substituted alkyl group or a substituted alkenyl group having two or more hydroxyl groups, R ₅₂ represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, or an aryl group, R _{51 and} R ₅₂ may be condensed with each other to form a lactone ring. ]

[0070]

[Chemical formula 24]

[Wherein R ₆₁ is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group,
It represents an acyl group, a sulfonyl group, a carbamoyl group or a sulfamoyl group, and R ₆₂ and R ₆₃ each represent an alkyl group substituted with a hydroxyl group and / or an alkoxy group. However, R ₆₂ and R ₆₃ each have at least one alcoholic hydroxyl group. ] In the general formulas [I] to [VI], R _{A1 to} R _A12 , R _A21 to
The alkyl group represented by R _A24 , R _{A41 to} R _A43 , R ₅₂ and R ₆₁ may be linear or branched, and preferably has 1 to 32 carbon atoms, for example, methyl group, ethyl group, isopropyl group, t -Butyl group, dodecyl group, heptadecyl group, 2-ethylhexyl group and the like are typical examples thereof.

R _{A1 to} R _A12 , R _{A21 to} R _A24 , R _{A41 to} R
_A43, alkenyl groups represented by R ₅₂ and R ₆₁ may be linear or branched, preferably one having 2 to 32 carbon atoms, such as vinyl group, propenyl group, 11-undecenyl group, a 1-methyl-propenyl group As a representative example thereof.

The substituted alkyl group or substituted alkenyl group having two or more hydroxyl groups represented by R ₅₁ is the above R _A1 ~
Any two or more carbon atoms of the alkyl group and alkenyl group of R _A12 , R _{A21 to} R _A24 , R _{A41 to} R _A43 , R ₅₂ and R ₆₁ (including those further substituted by a substituent) are hydroxyl groups. And a typical example thereof is a 1,2-dihydroxypropyl group, a 1,1-dihydroxymethylethyl group and the like.

The alkyl groups represented by R ₆₂ and R ₆₃ are the above R _{A1 to} R _A2 , R _{A21 to} R _A24 , R _{A41 to} R _A43 , R ₅₂ and R _52.
The carbon atom of the alkyl group of ₆₁ is substituted with a hydroxyl group and / or an alkoxy group, and each may have another substituent. R ₆₂ and R ₆₃ are preferably
− (CH ₂ CH ₂ O) _s H, − (CH ₂ CH ₂ CH ₂ O) _r H, − (CH ₂ CH (OH) CH ₂ O)
represents _t H. Here, s, r, and t each represent an integer of 1 to 5.

R _{A1 to} R _A12 , R _{A21 to} R _A24 , R _{A41 to} R
_A43, the cycloalkyl group represented by R ₅₂ and R _61, preferably has 3 to 12 carbon atoms, in particular 5-7, may have a branched structure, such as cyclohexyl group, cyclopentyl group, Typical examples thereof include a propyl group and a 2-methylcyclopropyl group.

R _{A1 to} R _A12 , R _{A21 to} R _A24 , R _{A41 to} R
_A43, The cycloalkenyl group represented by R ₅₂ and R _61, preferably has 3 to 12 carbon atoms, in particular 5-7, may have a branched structure, for example, 1-cyclohexenyl group, 2 -A typical example thereof is a cyclopentenyl group.

R _{A3 to} R _A12 , R _{A21 to} R _A24 , R _{A41 to} R
The aryl group represented by _A43 and R _52, carbon atoms 6
To 14 are preferred, and typical examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.

The above-mentioned alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group and aryl group may be further substituted with a substituent, and the substituent includes the following.

Alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio,
Each group such as alkenyl, halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl,
Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, Examples include aryloxycarbonyl and heterocyclic thio groups, spiro compound residues, bridged hydrocarbon compound residues, and hydroxyl groups.

As the acyl group represented by R _{A21 to} R _A24 , Y _A and R ₆₁ , — (O═) C—R _A3 (R _A3 is as described above) is preferable.

As the sulfonyl group represented by R _{A21 to} R _A24 and R ₆₁ , —SO ₂ —R _A4 (R _A4 is as described above) is preferable.

The phosphonyl group represented by R _{A21 to} R _A24 includes-(O =) P <(-O-R _A5 ) (-O-R _A6 ) (R _A5 and R _A6
Is as described above).

R _{A21 to} R _A24 , R _{A41 to} R _A43 , Y _A and R
_The carbamoyl group represented by ₆₁ includes -CON <(R _A9 ) (R
_A10 ) (R _A9 and R _A10 are as described above) are preferred.

As the sulfamoyl group represented by R _{A21 to} R _A24 , Y _A and R ₆₁ , —SO ₂ N <(R _A11 ) (R _A12 ) (R
_A11 and R _A12 are preferably as described above). The alkylene group represented by L preferably has 1 to 32 carbon atoms, and may be linear or branched. The arylene group represented by L is preferably a phenylyl group. The alkylene group and arylene group represented by L may further have a substituent,
Examples of the substituent include R _{A1 to} R _A12 and R _A21 to
The thing mentioned as a substituent which substitutes for R _{< A24>} , R _<A41> -R _{<A43 >} , R _{< 51 >} , R _{< 52 > and} R _{< 61} > -R < ₆₃ > is mentioned. In the general formula [I], R _A1 and R _A2 are not condensed with each other to form a ring, but R _A5 and R _A6 , R _A7 and R _A8 , R _A9 and R _A10 and R _A11 and R _A12 And may be condensed with each other to form a ring.

Among the polyhydric alcohols of the present invention, particularly preferred are the compounds represented by the above general formulas [II] and [III] and the following general formulas [VII] to [IX].

[0086]

[Chemical 25]

[Wherein, R ₇₁ , R ₇₂ and R ₇₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group or a sulfamoyl group. , P represents an integer of 1 to 20. When p is 2 or more, a plurality of R ₇₃ may be the same or different. However, p is 1
When any of R ₇₁ , R ₇₂ and R ₇₃ is a hydrogen atom, and when p is 2 or more, at least two of R ₇₁ , R ₇₂ and a plurality of R ₇₃ are hydrogen atoms. And not all are hydrogen atoms. ]

[0088]

[Chemical formula 26]

[In the formula, R _{81 to} R ₈₄ are each a hydrogen atom,
Represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group or a sulfamoyl group, and q is 1
Represents a whole number from 20 to 20, and when q is 2 or more, a plurality of R ₈₃ , R
₈₄ may be the same or different. However, q
When 1 represents 1, at least two of R ₈₁ , R ₈₂ , R _83, and R ₈₄ are hydrogen atoms, and not all are hydrogen atoms, and when q is 2 or more, R ₈₁ , R _At least two of ₈₂ , a plurality of R ₈₃ and a plurality of R ₈₄ are hydrogen atoms, and all are not hydrogen atoms. ]

[0090]

[Chemical 27]

[Wherein R _{91 to} R ₉₆ are each a hydrogen atom,
It represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group or a sulfamoyl group. However, at least two of R _{91 to} R ₉₆ are hydrogen atoms, and not all are hydrogen atoms. ] In the general formulas [VII] to [IX], R _{71 to} R ₇₃ , R ₈₁ to
Examples of the alkyl group, alkenyl group, cycloalkyl group and cycloalkenyl group represented by R ₈₄ and R _{91 to} R ₉₆ include
R _A1 in the above general formulas [I] to [VI]
_{Examples of} the alkyl group, alkenyl group, cycloalkyl group and cycloalkenyl group represented by R _A12 , R _{A21 to} R _A24 , R _{A41 to} R _A43 , R ₅₁ , R ₅₂ and R _{61 to} R ₆₃ are mentioned. To be

The above-mentioned alkyl group, alkenyl group, cycloalkyl group and cycloalkenyl group may be further substituted with a substituent, and the substituent is the above-mentioned R.
_{A1 to} R _A12 , R _{A21 to} R _A24 , R _{A41 to} R _A43 , R ₅₁ , R ₅₂
And those mentioned as the substituents for substituting R _{61 to} R ₆₃ .

As the acyl group represented by R _{71 to} R ₇₃ , R _{81 to} R ₈₄ and R _{91 to} R ₉₆ , — (O═) C—R _A3 (R _A3 is as described above) is preferable.

As the sulfonyl group represented by R _{71 to} R ₇₃ , R _{81 to} R ₈₄ and R _{91 to} R ₉₆ , —SO ₂ —R _A4 (RA ₄ is as described above) is preferable.

The phosphonyl group represented by R _{71 to} R ₇₃ , R _{81 to} R ₈₄ and R _{91 to} R ₉₆ is-(O =) P <(-O-R _A5 ).
(-O- _RA6 ) ( _RA5 and _RA6 are as described above) is preferred.

The carbamoyl group represented by R _{71 to} R ₇₃ , R _{81 to} R ₈₄ and R _{91 to} R ₉₆ includes -CON <(R _A9 ) (R _A10 ).
( _{RA 9} and _{RA 10} are as described above) are preferred.

As the sulfamoyl group represented by R _{71 to} R ₇₃ , R _{81 to} R ₈₄ and R _{91 to} R ₉₆ , --SO ₂ N <(R _A11 ) (R
_A12 ) (R _A11 and R _A12 are as described above) are preferred. Hereinafter, representative specific examples of the polyhydric alcohol of the present invention will be shown.
The present invention is not limited to these.

[0098]

[Chemical 28]

[0099]

[Chemical 29]

[0100]

[Chemical 30]

[0101]

[Chemical 31]

[0102]

[Chemical 32]

[0103]

[Chemical 33]

[0104]

[Chemical 34]

[0105]

[Chemical 35]

[0106]

[Chemical 36]

[0107]

[Chemical 37]

[0108]

[Chemical 38]

[0109]

[Chemical Formula 39]

[0110]

[Chemical 40]

[0111]

[Chemical 41]

[0112]

[Chemical 42]

[0113]

[Chemical 43]

[0114]

[Chemical 44]

[0115]

[Chemical formula 45]

[0116]

[Chemical formula 46]

In the present invention, the magenta coupler represented by the general formula [MI] (hereinafter referred to as magenta coupler [MI]) and the polyhydric alcohol of the present invention are
It is preferably contained in at least one of the green-sensitive silver halide emulsion layers.

In order to contain the magenta coupler [MI] and the polyhydric alcohol in the silver halide emulsion layer,
A conventionally known method, for example, a mixed solution of a high boiling point solvent such as a known dibutyl phthalate, tricresyl phosphate, etc., and a low boiling point solvent such as butyl acetate, ethyl acetate, etc., if necessary, with the magenta coupler and the polyhydric alcohol of the present invention. Alternatively, after dissolving in a solvent having only a low boiling point solvent, it is mixed with a gelatin aqueous solution containing a surfactant, and then emulsion-dispersed using a high-speed rotary mixer, a colloid mill, an ultrasonic disperser, or the like, and then in an emulsion. A method of directly adding 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 and the polyhydric alcohol may be separately dispersed by the above dispersion method and added to the silver halide emulsion, but both compounds are added. At the same time dissolve, disperse,
The method of adding to the emulsion is preferred.

The addition amount of the polyhydric alcohol of the present invention is preferably 2.0 or more in weight ratio with respect to the magenta coupler [MI] according to the present invention in the same silver halide emulsion layer, and is preferable. Is 2.0 or more and 8.0 or less, more preferably
The range is 2.0 or more and 5.0 or less. Further, the polyhydric alcohol of the present invention may be used alone or in combination of two or more kinds.

When two or more polyhydric alcohols of the present invention are used in combination, the total amount of plural polyhydric alcohols of the present invention is 2. 2 by weight ratio with respect to the magenta coupler of the present invention.
It may be 0 or more.

Further, it is preferable that the silver halide emulsion layer containing the coupler of the present invention contains at least one of the dye image stabilizers represented by the general formula [TI] or [T-II]. .

[0123]

[Chemical 47]

[In the formula, R ₂₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or the following residue.

[0125]

[Chemical 48]

Here, R ₂₁ a, R ₂₁ b and R ₂₁ c each represent a monovalent organic group. R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆
Each represents a hydrogen atom, a halogen atom, or a group capable of substituting for a benzene ring. R _{21 to} R ₂₆ may combine with each other to form a 5- or 6-membered ring. ]

[0127]

[Chemical 49]

[In the formula, R ₃₁ represents an aliphatic group or an aromatic group, and Y represents a group of non-metal atoms necessary for forming a 5- to 7-membered ring with a nitrogen atom. In the general formula [TI], the alkyl group, the aryl group and the heterocyclic group represented by R ₂₁ include the general formula [M-
I], an alkyl group represented by R, an aryl group,
The groups described as the heterocyclic group can be mentioned. Also, R
Examples of the monovalent organic group represented by ₂₁ a, R ₂₁ b and R ₂₁ c include an alkyl group, an aryl group, an alkoxy group, an aryloxy group and a halogen atom. R ₂₁ is preferably a hydrogen atom or an alkyl group. Examples of the group capable of substituting the benzene ring represented by R _{22 to} R ₂₆ include those represented by the general formula [MI] above.
In the above, the groups described as the substituent represented by R can be mentioned. R ₂₂ , R ₂₃ , R ₂₅ and R ₂₆ are each a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group,
An aryloxy group and an acylamino group are preferable, and R ₂₄ is preferably an alkyl group, a hydroxy group, an aryl group, an alkoxy group and an aryloxy group. R ₂₁ and R ₂₂ may be ring-closed to each other to form a 5- or 6-membered ring, and R ₂₄ at that time is preferably a hydroxy group, an alkoxy group or an aryloxy group. R ₂₁ and R ₂₂ may be closed to form a methylenedioxy ring. Further, R ₂₃ and R ₂₄ may be ring-closed to form a 5-membered hydrocarbon ring.
₂₁ is preferably an alkyl group, an aryl group, or a heterocyclic group.

Specific examples of the compound represented by formula [TI] are shown below.

[0130]

[Chemical 50]

[0131]

[Chemical 51]

In addition to the above specific examples, the above general formula [T-
Specific examples of the compound represented by the formula [I] are disclosed in JP-A-60-262.
Exemplified Compound A-described on pages 11 to 13 of Japanese Patent No. 159
1-A-28, the exemplified compounds PH-1 to PH-29 described on pages 8 to 10 of JP-A 61-145552, JP-A-1-306846.
Exemplified Compounds B-1 to 1 described on pages 6 to 7 of the publication
B-21, Exemplified compounds I-1 to I-13, I'-1 to I'-8, II-1 described on pages 10 to 18 of JP-A 2-958.
To II-12, II'-1 to II'-21, III-8 to III-14, IV
-1 to IV-24, V-13 to V-17, No. 10 of JP-A 3-39956
Exemplified compounds II-1 to II-33 described on pages 11 to 11 and the like can be mentioned.

Next, in the general formula [T-II], R
₃₁ represents an aliphatic group or an aromatic group, preferably an alkyl group, an aryl group or a heterocyclic group, and most preferably an aryl group. Examples of the heterocycle formed by Y together with the nitrogen atom include a piperidine ring, a piperazine ring, a morpholine ring, a thiomorpholine ring, a thiomorpholine-1,1-dione ring, and a pyrrolidine ring.

Specific examples of the compound represented by formula [T-II] are shown below.

[0135]

[Chemical 52]

In addition to the above specific examples, the above general formula [TI
Specific examples of the compound represented by I] include JP-A 2-16754
Exemplified compound B-1 described on pages 8 to 11 of Japanese Patent Publication No. 3
To B-65, exemplified compounds (1) to (120) described on pages 4 to 7 of JP-A-63-95439, and the like.

The addition amount of the compound represented by the above general formula [T-I] or [T-II] is preferably 5 to 500 mol%, more preferably 20 to 200 mol% based on the coupler of the present invention. Is.

Further, in the silver halide emulsion layer containing the coupler of the present invention and the polyhydric alcohol of the present invention, JP-A-61-158 is used.
The metal chelate compounds described in Nos. 329 and 62-183459 may be used. The silver halide used in the silver halide emulsion layer of the present invention includes any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide and the like. Can be mentioned.

The silver halide grains preferably used in the present invention have a silver chloride content of 95 mol% or more, a silver bromide content of 5 mol% or less, and a silver iodide content of 0.5 mol%.
The following is preferable. More preferably, it is a silver chlorobromide having a silver bromide content of 0.1 to 2 mol%. The silver halide grains may be used alone or in combination with other silver halide grains having different compositions. Further, it may be used as a mixture with silver halide grains having a silver chloride content of 95 mol% or less. Further, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 95 mol% or more, the silver chloride content in the total silver halide grains contained in the emulsion layer is 95 mol%. The proportion of the above silver halide grains is 60% by weight or more, preferably 80% by weight or more. The composition of the silver halide grain may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. When the composition inside and outside the particle is different, the composition may continuously change or may be discontinuous.

The grain size of the silver halide grain is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.2.
It is in the μm range.

The grain size distribution of the silver halide grains may be polydisperse or monodisperse. Monodisperse silver halide grains having a variation coefficient of 0.22 or less, more preferably 0.15 or less in the grain size distribution of silver halide grains are preferred. 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 = standard deviation of grain size distribution / average grain size The silver halide grains used in the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method.
The particles may be grown at one time, or may be grown after forming seed particles. The method for making seed particles and the method for growing seed particles may be the same or different. Further, as a form of reacting the soluble silver salt and the soluble halogenated salt, a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc.,
Any of these may be used, but those obtained by the simultaneous mixing method are preferable. Further, as one form of the simultaneous mixing method, the pAg controlled double jet method described in JP-A-54-48521 can be used.

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

The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. Also, U.S. Pat.Nos. 4,183,756 and 4,225,666,
55-26589, Japanese Patent Publication No. 55-42737, etc., The Journal
Of Photographic Science (J.Photgr.Sc
It is also possible to prepare particles having a shape of octahedron, tetrahedron, dodecahedron, etc. by the method described in the literatures such as i.), 21 , 39 (1973) and use them. Further, grains having twin planes may be used.

The silver halide grains used in the present invention are
The particles may have a single shape, or particles having various shapes may be mixed.

In the present invention, in the process of forming and / or growing silver halide grains, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt) ), An iron salt (including a complex salt) is used to add a metal ion to the inside of the particle and / or the surface of the particle so that the metal ion can be incorporated. Alternatively, reduction sensitizing nuclei can be provided on the grain surface.

In the emulsion containing silver halide grains, unnecessary soluble salts may be removed after the growth of silver halide grains has been completed, or they may be contained therein.

In the present invention, the silver halide grain used in the emulsion may be a grain in which a latent image is mainly formed on the surface, or may be a grain mainly formed inside the grain. Grains in which the latent image is mainly formed on the surface are preferable.

In the present invention, the emulsion is chemically sensitized by a conventional method. That is, a sulfur-containing compound capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds. Sensing methods and the like can be used alone or in combination.

Further, the emulsion can be optically sensitized to a desired wavelength region by using a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye and a hemioxanol dye can be used. Specific examples thereof include the exemplified compound BS-described in JP-A-3-274548, pages 20 to 21.
1-BS-9, GS-1 to GS-5, RS-1 to RS-
8 and IRS-1 to IRS-10. Examples of the supersensitizer that can be used in combination with these include Exemplified Compounds SS-1 to SS-9 described in JP-A-3-274548, page 22.

The dye-forming coupler used in the light-sensitive material of the present invention is usually selected so that a dye which absorbs the light in the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer, and it is blue-sensitive. Yellow dye-forming coupler in the emulsion layer, magenta dye-forming coupler in the green-sensitive emulsion layer,
A cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, the color light-sensitive material may be produced by a method different from the above combination depending on the purpose.

In the present invention, an acylacetanilide type coupler can be preferably used as the yellow dye forming coupler.

Of these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous.

Specific examples of the yellow couplers preferably used in the present invention will be given below.

[0155]

[Chemical 53]

[0156]

[Chemical 54]

[0157]

[Chemical 55]

[0158]

[Chemical 56]

Further, in addition to the above compounds, JP-A-63-856
No. 31, pp. 7-16, exemplary compounds Y-1 to Y-146, 6
3-97951, Exemplified compounds Y-1 to Y-9 described on pages 6 to 10
8. Exemplified compound Y-described in JP-A 1-156748, pages 18 to 20
1-Y-24, 2-298943, Exemplified compounds I-1 to I-50 described on pages 4 to 7 and Exemplified compounds Y-1 to Y-described on JP-A No. 62-215272, pages 114 to 120. You can name 48.

In the present invention, as the magenta dye forming coupler, known couplers such as 5-pyrazolone type, pyrazoloazole type and pyrazolobenzimidazole type couplers can be used.

In the present invention, naphthol type and phenol type couplers can be preferably used as the cyan dye forming coupler.

Particularly when the present invention is used as a light-sensitive material for direct appreciation such as color paper, in view of fastness of dye image and color reproducibility, for example, US Pat. No. 2,895,826,
JP-A-50-112038, 53-109630, 55-163537,
2,5-diacylaminophenol cyan couplers disclosed in JP-A-63-96656 and U.S. Pat.
Phenol cyan couplers having an alkyl group having 2 or more carbon atoms at the 5-position described in 4,443,536 are advantageously used.

In addition to naphthol-based and phenol-based cyan couplers, JP-A 1-156748, 3-174153,
Imidazole-based cyan couplers disclosed in 3-196039 and the like, and JP-A-2-136854 and pyrazoloazole-based cyan couplers disclosed in JP-A-3-96039 and the like, pyrazoloazine-based cyan couplers, and further JP-A 3-103848, same
The hydroxypyridine cyan couplers and hydroxydiazine cyan couplers disclosed in 3-103849, and the aminopyridine cyan couplers disclosed in JP-A-3-206450 are color reproducibility, image storability, and color restoration. It has excellent properties and is advantageously used.

Specific examples of the cyan coupler used in the present invention are shown below.

[0165]

[Chemical 57]

[0166]

[Chemical 58]

[0167]

[Chemical 59]

In addition to the above-mentioned compounds, as phenolic cyan couplers, the exemplified compounds C-1 to C-31 described in JP-A-63-96656, pages 4 to 6 and JP-A 1-196048, pages 10 to 13 are described. Exemplified compounds III-1 to III-31, IV-1 to IV-2
0, exemplary compound C-described in JP-A-3-109549, pages 9 to 11
1 to C-22, and the exemplified compounds C-1 to C-42 described on pages 99 to 103 of JP-A No. 62-215272. Examples of cyan couplers other than phenols are JP-A-2-136854. Exemplified Compounds A-1 to A-13 and B-1 to
B-16, C-1 to C-8, D-1 to D-8, JP-A-3-10
Exemplified compounds (1) to (69) described on pages 7 to 13 of 3848, and Exemplified compounds C-1 to C-103 and D-1 described on pages 10 to 16 and 18 to 20 of JP-A No. 3-196039. -D-31 etc. can be mentioned.

Hydrophobic compounds such as dye-forming couplers are usually dissolved in a high-boiling organic solvent having a boiling point of about 150 ° C. or higher or a water-insoluble polymer compound in combination with a low-boiling and / or water-soluble organic solvent, if necessary. Then, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, emulsifying and dispersing by using a dispersing means such as a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic device, and the like hydrophilic colloid. It may be added in the layer.

Examples of the high boiling point organic solvent used in the present invention include esters such as phthalic acid ester and phosphoric acid ester, organic acid amides, ketones, hydrocarbon compounds, etc., in addition to the polyhydric alcohol of the present invention. . Specific examples thereof include the exemplified compounds A-1 to A-120 described on pages 4 to 7 of JP-A 1-196048, and the exemplified compounds II-1 to II-29 and 14 described on pages 8 to 9 Exemplified compound H- described on page 15
1 to H-22, Exemplified Compounds S-1 to S-69 described on pages 3 to 7 of JP-A 1-209446, and Exemplified Compounds I-1 to I described on pages 10 to 12 of JP-A-63-253943. -95 etc. can be mentioned.

Water-insoluble and organic solvent-soluble polymers used for dispersing couplers and the like include (1) vinyl polymers and copolymers, (2) polycondensates of polyhydric alcohols and polysalt acid, ( 3) Polyester obtained by the ring-opening polymerization method, (4) In addition, polycarbonate resin, polyurethane resin, polyamide resin and the like can be mentioned.

The number average molecular weight of these polymers is not particularly limited, but is preferably 200,000 or less, more preferably 5,
It is 000-100,000.

Specific examples of polymers preferably used are shown below. However, the copolymer shows the weight ratio of the monomers.

(PO-1) poly (Nt-butylacrylamide) (PO-2) Nt-butylacrylamide-methylmethacrylate copolymer (60:40) (PO-3) polybutylmethacrylate (PO-4) methylmethacrylate -Styrene copolymer (90:10) (PO-5) Nt-butylacrylamido-2-methoxyethyl acrylate copolymer (55:45) (PO-6) ω-methoxy polyethylene glycol acrylate (addition mole number n = 9) -Nt-butylacrylamide copolymer (25:75) Further, in addition to the above compounds, exemplified compounds P-1 to P-200 described in JP-A 64-537, pp. 10 to 15 may be mentioned. it can.

The light-sensitive material of the present invention contains a color antifoggant,
Image stabilizer, hardener, plasticizer, anti-irradiation dye, polymer latex, ultraviolet absorber, formalin scavenger, development accelerator, development retarder, optical brightener, matting agent, lubricant, antistatic agent, interface An activator or the like can be optionally used. These compounds are described in, for example, JP-A Nos. 62-215272 and 63-46436. Further, the light-sensitive material of the present invention can form an image by performing color development processing known in the art.

[0176]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side on which the emulsion layer was coated, a molten polyethylene containing 13% by weight of surface-treated anatase type titanium oxide dispersed was laminated to prepare a reflective support.

Each layer having the constitution shown in Table 1 and Table 2 was coated on this reflective support to prepare a multilayer color light-sensitive material sample 101. The coating liquid was prepared as follows.

First Layer Coating Liquid Yellow coupler (YC-13) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34 g, (ST-
5) Ethyl acetate (60 cc) was added to 3.34 g, stain inhibitor (HQ-7) 0.33 g, compound A 5.0 g and high boiling point organic solvent (DBP) 5.0 g to dissolve, and this solution was added with 20% surfactant (S
U-1) 220 cc of 10% gelatin aqueous solution containing 7 cc was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a coating solution for the first layer.

The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer so that the coating amounts were as shown in Tables 1 and 2.

Further, as a hardener (H-1), (H-2)
Was added. As a coating aid, a surfactant (SU-
2) and (SU-3) were added to adjust the surface tension. Further, F-1 was added to each layer so that the total amount was 0.04 g / m ² .

[0182]

[Table 1]

[0183]

[Table 2]

SU-1: di (2-ethylhexyl) sulfosuccinate sodium salt SU-2: sodium tri-i-propylnaphthalene sulfonate SU-3: di (2,2,3,3,4) sulfosuccinate , 4,5,5-Octafluoropentyl) / sodium salt DBP: Dibutylphthalate DOP: Dioctylphthalate DIDP: Di-i-decylphthalate PVP: Polyvinylpyrrolidone H-1: Tetrakis (vinylsulfonylmethyl) methane H-2: 2 , 4-Dichloro-6-hydroxy-s-triazine ・
Sodium Compound A: pt-octylphenol

[0185]

[Chemical 60]

[0186]

[Chemical formula 61]

[0187]

[Chemical formula 62]

[0188]

[Chemical formula 63]

[0189]

[Chemical 64]

(Preparation of blue-sensitive silver halide emulsion) The following (A) was added to 1 liter of a 2% gelatin aqueous solution kept at 40 ° C.
30) while controlling the liquids) and (B liquid) to pAg = 7.3 and pH = 3.0
Simultaneously added over the course of minutes,
Simultaneous addition was carried out over 180 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water added 200 cc (Solution B) Silver nitrate 10 g Water added 200 cc (Solution C) K ₂ IrCl ₆ 2 × 10 ^-8 mol / mol Ag Chloride Sodium 102.7 g K ₄ Fe (CN) ₆ 1 × 10 ^-5 mol / mol Ag potassium bromide 1.0 g Water added 600 cc (D liquid) Silver nitrate 300 g Water added 600 cc After addition of Kao Atlas Demol N 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate were used for desalting, and then mixed with an aqueous solution of gelatin to obtain a single particle having an average particle size of 0.85 μm, a particle size distribution variation coefficient of 0.07, and a silver chloride content of 99.5 mol%. A dispersed cubic emulsion EMP-1 was obtained.

The following compounds were used for EMP-1.
Optimal chemical sensitization was performed at 60 ° C. to obtain a blue-sensitive silver halide emulsion for comparison (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ^-4 mol / mol AgX (preparation of green-sensitive silver halide emulsion) (solution A) and solution B
A monodisperse cubic emulsion E having an average grain size of 0.43 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (C liquid) are changed.
MP-2 was obtained.

The following compounds were used for EMP-2.
Optimal chemical sensitization was carried out at 55 ° C. to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (red Preparation of Sensitive Silver Halide Emulsion) (Solution A) and (Solution B)
A monodisperse cubic emulsion EMP with an average grain size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% in the same manner as EMP-1, except that the addition time of (C liquid) and the addition time of (C liquid) and (D liquid) are changed.
-3 was obtained.

The following compounds were used for the above EMP-3.
Optimal chemical sensitization was carried out at 60 ° C. to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitization Dye RS-2 1 × 10 ⁻⁴ mol / mol AgX The sample thus obtained is referred to as Sample 101 (for comparison).

STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole

[0199]

[Chemical 65]

Next, the high boiling point organic solvent D of the third layer of Sample 101 was used.
Samples 102 to 160 were prepared by replacing OP with the comparative high boiling point organic solvents shown in Tables 3, 4 and 5 below and the polyhydric alcohol of the present invention.

The thus-prepared sample was wedge-exposed with green light according to a conventional method, and then processed according to the following processing steps.

Processing process Temperature Time Color development 35.0 ± 0.3 ℃ 45 seconds Bleach-fixing 35.0 ± 0.5 ℃ 45 seconds Stabilization 30-34 ℃ 90 seconds Dry 60-80 ℃ 60 seconds Composition of each processing solution is as follows. Show.

The replenishing amount of each processing solution is 80 ml per 1 m ^{2 of the} silver halide color photographic light-sensitive material.

Color developer tank solution Replenisher Pure water 800ml 800ml Triethanolamine 10g 18g N, N-diethylhydroxylamine 5g 9g Potassium chloride 2.4g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0g 1.8g N-ethyl -N-β-Methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4g 8.2g Optical brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.0g 1.8g Potassium carbonate 27g 27g Water In addition, the total volume is 1000 ml, and the pH of the tank liquid is
Is adjusted to 10.10 and the pH of the replenisher is adjusted to 10.60.

Bleach-fixing solution (tank solution and replenisher are the same) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water was added. Bring the total volume to 1000 ml and adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution (same as tank solution and replenisher) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediamine Tetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Add water to bring the total volume to 1000 ml and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide. Adjust to.

The following evaluations were performed using the obtained samples.

<Light resistance> The obtained sample was stored in the sunlight for 2 months, and the residual ratio (%) of the dye image at the initial density of 1.0 was determined.

<Color development> The maximum color density (Dmax) was determined by sensitometry.

<Stability of Magenta Coupler Dispersion Liquid> Further, the magenta coupler dispersion liquid added to the coating liquid of the third layer of each sample was stored at 40 ° C. for 12 hours with aging, and the magenta coupler dispersion liquid was stored by aging. The increase width (Δχ) of turbidity was calculated. The smaller this value is, the more excellent the stability of the dispersion liquid of the magenta coupler is, and the better the suitability for producing the light-sensitive material.

The above results are shown in Tables 3, 4 and 5.

[0212]

[Table 3]

[0213]

[Table 4]

[0214]

[Table 5]

Comparative HBS1; tricresyl phosphate

[0216]

[Chemical formula 66]

Comparative HBS2; CH ₃ (CH ₂ ) ₇ CH = (CH ₂ ) ₈ OH (high-boiling organic solvent described in JP-A-4-265975). It can be seen that all the samples of the present invention containing alcohol in a weight ratio of 2.0 or more with respect to the magenta coupler of the present invention are excellent in light resistance and stability of the magenta coupler dispersion. In addition, the sample of the present invention is excellent in color development and sufficiently high.
Dmax is obtained.

Among the samples of the present invention, the polyhydric alcohol of the present invention has a weight ratio of 2.0 to the magenta coupler of the present invention.
It can be seen that the sample containing 5.0 or less is particularly excellent in light resistance and stability of the magenta coupler dispersion.

Example 2 Magenta coupler M-7 of the third layer of Sample 101 of Example 1
To the magenta couplers shown in Tables 6 and 7 in equimolar numbers
Sample 20 in which the layer high boiling organic solvent DOP was replaced with the comparative high boiling organic solvent shown in Tables 6 and 7 and the polyhydric alcohol of the present invention
1-244 were prepared. The same evaluation as in Example 1 was performed using the obtained sample.

The results are shown in Tables 6 and 7.

[0221]

[Table 6]

[0222]

[Table 7]

As is clear from Tables 6 and 7, the magenta couplers of the present invention all showed significant improvement in light resistance.

[0224]

According to the present invention, firstly, it is possible to provide a silver halide photographic light-sensitive material having improved light resistance of a dye image and excellent image storability.

Secondly, a silver halide photographic light-sensitive material excellent in color reproducibility can be provided.

Thirdly, in the production of a light-sensitive material, it is possible to provide a silver halide photographic light-sensitive material which is excellent in stability over time of a dispersion containing a coupler and is excellent in production suitability.

Claims (11)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers is represented by the following general formula [MI]. The dye image-forming coupler and the polyhydric alcohol are contained in the same silver halide emulsion layer. A silver halide color photographic light-sensitive material containing the above. [Chemical 1] [In the formula, Z represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent. R represents a hydrogen atom or a substituent. ] 2. The polyhydric alcohol is contained in a weight ratio of 2.0 to 5.0 with respect to the dye image-forming coupler represented by the general formula [MI] contained in the same silver halide emulsion layer. A silver halide color photographic light-sensitive material according to claim 1, wherein 3. The dye image-forming coupler represented by the general formula [MI] is represented by the following general formula [M-II] or [M-II].
The silver halide color photographic light-sensitive material according to claim 1 or 2, which is a dye image-forming coupler represented by I]. [Chemical 2] Wherein, R ₁ to R ₃ and X are respectively the same as R and X in the general formula (M-I). ] 4. A dye image-forming coupler represented by the general formula [MI] is represented by the following general formula [M-VIII] or [MI].
The silver halide color photographic light-sensitive material according to claim 1 or 2, which is a dye image-forming coupler represented by X]. [Chemical 3] [In the formula, X has the same meaning as X in the formula [MI]. R ₉ and R ₁₀ represent an alkyl group. ] [Chemical 4] [In the formula, R ₁₁ and X are each represented by the general formula [M-
It is synonymous with R and X in I]. R ₁₂ represents a hydrogen atom or a substituent. R ₁₃ and R ₁₄ represent a substituent. n represents an integer of 0 to 3. R ₁₂ , R ₁₃ and R ₁₄
The substituent represented by is the same as the substituent represented by R in the general formula [MI]. ] 5. The silver halide color photographic light-sensitive material according to claim 4, wherein R ₉ in the general formula [M-VIII] is a secondary or tertiary alkyl group. 6. The polyhydric alcohol is represented by the following general formula [I]:
It is a compound represented by these 1-5.
The described silver halide color photographic light-sensitive material. General formula [I] R _<A1 > -O-R _<A2> [In formula, R _<A1> represents an alkyl group, an alkenyl group, a cycloalkyl group, or a cycloalkenyl group, R _<A2> is an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group. Group,-(O =)-R _A3 , -SO ₂ -R _A4 ,-(O =) P <(-O-R
_A5 ) (− O−R _A6 ), − (O =) P <(R _A7 ) (R _A8 ), −CON <(R _A9 ).
Represents (R _A10 ) or —SO ₂ N <(R _A11 ) (R _A12 ). Where R _A3
To R _A9 and R _A11 each represent an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group or an aryl group, and R _A10 and R _A12 represent a hydrogen atom or an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, Represents an aryl group. However, an alkyl group represented by R _A1 , an alkenyl group, a cycloalkyl group, a cycloalkenyl group and / or an alkyl group represented by R _A2 , an alkenyl group,
Cycloalkyl group, cycloalkenyl group and / or R _A3
At least one position on the carbon atom of the alkyl group, alkenyl group, cycloalkyl group, or cycloalkenyl group represented by R _A12 is substituted with a hydroxyl group, and the total sum of alcoholic hydroxyl groups in the molecule is 2 or more. And then R _A1 and R
It does not _fuse with _A2 to form a ring. ] 7. The polyhydric alcohol has the following general formula [II]:
Or a compound represented by [III], wherein the silver halide color photographic light-sensitive material according to claims 1 to 5. [Chemical 5] [Wherein R _A21 , R _A22 , R _A23 and R _A24 are each a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group,
It represents a cycloalkenyl group, an aryl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, and a sulfamoyl group. However, at least two of R _A21 , R _A22 , R _A23 and R _A24 are hydrogen atoms, and not all are hydrogen atoms. ] 8. The polyhydric alcohol has the following general formula [IV]:
It is a compound represented by these 1-5.
The described silver halide color photographic light-sensitive material. [Chemical 6] [Wherein R _A41 , R _A42 and R _A43 are each a hydrogen atom,
Represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or a carbamoyl group, L
Represents an alkylene group or an arylene group, Y _A represents a hydrogen atom, a carbamoyl group, a sulfamoyl group or an acyl group, and m represents 0 or 1. ] 9. The polyhydric alcohol is represented by the following general formula [V]:
It is a compound represented by these 1-5.
The described silver halide color photographic light-sensitive material. [Chemical 7] [In the formula, R ₅₁ represents a substituted alkyl group or a substituted alkenyl group containing two or more hydroxyl groups, R ₅₂ represents an alkyl group,
It represents an alkenyl group, a cycloalkyl group, a cycloalkenyl group, or an aryl group, which may be condensed with R _{51 to} R ₅₂ to form a lactone ring. ] 10. The polyhydric alcohol is represented by the following general formula [V
A compound represented by the formula [I].
~ 5 silver halide color photographic light-sensitive material. [Chemical 8] [In the formula, R ₆₁ represents a hydrogen atom, an alkyl group, an alkenyl group,
It represents a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a carbamoyl group or a sulfamoyl group, and R ₆₂ and R ₆₃ each represent an alkyl group substituted with a hydroxyl group and / or an alkoxy group. However, R ₆₂ and R ₆₃
Each have at least one alcoholic hydroxyl group. ] 11. The silver halide color according to claim 6, wherein the polyhydric alcohol represented by the general formula [I] is a compound represented by the following general formulas [VII] to [IX]. Photographic material. [Chemical 9] [Wherein R ₇₁ , R ₇₂ and R ₇₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group or a sulfamoyl group, and p is 1 to 20
Represents the integer. When p is 2 or more, a plurality of R ₇₃ may be the same or different. However, when p represents 1, R ₇₁ ,
When any two of R ₇₂ and R ₇₃ are hydrogen atoms and p is 2 or more, at least two of R ₇₁ , R ₇₂ and a plurality of R ₇₃ are hydrogen atoms, and all are hydrogen atoms. Never be. ] [Chemical 10] [In the formula, R _{81 to} R ₈₄ are each a hydrogen atom, an alkyl group,
An alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, a sulfamoyl group, q represents an integer of 1 to 20, and when q is 2 or more, a plurality of R ₈₃ , R ₈₄ may be the same or different. However, when q represents 1, at least two of R ₈₁ , R ₈₂ , R _83, and R ₈₄ are not hydrogen atoms, and all are not hydrogen atoms.
When q is 2 or more, at least two of R ₈₁ , R ₈₂ , a plurality of R ₈₃ and a plurality of R ₈₄ are hydrogen atoms, and all are not hydrogen atoms. ] [Chemical 11] [In the formula, R _{91 to} R ₉₆ are each a hydrogen atom, an alkyl group,
It represents an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, or a sulfamoyl group. However, at least two of R _{91 to} R ₉₆ are hydrogen atoms, and not all are hydrogen atoms. ]