JPH0950100A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance color development performance and color reproduction performance by incorporating a specified cyan coupler in a red-sensitive silver halide emulsion layer and a specified yellow coupler in a blue-sensitive silver halide emulsion layer. SOLUTION: This photosensitive material comprises photographic constituent layers including a blue-, green-, and red-sensitive silver halide emulsion layers on a support, and the red-sensitive silver halide emulsion layer contains at least one kind of cyan coupler selected from formulae I and II and the blue- sensitive silver halide emulsion layer contains at least one kind of yellow coupler selected from formula III. In formulae I-III, each of R1 and R3 is a branched alkyl or substituted alkyl or such aryl group or a heterocyclic group: each of R2 and R4 is a substituent: each of X1 -X3 is an H atom or a group to be released by reaction with the oxidation product of a color developing agent; R<11> is a nonmetallic atomic group necessary to form a 5-membered unsaturated hetero ring; R<12> is an H atom or an alkyl group or the like; R<13> is an alkyl or alkenyl group or the like; and Y is an N or O atom.

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 which is excellent in color developability and color reproducibility of the light-sensitive material and is also excellent in rapid processability.

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material (hereinafter, also simply referred to as a "light-sensitive material") for direct viewing, for example, a color photographic paper, a yellow coupler is usually used as a color forming agent for forming a dye image. , Magenta couplers and cyan couplers. These couplers are required to have basic properties such as color reproducibility, color developability and storage durability of the dye image to be obtained. In recent years, in particular, in order to faithfully reproduce the original color of the object, color reproduction There is a growing demand from users to improve the quality.

[0003] As a cyan image forming coupler, a phenol or naphthol coupler has been widely used. However, cyan images obtained from these phenol or naphthol couplers have a serious problem in color reproduction. That is, the absorption on the short-wave side of the absorption is poor, and the green region also has unnecessary absorption, that is, irregular absorption. For this reason, in the negative film, irregular absorption due to masking or the like must be corrected, and in the case of paper, there is no correction means, and the color reproducibility is considerably deteriorated at present.

For the purpose of improving color reproducibility, Japanese Patent Application Laid-Open
250649, 63-250650, 64-5
No. 54 and the like propose a pyrazoloazole type cyan coupler. However, these couplers have an electron-withdrawing group and a hydrogen-bonding group introduced in order to satisfy the absorption wavelength of the coloring dye to be formed. It was not a satisfactory level.

Further, in recent years, in light-sensitive materials for color photography and printing, the printing process and the developing process have been shortened and speeded up, and it is more and more strongly required that rapid processing is possible. It was

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material which is excellent in color development and color reproducibility of the light-sensitive material and is also excellent in rapid processability.

[0007]

The above object of the present invention is achieved by the following constitution.

(1) On a support, there is provided a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer. Contains at least one cyan coupler represented by the general formula (I) or (II) [Chemical formula 1], and the blue-sensitive silver halide emulsion layer is represented by the general formula (1) [Chemical formula 2]. A silver halide color photographic light-sensitive material containing at least one yellow coupler represented.

(2) On the support, there is provided a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer. Containing at least one cyan coupler represented by the general formula (I) or (II), and the yellow represented by the general formula (2) [Chemical Formula 4] in the blue-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material containing at least one coupler.

(3) A photographic constitutional layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer is provided on a support, and the red-sensitive silver halide emulsion layer. Containing at least one cyan coupler represented by the general formula (I) or (II), and the yellow represented by the general formula (3) [Chemical Formula 5] in the blue-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material containing at least one coupler.

(4) On the support, there is provided a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer. Yellow containing at least one cyan coupler represented by the general formula (I) or (II) and having a blue-sensitive silver halide emulsion layer represented by the general formula (4) A silver halide color photographic light-sensitive material containing at least one coupler.

Hereinafter, the present invention will be described in detail.

First, the cyan couplers represented by the general formulas (I) and (II) of the present invention will be described in detail.

[0014]

[Chemical 7]

In the formula, R ₁ and R ₃ each represent a branched alkyl group, a substituted alkyl group, a substituted aryl group or a heterocyclic group, and R ₂ and R ₄ each represent a substituent. X ₁ and X ₂ each represent a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent.

In the above general formulas (I) and (II), the branched alkyl group represented by R ₁ and R ₃ is i-propyl, t-butyl, sec-butyl, i-butyl, t.
Each group such as -octyl can be mentioned.

As the alkyl component of the substituted alkyl group,
It may be linear, branched or cyclic, and may be methyl, ethyl,
Butyl, i-propyl, t-butyl, sec-butyl,
Each group such as i-butyl, t-octyl and cyclohexyl can be mentioned.

As the aryl component of the substituted aryl group,
A phenyl group can be mentioned.

Examples of the heterocyclic group include 2-furyl, 2-thienyl, 2-imidazolyl, 2-thiazolyl, 3-isoxazolyl, 3-pyridyl, 2-pyridyl, 2-pyrimidyl, 3-pyrazolyl, 2-benzothiazolyl and the like. Each group can be mentioned. These heterocyclic groups may have a substituent.

The substituent of the substituted alkyl group, the substituted aryl group and the heterocyclic group is not particularly limited, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl. Examples of each group include halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, sulfonyloxy. , Carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio Thioureido, carboxyl, hydroxyl, mercapto, nitro, each group such as sulfo, and a spiro compound residue, bridged hydrocarbon compound residue and the like are also mentioned.

In the general formulas (I) and (II), the substituent represented by R ₂ and R ₄ is not particularly limited, but is typically alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, Examples of the groups include alkenyl and cycloalkyl groups. In addition to these, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl,
Carbamoyl, sulfamoyl, cyano, alkoxy,
Aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino,
Alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, sulfo, etc., and spiro Compound residues and bridged hydrocarbon compound residues are also included.

In the above-mentioned substituents for the branched alkyl group represented by R ₁ and R ₃ , the substituted alkyl group, the substituted aryl group or the heterocyclic group, and the substituents represented by R ₂ and R ₄ ,
The alkyl group preferably has 1 to 32 carbon atoms,
It may be linear or branched.

The aryl group is preferably a phenyl group.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and the aryl component in the alkylthio group and the arylthio group include the alkyl group and the aryl group in the substituent represented by R ₂ and R ₄ .

The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched. The cycloalkenyl group has 3 to 1 carbon atoms.
2, especially 5 to 7, are preferable.

The sulfonyl group is an alkylsulfonyl group, an arylsulfonyl group or the like; the sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group or the like;
The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; The acyl group is an alkylcarbonyl group, an arylcarbonyl group, etc .; The carbamoyl group is an alkylcarbamoyl group, an arylcarbamoyl group. Etc .; as sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, etc .; as acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc .; as sulfonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, etc. A carbamoyloxy group as an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; a ureido group as an alkylureido group, an arylureido group, etc .; sulfamoylamino As alkylsulfamoyl group, an aryl sulfamoylamino group such as, is preferably a 5- to 7-membered as heterocyclic group, specifically 2-
Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 1-pyrrolyl, 1-tetrazolyl group, etc .; The heterocyclic oxy group is preferably one having a 5- to 7-membered heterocycle, for example, 3,4,5,5. 6-Tetrahydropyranyl-2-oxy, 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, 2-benzothiazoli Ruthio, 2,4-diphenoxy-1,3,5-triazole-6-thio group, etc .; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group as succinimide, 3
-Heptadecyl succinimide group, phthalimide group, glutarimide group, etc .; spiro compound residue as spiro [3.3] heptane-1-yl etc .; bridged hydrocarbon compound residue as bicyclo [2.2.1] heptane-1-yl, tricyclo [3.3.1.1 ^3.7] decan-1-yl, 7,7-dimethyl - bicyclo [2.2.1] heptane-1-yl, and the like.

The substituent represented by R ₂ and R ₄ is preferably an alkyl group or an aryl group, and particularly preferably an aryl group.

The above group may further have a substituent such as a long chain hydrocarbon group or a diffusion resistant group such as a polymer residue.

Examples of the group represented by X ₁ and X ₂ which can be split off by the reaction with the oxidation product of the color developing agent are, for example, a halogen atom (chlorine, bromine, fluorine, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, Sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocycle thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded by N atom,
Examples include groups such as alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl.

X ₁ and X ₂ are preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a nitrogen-containing heterocyclic group bonded by an N atom, and the like.

Of the cyan couplers represented by the general formulas (I) and (II), those represented by the general formula (I) are preferable.

Specific compounds of the cyan couplers represented by the general formulas (I) and (II) (referred to as the cyan coupler of the present invention) are shown below, but the present invention is not limited thereto.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

[Chemical 12]

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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The cyan coupler of the present invention is usually 1 × 10 ⁻³ to 1 mol, preferably 1 ×, per mol of silver halide.
It can be used in the range of 10 ⁻² to 8 × 10 ⁻¹ mol.

The cyan coupler of the present invention can be used in combination with other types of cyan couplers.

Next, the yellow couplers represented by the general formulas (1) to (4) will be sequentially described.

[0051]

[Chemical 21]

In the formula, R ¹¹ is

[0053]

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And represents a group of non-metal atoms necessary for forming a 5-membered unsaturated heterocycle. R ¹² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aromatic group or a heterocyclic group, and R ¹³ represents an alkyl group, an alkenyl group, an alkynyl group, an aromatic group, an alkoxy group, an aryloxy group, a heterocyclic group. It represents a group or -NR ¹⁴ R ¹⁵ groups. R ¹⁴ and R ¹⁵
Each represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aromatic group or a heterocyclic group, and X ₃ represents a group capable of splitting off upon reaction with an oxidized product of a color developing agent. Y represents a nitrogen atom or an oxygen atom, and in the case of an oxygen atom, R ¹² does not exist.

In the general formula (1),

[0056]

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In the heterocycle represented by, two nitrogen atoms (when Y is a nitrogen atom), two other ring-forming atoms other than one carbon atom are a carbon atom, a nitrogen atom, a sulfur atom and selenium, respectively. Atoms or tellurium atoms, but preferred are carbon and nitrogen atoms. This heterocycle may be substituted and may have another condensed ring. These fused rings may be further substituted.

As the above-mentioned heterocycle, those represented by the following general formulas (A) and (B) are particularly preferable.

[0059]

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In the general formulas (A) and (B), R ¹² has the same meaning as R ¹² in the general formula (1).
In, Y ′ and Z ′ each represent a carbon atom or a nitrogen atom. The heterocycles represented by the general formulas (A) and (B) may have a substituent.

In the general formula (1), R ¹² , R ¹³ , and R ¹⁴
And the alkyl group represented by R ¹⁵ has 1 to 30 carbon atoms.
And particularly preferably 1 to 20 and may be linear or branched, chained or cyclic, for example, methyl, ethyl, propyl, i-propyl, i-amyl, 2-ethylhexyl, dodecyl, cyclohexyl and the like. However, these may be further substituted.

The alkenyl group represented by R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ has 2 to 30 carbon atoms, particularly 2 to 20 carbon atoms.
Is preferable, and may be linear or cyclic, and examples thereof include vinyl, allyl, 1-methylvinyl, 1-cyclopentenyl, 1-cyclohexenyl, and the like, which may be further substituted.

The alkynyl group represented by R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ has 2 to 30 carbon atoms, particularly 2 to 20 carbon atoms.
Are preferred, for example ethynyl, 1-propynyl, 3,3
-Dimethyl-1-butynyl and the like, which may be further substituted.

The aromatic group represented by R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and anthracenyl. These may be further substituted.

The heterocyclic group represented by R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is preferably a 5- to 7-membered ring, the hetero atom is preferably nitrogen, oxygen or sulfur atom and has 1 to 10 carbon atoms.
10 is preferable, for example, 2-furyl, 2-thienyl, 2
-Pyridyl, 2-pyrimidyl, 2-imidazolyl, 2-
(1,3-oxazolyl) and the like, which may be further substituted.

The alkoxy group represented by R ¹³ is represented by --OR ¹⁶ , in which R ¹⁶ represents an alkyl group, an alkenyl group or an alkynyl group, which are synonymous with the above-mentioned alkyl group, alkenyl group and alkynyl group. , For example, methoxy, ethoxy, propyloxy, i-propyloxy,
Examples thereof include i-amyloxy, 2-ethylhexyloxy, lauryloxy, allyloxy, cyclohexyloxy, vinyloxy and ethynyloxy, which may be further substituted.

The aryloxy group represented by R ¹³ is --OR.
Represented by ¹⁶ ', wherein R ¹⁶ ' has the same meaning as the above aromatic group, and examples thereof include phenoxy, 1-naphthoxy, 2-naphthoxy, 1-anthryloxy, 9-anthryloxy, and the like. These may be further substituted.

The heterocyclic oxy group represented by R ¹³ is --O.
"Represented by, wherein R ¹⁶ 'R ¹⁶ has the same meaning as the heterocyclic group described above, for example 2-furyl-oxy, 2-thienyloxy, 2-pyridyloxy, 2-pyrimidyloxy, 2
Examples thereof include imidazolyloxy and 2- (1,3-oxazolyl) oxy, which may be further substituted.

In the general formula (1), R ¹¹ , R ¹² , R ¹³ ,
R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁶ ′, R ¹⁶ ″ and the general formula (A),
Examples of the substituent capable of substituting the heterocycle represented by (B) include
For example, an alkyl group (synonymous with an alkyl group represented by R ^{12 to} R ¹⁵ ), an alkenyl group (synonymous with an alkenyl group represented by R ^{12 to} R ¹⁵ ), an alkynyl group (alkynyl represented by R ^{12 to} R ¹⁵ ) Group), an aromatic group (synonymous with the aromatic group represented by R ^{12 to} R ¹⁵ ), a heterocyclic group (synonymous with the heterocyclic group represented by R ^{12 to} R ¹⁵ ), a halogen atom (fluorine, Chlorine, bromine atom), a cyano group, a nitro group or the following groups.

--NR ¹⁷ R ¹⁸ , --OR ¹⁷ , --OCOR ¹⁷ ,
^{-OCONR 17 R 18, -OSiR 17 R} 18 R 19, -OSO
_{^{2 R 17, -N (R 17}} ) COR 18, -N (R 17) CONR
¹⁸ R ¹⁹ , -N (COR ¹⁷ ) (COR ¹⁸ ), -N (R ¹⁷ )
_{^{SO 2 NR 18 R 19, -N}} (R 17) COOR 18, -N (R
_{^{17) SO 2 R 18, -CONR}} 17 R 18, -COR 17, -C
OOR ¹⁷ , -SO ₂ NR ¹⁷ R ¹⁸ , -SO ₂ R ¹⁷ , -SOR
¹⁷ , -SR ¹⁷ , -SiR ¹⁷ R ¹⁸ R ¹⁹ , -SO ₂ NHCO
R ¹⁷ , -SO ₂ NHCOOR ¹⁷ , -CONHCOR ¹⁷ ,
_{^{-CONHSO 2 R 17, -CONHSO 2 NR}} 17 R 18, -
PO (OR ¹⁷ ) ₂ where R ^{17 to} R ¹⁹ are each a hydrogen atom or an alkyl group (R ¹²
Alkyl group as defined represented by to R ^15), alkenyl groups as defined represented by alkenyl groups (R ¹² ~R ^15), an alkynyl group as defined represented by alkynyl groups (R ¹² ~R ^15),
An aromatic group (synonymous with the aromatic group represented by R ^{12 to} R ¹⁵ ) or a heterocyclic group (synonymous with the heterocyclic group represented by R ^{12 to} R ¹⁵ ) is represented.

In the general formula (1), preferable R ¹³ is —NR ¹⁴ R ¹⁵ , and particularly preferable is —NH.
R ¹⁴ .

When R ¹³ is represented by —NHR ¹⁴ , R ¹⁴ is preferably an aromatic group, and particularly preferably a phenyl group.

In the general formula (1), it is a group capable of splitting off upon reaction with X ₃ hydrogen atom or an oxidized product of a color developing agent. When the coupler is used as a photographically useful group-releasing coupler such as a DIR coupler, It should use one that combines the properties of a photographically useful group or its precursor as X _3.

As the above X ₃ , a known group capable of leaving can be used. Further, a known photographically useful group or its precursor can be used, and specific examples thereof include those described in JP-A-4-184433.

Specific examples of the coupler represented by formula (1) are shown below, but the invention is not limited thereto.

[0076]

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[0077]

[Chemical formula 26]

[0078]

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[0079]

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[0080]

[Chemical 29]

The yellow coupler represented by formula (1) can be synthesized by the method described in JP-A-4-184433, pages 27-32.

The coupler represented by formula (2) will be described.

[0083]

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In the formula, R ²¹ represents a monovalent substituent except a hydrogen atom, and Q is selected from a 3- to 6-membered hydrocarbon ring together with a carbon atom or at least one N, S, O or P. It represents a group of non-metal atoms necessary for forming a 3- to 6-membered heterocycle containing a hetero atom in the ring. R ²² is a hydrogen atom, a halogen atom,
Represents an alkoxy group, an aryloxy group, an alkyl group or an amino group, R ²³ represents a group capable of substituting for a benzene ring,
m represents an integer of 0 to 4. When m is 2 or more, plural R ²³
May be the same or different. X ₄ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent.

Examples of R ²³ include halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, Alkylsulfonyl group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, alkoxysulfonyl group, acyloxy group, nitro group, heterocyclic group, cyano group, acyl group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group , and examples of X _4, heterocyclic group bonded to a coupling active site via a nitrogen atom, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclic oxy group, a halo Is down atom and the like.

When the substituent in the general formula (2) is an alkyl group or contains an alkyl group, the alkyl group is linear, branched or cyclic and may be substituted unless otherwise specified. An alkyl group which may contain a saturated bond (methyl,
i-propyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl, 2-ethylhexyl, 1,1,
3,3-tetramethylbutyl, dodecyl, hexadecyl, allyl, 3-cyclohexenyl, oleyl, benzyl, trifluoromethyl, hydroxymethylmethoxyethyl, ethoxycarbonylmethyl, phenoxyethyl and the like).

When the substituent in the general formula (2) is an aryl group or contains an aryl group, unless otherwise specified, the aryl group may be an optionally substituted monocyclic or condensed ring aryl group (phenyl group). , 1-naphthyl, p-tolyl, o
-Tolyl, p-chlorophenyl, 4-methoxyphenyl, 8-quinolyl, 4-hexadecyloxyphenyl,
Pentafluorophenyl, p-hydroxyphenyl, p
-Cyanophenyl, 3-pentadecylphenyl, 2,4
-Di-t-pentylphenyl, p-methanesulfonamidophenyl, 3,4-dichlorophenyl).

When the substituent in the general formula (2) is a heterocyclic group or contains a heterocyclic group, the heterocyclic group is selected from O, N, S, P, Se and Te unless otherwise specified. A 3- to 8-membered optionally substituted monocyclic or condensed-ring heterocyclic group containing at least one hetero atom in the ring (2-furyl, 2-
Pyridyl, 4-pyridyl, 1-pyrazolyl, 1-imidazolyl, 1-benzotriazolyl, 2-benzotriazolyl, succinimide, phthalimide, 1-benzyl-
2,4-imidazolidindione-3-yl) and the like.

The substituents preferably used in formula (2) will be described below.

R ²¹ is preferably a halogen atom, a cyano group, or a monovalent group having 1 to 30 total carbon atoms (hereinafter abbreviated as C number) which may be substituted (for example, an alkyl group or an alkoxy group) or a C number. A monovalent group of 6 to 30 (for example, an aryl group, an aryloxy group), and the substituent thereof is, for example, a halogen atom, an alkyl group, an alkoxy group,
There are nitro group, amino group, carbonamido group, sulfonamide group, acyl group and the like.

Q is preferably a hydrocarbon ring having 3 to 30 carbon atoms, which may be substituted with any of 3 to 6 members together with C, or at least 1 hetero atom selected from N, S, O and P. Represents a group of non-metal atoms necessary for forming a heterocycle having a C number of 2 to 30, which includes in the ring. The ring formed by Q together with C may contain an unsaturated bond in the ring.

Examples of the ring formed by Q together with C include cyclopropane, cyclobutane, cyclopentane, cyclopropene, cyclobutene, cyclopentene, oxetane,
Examples thereof include rings such as oxolane, 1,3-dioxolane, thietane, thiolane and pyrrolidine. Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an acyl group, an alkoxy group, an aryloxy group,
Cyano group, alkoxycarbonyl group, alkylthio group,
An arylthio group etc. are mentioned.

In the general formula (2), R ²² is preferably a halogen atom, either of which may be substituted, and C number of 1 to 30.
Alkoxy group, aryloxy group having 6 to 30 C, C
It represents an alkyl group having 1 to 30 or an amino group having 0 to 30 carbon atoms, and examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.

R ²³ is preferably a halogen atom, any of which may be substituted, an alkyl group having a C number of 1 to 30, and a C number of 6 to
30 aryl group, C number 1 to 30 alkoxy group, C number 2 to 30 alkoxycarbonyl group, C number 7 to 30 aryloxycarbonyl group, C number 1 to 30 carbonamido group, C number 1 to 30 Sulfonamide group, C number 1-3
0 carbamoyl group, C number 0 to 30 sulfamoyl group, C number 1 to 30 alkylsulfonyl group, C number 6 to 3
0 aryl sulfonyl group, C number 1-30 ureido group, C number 0-30 sulfamoylamino group, C number 2
30 alkoxycarbonylamino group, C 1-30 heterocyclic group, C 1-30 acyl group, C 1-30 alkylsulfonyloxy group, C 6-30 arylsulfonyloxy group, Examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group and an arylsulfonyl group. , Acyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonylamino group, sulfamoylamino group, ureido group, cyano group, nitro group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, An alkylsulfonyloxy group,
Aryl sulfonyloxy group etc. are mentioned.

M is preferably an integer of 1 or 2 and R
The substitution position of ²³ is

[0096]

[Chemical 31]

On the other hand, the meta position or the para position is preferred.

X ₄ preferably represents a heterocyclic group or an aryloxy group bonded to the coupling active position by a nitrogen atom.

When X ₄ represents a heterocyclic group, X ₄ is preferably a 5- to 7-membered monocyclic or condensed-ring heterocyclic group which may be substituted, and examples thereof include succinimide and maleinimide. , Phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, l, 2,4-triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-dione,
Thiazolidine-2,4-dione, imidazolidine-2-
On, oxazolidin-2-one, thiazolidine-2-
On, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2,6 -Dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6
-Pyridazone-2-pyrazone, 2-amino-1,3,4
-Thiazolidine, 2-imino-1,3,4-thiazolidin-4-one and the like, and these heterocycles may be substituted. As the substituent, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a sulfo group,
Alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, amino group, carbonamido group, sulfone Examples thereof include an amide group, a carbamoyl group, a sulfamoyl group, a ureido group, an alkoxycarbonylamino group and a sulfamoylamino group.

When X ₄ represents an aryloxy group, X ₄ preferably represents an aryloxy group having a C number of 6 to 30, and X ₄
When is a heterocycle, it may be substituted with a group selected from the substituent group mentioned above. Examples of the substituent of the aryloxy group include a halogen atom, a cyano group, a nitro group, a carboxyl group, a trifluoromethyl group, an alkoxycarbonyl group,
A carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or a cyano group is preferable.

Substituents particularly preferably used in formula (2) will be described below. R ²¹ is particularly preferably a halogen atom or an alkyl group, and most preferably a methyl group.

Q, which is a non-metal atom group forming a 3- to 6-membered hydrocarbon ring with C, is, for example, (a), (b),
It is (c).

[0103]

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Here, R represents a hydrogen atom, a halogen atom or an alkyl group. However, a plurality of R may be the same or different.

Most preferably, Q is (a) which forms a 3-membered ring with C to which it is bonded.

R ²² is particularly preferably a chlorine atom, a fluorine atom, an alkyl group having a C number of 1 to 6, (methyl, trifluoromethyl, ethyl, i-propyl, t-butyl etc.),
It is an alkoxy group having a C number of 1 to 8 (methoxy, ethoxy, methoxyethoxy, butoxy, etc.) and an aryloxy group having a C number of 6 to 24 (phenoxy group, p-tolyloxy, p-methoxyphenoxy, etc.), and most preferably chlorine. atom,
A methoxy group or a trifluoromethyl group.

R ²³ is particularly preferably a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, and most preferably an alkoxy group or an alkoxycarbonyl group. ,
It is a carbonamide group or a sulfonamide group.

X ₄ is particularly preferably the following formula (X-
1), a group represented by (X-2) or (X-3).

[0109]

[Chemical 33]

In the formula (X-1), Z is the following (d) to
The structure of (j) is shown.

[0111]

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Here, R ₄ , R ₅ , R ₈ and R ₉ are each a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or amino. represents a group, each R ₆ and R ₇ are hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group, each R ₁₀ and R ₁₁ represents a hydrogen atom, an alkyl group or an aryl Represents a group. R ₁₀
And R _ll may combine with each other to form a Benzen ring,
R ₄ and R ₅ , R ₅ and R ₆ , R ₆ and R ₇ or R ₄ and R ₈ are bonded to each other to form a ring (a ring such as cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine or piperidine). May be.

Among the heterocyclic groups represented by the formula (X-1), a particularly preferable one is a heterocyclic group in which Z is (d), (f) or (g). C of the heterocyclic group represented by the formula (X-1)
The number is 2 to 30, preferably 4 to 20, and more preferably 5.
~ 16.

[0114]

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In formula (X-2), at least one of R ₁₂ and R ₁₃ is a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group, a carbonamide group, a sulfonamide group, It is a group selected from a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and the other is a hydrogen atom, an alkyl group or an alkoxy group. R ₁₄ represents the same group as R ₁₂ or R _13, and n
Represents an integer of 0 to 2.

The C number of the aryloxy group represented by the formula (X-2) is 6 to 30, preferably 6 to 24, and more preferably 6 to 15.

[0117]

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In formula (X-3), W represents a non-metal atom group necessary for forming a pyrrole, pyrazole, imidazole or triazole ring with N. The ring represented by (X-3) may have a substituent, and preferred examples of the substituent include a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, an alkyl group, an aryl group, an amino group,
Mention may be made of alkoxy groups, aryloxy groups or carbamoyl groups.

The C number of the heterocyclic group represented by the formula (X-3) is 2 to 30, preferably 2 to 24, more preferably 2-1.
It is 6.

Most preferably, X ₄ is a group represented by the formula (X-1).

The coupler represented by the general formula (2) has a substituent R ²¹ , Q, X ₄ or

[0122]

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In the above, a dimer or a multimer having a valence of 2 or more may be bonded to each other.
In this case, the number of carbon atoms may be out of the specified range for each substituent.

Preferable specific examples of each substituent in the general formula (2) include JP-A-4-184433, 36 to 39.
It is shown on the page.

Next, the coupler represented by the general formula (3) will be described.

[0126]

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In the formula, R ³¹ and R ³² each represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group,
³³ represents an alkyl group, a cycloalkyl group or an aryl group. R ³⁴ , R ³⁵ and m ′ are R ²² and R in the general formula (2).
It is synonymous with ²³ and m, respectively. X ₅ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent.

Typical examples of the couplers represented by formulas (2) and (3) are shown below.

[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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The coupler represented by the general formula (2) is prepared by the method described in Kahei 4-184433, pages 47 to 48, and the coupler represented by the general formula (3) is disclosed in JP-A-63-1.
23047 and US Pat. No. 5,118,599.

Next, the coupler represented by the general formula (4) will be described.

[0137]

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In the formula, R ⁴¹ is a nitrogen atom, an oxygen atom or a carbon atom and is a group bonding to> C═O, R ⁴² is a carbamoyl group or a sulfonyl group, and Ar is an aromatic group or a heterocyclic group. Represent

Representative examples of the compound represented by formula (4) are shown below.

[0140]

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[0141]

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[0142]

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[0143]

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General formulas (1), (2), (3) and (4)
The yellow coupler represented by can be used in combination of two or more kinds, or can be used in combination with other known yellow couplers.

General formulas (1), (2), (3) and (4)
The coupler represented by the formula (1) is 1.
It can be used in the range of 0 to 1.0 × 10 ⁻³ mol, preferably 5.0 × 10 ^{−1 to} 5.0 × 10 ⁻² mol,
More preferably, it is in the range of 4.0 × 10 ^{−1 to} 2.0 × 10 ⁻¹ mol.

In order to incorporate the cyan coupler and yellow coupler of the present invention into a light-sensitive material, known techniques used in ordinary couplers can be applied. That is, it is preferable that the coupler is dissolved in a high boiling point solvent, if necessary in combination with a low boiling point solvent, dispersed in the form of fine particles and added to the silver halide emulsion. At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber, an anti-fading agent, etc. may be used in combination.

When the color light-sensitive material of the present invention is used as a full-color light-sensitive material, a magenta coupler is used in addition to the cyan coupler and the yellow coupler according to the present invention. The magenta coupler is not particularly limited, and known ones such as a 5-pyrazolone type coupler, a pyrazolobenzimidazole type coupler, a pyrazolotriazole type coupler, and a closed acylacetonitrile type coupler can be used.

The silver halide grains contained in the silver halide emulsion layer include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and the like in the art. It may be any silver halide grain used and is not particularly limited.

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. Also, when the composition inside and outside the particle is different, the composition may change continuously,
It may be discontinuous.

The grain size of the silver halide grains 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 2.5 μm. It is in the range of 1.2 μm. The particle diameter can be measured by various methods generally used in the technical field. As a typical method, Lapland's “particle size analysis method” (ASTM.
Symposium on Right Microscopy, 19
55, pp. 94-122) or "The Theory of Photographic Process"
(Co-written by Mies and James, 3rd edition, published by Macmillan, Inc. (1966), Chapter 2).

The particle diameter can be measured by using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately represented as diameter or projected area.

The grain size distribution of silver halide grains may be polydisperse or monodisperse. Preferably, they are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, in the particle size distribution of the silver halide grains. The coefficient of variation is calculated as follows.

Coefficient of variation = standard deviation of grain size distribution / average grain size The silver halide grains 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 seed particles have been produced. The method for producing seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halogen salt may be any one of a forward mixing method, a back mixing method, a simultaneous mixing method and a combination thereof, but a method obtained by the simultaneous mixing method is 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.

If necessary, a silver halide solvent such as thioether 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 may have any shape. One preferable example is a cube having a {100} plane as a crystal surface.

Further, particles having a shape such as octahedron, 14-sided body or 12-sided body can also be used. Further, particles having a twin plane may be used.

As the silver halide grains, grains having a single shape may be used, or grains having various shapes may be mixed.

The silver halide grains have a grain-forming process and / or
Alternatively, during the growth process, metal ions are added using a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt, an iron salt or a complex salt, and are contained inside the particles and / or on the surface of the particles. The reduction sensitization nucleus can be provided inside the grains and / or on the grain surface by placing the grains in an appropriate reducing atmosphere.

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. The removal of the salts can be carried out according to the method described in Research Disclosure (RD) 17643.

The silver halide grain used in the present invention is preferably a grain in which a latent image is mainly formed on the surface,
The particles may have a latent image formed inside the particles.

In the present invention, a chalcogen sensitizer can be used. Chalcogen sensitizer is sulfur sensitizer,
It is a general term for selenium sensitizers and tellurium sensitizers, but sulfur sensitizers and selenium sensitizers are preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like. Others, US Pat. Nos. 1,574,944 and 2,410,689
No. 2,278,947 and No. 2,728,668
Nos. 3,501,313, 3,656,955
The sulfur sensitizers described in, for example, Japanese Laid-Open Patent Application (OLS) 1,422,869, JP-A-56-24937 and JP-A-55-45016 can also be used. The addition amount of the sulfur sensitizer varies over a considerable range depending on various conditions such as pH, temperature and size of silver halide grains, but as a guide, it is 10 ^-7 per mol of silver halide.
It is preferably about 10 ^-1 mol.

The emulsion of the present invention can be used in combination with a reduction sensitization method using a reducing substance and a noble metal sensitization method using a noble metal compound.

The light-sensitive material may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation.

The photographic material can contain various photographic additives in addition to the above. For example, antifoggants, development accelerators, development retarders, bleaching accelerators, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants Agents, plasticizers, wetting agents and the like can be used (for these, see RD 17643).

Further, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, an antifoggant, a chemical sensitizer by coupling with a competitive coupler and an oxidized product of a developing agent. Compounds that release photographically useful fragments such as sensitizers, spectral sensitizers and desensitizers can be used.

The support of the light-sensitive material of the present invention is, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper,
There are glass plates, polyester films such as cellulose acetate, cellulose nitrate and polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films and the like, and in the case of a transparent support, a reflective layer may be used together. These supports are appropriately selected according to the purpose of use of the light-sensitive material.

The emulsion layer and other constituent layers are coated by dipping coating, air doctor coating, curtain coating,
Various coating methods such as hopper coating can be used.
Also, US Pat. Nos. 2,781,791 and 2,941,8
A simultaneous coating method of two or more layers according to the method described in No. 98 can also be used.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined, but a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion are sequentially provided from the support side. The arrangement of layers is preferable.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose, and further various layers such as a filter layer, an anti-curl layer, a protective layer and an antihalation layer are constituted. The layers can be appropriately combined and used.

A hydrophilic colloid can be used as a binder in these constituent layers, and gelatin is preferably used. Further, the various photographic additives mentioned in the above description of the emulsion layer can be contained in the layer.

The processing method of the light-sensitive material of the present invention is not particularly limited, and any generally known processing method can be applied. For example, as a typical example thereof, a method of performing bleach-fixing treatment after color development, and further performing washing and / or stabilizing treatment if necessary, a method of performing bleaching and fixing separately after color development, and further performing as necessary. The method for carrying out washing and / or stabilizing treatment may be carried out by any method, but the color light-sensitive material of the present invention is rapidly treated in the steps of color development, bleach-fixing and washing (or stabilization). It is suitable for

[0173]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 On a support having polyethylene laminated on one side of a paper support and polyethylene containing titanium oxide on the other side, a polyethylene layer containing titanium oxide was added to each layer having the following constitution. Was coated on the side of to prepare a multilayer color light-sensitive material sample 1. The coating liquid was prepared as follows.

First Layer Coating Liquid Yellow coupler (YY-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, (ST-2) 6.67
g, additive (HQ-1) 0.67 g, irradiation prevention dye (AI-3) 0.33 g, high boiling organic solvent (D
NP) 6.67 g was dissolved by adding 60 cc of ethyl acetate.
This solution was emulsified and dispersed in 220 cc of a 10% aqueous gelatin solution containing 7 cc of 20% surfactant (SU-1) using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardening agent, the second and fourth layers (H
-1) and (H-2) were added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The amount of addition in the light-sensitive material indicates the number of grams per 1 m ² unless otherwise specified.

[0178]

[Table 1]

[0179]

[Table 2]

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: Di (2-2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) -sodium salt DBP: dibutyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone HQ-1: 2,5-di-t-octyl hydroquinone HQ-2: 2 , 5-Di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-Dimethyl-4-hexyloxycarbonyl) butylhydroquinone H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium

[0181]

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[0182]

[Chemical 51]

[0183]

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[0184]

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(Method for preparing blue-sensitive silver halide emulsion) 4
In 1000 cc of a 2% aqueous gelatin solution kept at 0 ° C,
The following (solution A) and (solution B) were subjected to pAg = 6.5, pH =
At the same time over 30 minutes while controlling to 3.0,
Solution) and (Solution D) were added simultaneously over 180 minutes while controlling pAg = 7.3 and pH = 5.5. The pH is controlled using an aqueous solution of sulfuric acid or sodium hydroxide, and pAg
For the control, a control liquid having the following composition was used. The composition of the control liquid is a mixed halide salt aqueous solution composed of sodium chloride and potassium sulfide, the ratio of chloride ion to bromide ion is 99.8: 0.2, and the concentration of the control liquid is solution A,
When mixing liquid B, 0.1 mol / liter, liquid C,
The amount was 1 mol / liter when the liquid D was mixed.

(Liquid A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to make 200 cc.

(Liquid B) Silver nitrate 10 g Water was added to make 200 cc.

(Liquid C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to finish to 600 cc.

(Solution D) 300 g of silver nitrate Water was added to finish to 600 cc.

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
After desalting using a 5% aqueous solution and a 2.0% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to have an average particle diameter of 0.85 μm, a coefficient of variation of 0.07, and a silver chloride content of 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (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 Sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (preparation method of green-sensitive silver halide emulsion) (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) in the same manner as in EMP-1 except that the average particle diameter was 0.4.
A monodispersed cubic emulsion EMP-2 having a size of 3 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-2:
Chemical ripening was carried out at 5 ° C. for 120 minutes 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 (Preparation method of red-sensitive silver halide emulsion) (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) were changed in the same manner as in EMP-1 except that the average particle diameter was 0.5.
A monodispersed cubic emulsion EMP-3 having a thickness of 0 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-3:
Chemical ripening was performed at 0 ° C. for 90 minutes 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 STAB-1: 1- (3-acetamido) phenyl-5-mercaptotetrazole

[0197]

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The yellow coupler (YY) of the first layer of Sample 1
Samples 2 to 20 were prepared in the same manner except that the cyan couplers (Comparison a) of the first layer and the fifth layer (comparative a) were changed to the combinations shown in Table 3 in equimolar amounts.

The characteristics of the sample thus obtained were evaluated by the following methods.

<< Relative Sensitivity >> Each sample was subjected to gradation exposure for sensitometry in 0.5 seconds and then subjected to the following development processing. An optical densitometer (Konica Corporation:
The density was measured using a PDA-65 type) to determine the sensitivity of the red-sensitive layer and the maximum density (Dmax) of the blue-sensitive layer.

<< Rapid processing property >> After each sample was exposed to light in the same manner as above, the color development time during the same processing step was set to 3
The same processing was performed except that the time was set to 0 second, and the maximum density (Dmax ') of the blue sensitive layer was obtained and used as an index of rapid processing property. The smaller the difference from the Dmax, the better the rapid processability.

<< Color Reproducibility >> First, a color negative film (Konica Color LV-400: manufactured by Konica) and a camera (Konica FT-1: manufactured by Konica) were used to photograph a color checker manufactured by Macbeth. Subsequently, color negative development processing (CNK-4: manufactured by Konica) was performed, and the obtained negative image was printed on each sample with a size of 82 mm × 117 mm using a Konica color printer (CL-P2000: manufactured by Konica). (Printer conditions are set for each sample so that the gray on the color checker becomes gray on the print). The color reproducibility of the obtained practical print was visually evaluated on a 5-point scale.

The processing conditions are as follows.

(Processing conditions) Processing process Temperature Time Color development 35.0 ± 0.3 ° C. 45 seconds Bleach fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Drying 60-80 C. 60 seconds Color developing solution Pure water 800 cc Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediamine Tetraacetic acid 1.0 g Catechol-3,5-disulfonic acid disodium salt 1.0 g Diethylene glycol 10 g N-Ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate (CD-3) 4 0.5g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.0g Potassium carbonate Um 27 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.10.

Bleach-fixing solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 cc Ammonium sulfite (40% aqueous solution) 27.5 cc Adjust the pH to 5.7 with potassium or glacial acetic acid.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1 -Diphosphonic acid 2.0 g o-Phenylphenol sodium 1.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

The results are shown in Table 3.

[0208]

[Table 3]

As is clear from Table 3, Samples 1 and 2 using the cyan couplers other than the present invention and the yellow couplers other than the present invention have sufficient sensitivity, maximum density, rapid processability and color reproducibility. Is hard to say. In addition, Samples 3 and 4 using the cyan coupler outside the present invention and the yellow coupler according to the present invention
Shows a slight improvement in rapid processability and color reproducibility, but is still insufficient, and it cannot be said that other performance is sufficient.

On the other hand, Sample 5 using the cyan coupler of the present invention and the yellow coupler other than the present invention shows some effects on the sensitivity, the maximum density and the color reproducibility, but it is still insufficient, and it is rapid. It is hard to say that the processability is sufficient.

On the other hand, Samples 6 to 20 of the present invention are all high in sensitivity and maximum density and have good rapid processability.
The color reproducibility is also very good.

Example 2 A sample was prepared in the same manner as in Example 1 except that the yellow coupler of the first layer was changed as shown in Table 4, and the same evaluation as in Example 1 was carried out. .

The results are also shown in Table 4.

[0214]

[Table 4]

As is clear from Table 4, Samples 1 and 2 using the cyan couplers other than the present invention and the yellow couplers other than the present invention have sufficient sensitivity, maximum density, rapid processability and color reproducibility. Is hard to say. Samples 23 and 24 using the cyan coupler other than the present invention and the yellow coupler of the present invention show some improvement in rapid processability and color reproducibility, but they are still insufficient and other performances are sufficient. It is hard to say.

On the other hand, Sample 5 using the cyan coupler of the present invention and the yellow coupler other than the present invention shows some effects on the sensitivity, the maximum density and the color reproducibility, but it is still insufficient, and it is rapid. It is hard to say that the processability is sufficient.

On the other hand, the samples 26 to 40 of the present invention are
All of them have high sensitivity, high maximum density, good rapid processability, and very good color reproducibility.

Example 3 A sample was prepared in the same manner as in Example 1 except that the yellow coupler in the first layer was changed as shown in Table 5, and the same evaluation as in Example 1 was carried out. .

The results are also shown in Table 5.

[0220]

[Table 5]

As is clear from Table 5, Samples 1 and 2 using the cyan coupler outside the present invention and the yellow coupler outside the present invention are not sufficient in terms of sensitivity, maximum density, rapid processability and color reproducibility. Hard to say. Samples 43 and 44 using the cyan coupler of the present invention and the yellow coupler of the present invention show some improvement in rapid processability and color reproducibility, but they are still insufficient and other performances are sufficient. It is hard to say.

On the other hand, Sample 5 using the cyan coupler of the present invention and the yellow coupler other than the present invention shows some effects on the sensitivity, the maximum density and the color reproducibility, but it is still insufficient, and it is rapid. It is hard to say that the processability is sufficient.

On the other hand, the samples 46 to 60 of the present invention are
All of them have high sensitivity, high maximum density, good rapid processability, and very good color reproducibility.

Example 4 A sample was prepared in the same manner as in Example 1 except that the yellow coupler in the first layer was changed as shown in Table 6, and the same evaluation as in Example 1 was performed. It was

The results are also shown in Table 6.

[0226]

[Table 6]

As is clear from Table 6, Samples 1 and 2 using the cyan couplers outside the present invention and the yellow couplers outside the present invention have sufficient sensitivity, maximum density, rapid processability and color reproducibility. Is hard to say. Samples 63 and 64 using the cyan coupler of the present invention and the yellow coupler of the present invention show some improvement in rapid processability and color reproducibility, but are still insufficient, and other performances are sufficient. It is hard to say.

On the other hand, Sample 5 using the cyan coupler of the present invention and the yellow coupler other than the present invention shows some effects on the sensitivity, the maximum density and the color reproducibility, but it is still insufficient, and it is rapid. It cannot be said that the processability is sufficient.

On the other hand, the samples 66 to 80 of the present invention are
All of them have high sensitivity, high maximum density, good rapid processability, and very good color reproducibility.

[0230]

According to the present invention, it is possible to provide a color light-sensitive material which is excellent in color developing property, color reproducibility and rapid processing property.

Claims (4)

[Claims] 1. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the cyan represented by the following general formula (I) or general formula (II) is contained in the red-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material comprising at least one coupler and at least one yellow coupler represented by the following general formula (1) in a blue-sensitive silver halide emulsion layer. Embedded image [In the formula, R ₁ and R ₃ each represent a branched alkyl group, a substituted alkyl group, a substituted aryl group or a heterocyclic group, and R ₂ and R ₄ each represent a substituent. X ₁ and X ₂ each represent a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ] [Chemical 2] [In the formula, R ¹¹ is Represents a non-metal atom group necessary for forming a 5-membered unsaturated heterocycle. R ¹² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aromatic group or a heterocyclic group, and R 12
¹³ represents an alkyl group, an alkenyl group, an alkynyl group, an aromatic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group or a —NR ¹⁴ R ¹⁵ group. R ¹⁴ and R ¹⁵ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aromatic group or a heterocyclic group, and X ₃ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent. Represents Y represents a nitrogen atom or an oxygen atom, and in the case of an oxygen atom, R ¹² does not exist. ] 2. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer contains the cyan represented by the general formula (I) or the general formula (II). A silver halide color photographic light-sensitive material comprising at least one coupler and at least one yellow coupler represented by the following general formula (2) in a blue-sensitive silver halide emulsion layer. Embedded image [In the formula, R ²¹ represents a monovalent substituent except a hydrogen atom, and Q ²¹
Is a non-requisite for forming a 3- to 6-membered hydrocarbon ring together with a carbon atom or a 3- to 6-membered heterocyclic ring containing at least one hetero atom selected from N, S, O and P in the ring. Represents a group of metal atoms. R ²² represents a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkyl group or an amino group, R ²³ represents a group capable of substituting on the benzene ring, and m represents 0 to 0.
Represents an integer of 4. When m is 2 or more, plural R ²³ may be the same or different. X ₄ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ] 3. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer contains the cyan represented by the general formula (I) or the general formula (II). A silver halide color photographic light-sensitive material comprising at least one coupler and at least one yellow coupler represented by the following general formula (3) in the blue-sensitive silver halide emulsion layer. Embedded image [In the formula, R ³¹ and R ³² are each a hydrogen atom, an alkyl group,
It represents a cycloalkyl group or an aryl group, and R ³³ represents an alkyl group, a cycloalkyl group or an aryl group. R ³⁴ ,
R ³⁵ and m ′ are R ²² , R ²³ and m in the general formula (2).
And are synonymous with each other. X ₅ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ] 4. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer contains the cyan represented by the general formula (I) or the general formula (II). A silver halide color photographic light-sensitive material comprising at least one coupler and at least one yellow coupler represented by the following general formula (4) in the blue-sensitive silver halide emulsion layer. [Chemical 6] [Wherein R ⁴¹ is a nitrogen atom, an oxygen atom or a carbon atom> C
Represents a group bonded to ═O, R ⁴² represents a carbamoyl group or a sulfonyl group, and Ar represents an aromatic group or a heterocyclic group. ]