JPH07152128A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material superior in color reproduction performance and sharpness by incorporating a specified photographic cyan coupler in a silver halide emulsion layer. CONSTITUTION:This photosensitive material contains a white pigment in at least one hydrophilic colloidal layer formed between a support the silver halide emulsion layer and at least one of photgraphic cyan couplers represented by formulae I and II and the like in at least one of the silver halide emulsion layers. In formulae I and II, R11 is a monovalent substituent; R12 is a monovalent substituent; m is a number of R11; Z11 is a nonmetallic atomic group necessary to form an N-containing heterocycle optionally condensed with a benzene ring or the like; X11 is H or a group to be released by reaction with the oxidation product of a color developing agent; each of R21 and Y21 is H or a substituent; X21 is H or a group to be released by reaction with the oxidation product of a color developing agent; and Z21 is a nonmetallic atomic group necessary to form an N-containing N-membered ring.

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,
The present invention relates to a silver halide color photographic light-sensitive material having sharpness.

[0002]

2. Description of the Related Art With the spread of color photographic light-sensitive materials, the demand for high-quality images is increasing. Under such circumstances, studies on color reproducibility, sharpness, image storability improvement and the like have been widely conducted in color print photosensitive materials.

In a color photographic light-sensitive material, an image is formed by reacting an aromatic primary amine developing agent which has been oxidized by color development after exposing the material and a coupler. Generally, in this method, color reproduction by a subtractive color method is used, and in order to reproduce blue, green, and red, yellow, magenta, and cyan color images having complementary colors are formed.

Phenolic couplers are generally well known as cyan couplers for forming a cyan dye image. However, the phenolic cyan couplers used conventionally have improper absorption in the short wavelength region,
It is not preferable in terms of color reproducibility.

In recent years, cyan couplers having high color forming properties, image storability and excellent color reproducibility have been proposed by improving the color forming properties of phenolic cyan couplers, the image storability of the color forming dyes, and the color image absorption properties. Has been done.

EP (European Patent) Nos. 249,453A and 30
No. 4,856A, No. 320,778A, No. 354,549A, and the like propose imidazole-type couplers, and the color-developing dyes thereof have small improper absorption on the short wavelength side and have improved color reproduction. However, the color reproducibility is insufficient, and the coupling activity and the image storability also pose practical problems.

JP-A 64-552, 64-553, 64-555
The pyrazoloazole couplers described in Nos. 64-556 and 64-557 have improved short-wavelength improper absorption as compared with conventional cyan coloring dyes. In addition, Japanese Patent Laid-Open No. 4-2047
No. 28, No. 5-158196, No. 5-165169, and No. 5-165170, ureido cyan couplers having an acylamino group substituted with a heterocyclic group at the 5-position are disclosed in JP-A-4-142537 and JP-A-4-12537. 2048
No. 43, No. 4-212151, and the like, naphthol-based cyan couplers that produce a dye having sharp spectral absorption by aggregation in a light-sensitive material are also disclosed in JP-A Nos. 5-150418 and 5-150420.
Nos. 5-150423 and 5-150424 propose pyrrolotriazole-based cyan couplers, which give cyan images with excellent spectral absorption characteristics with extremely small unnecessary color reproduction in the blue and green regions. The color development and the image storability are also improved. However, it has been unsatisfactory to the recent high demand for color reproducibility of the light-sensitive material.

On the other hand, it is also effective to suppress light scattering in the film as one factor for reducing the improper absorption of the coloring dye and sharpening the absorption of the dye. In this regard,
It is known that various methods for enhancing sharpness have a close relationship with so-called sharpness, and also narrow the half-value width of dye absorption and thus improve color reproducibility.

Irradiation and halation are generally known as factors affecting sharpness. The former is brought about by the scattering of incident light by oil droplets such as silver halide grains and couplers dispersed in a gelatin film, and its degree mainly depends on the gelatin amount, silver halide amount, and oil droplet amount. The latter depends on the degree of light reflection from the support, and on the reflectance and refractive index of the support.

Dye improvements have been made to prevent irradiation. For example, JP-A-50-145125,
52-20830, 50-111641, 61-148448, 61-1
Improvements are described in the specifications of 51650, 62-275562, and 62-283336.

As a method for preventing halation, a method of providing an antihalation layer is known. For example, JP-A-55-3
Improvements are described in the specifications of 3172, 59-193447, and 62-33448.

However, in these methods, the sharpness is improved and the sensitivity is remarkably lowered, and it is difficult to improve the sharpness while maintaining the practically sufficient sensitivity only by such means.

Because of these difficulties, improvements in supports have also been investigated. As a support for color print photosensitive materials,
In recent years, water-resistant support laminated with polyolefin on the surface of base paper has been used to speed up the development process.For sharpness and white background, white pigment such as titanium oxide is dispersed in the polyolefin layer on the photographic emulsion side. I am letting you. To improve the sharpness, JP-A-54-46035, JP-A-64-18144 and JP-A-
As shown in the specification of 2-71256, it is effective to combine the technique of using a paper support filled with a large amount of white pigment in the polyolefin resin layer on the side where the photographic emulsion is coated, but the filling rate is increased. And the polyethylene layer has a serious disadvantage that the smoothness is deteriorated and the adhesion between the polyethylene layer and the emulsion layer is deteriorated.

[0014]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material having excellent color reproducibility and sharpness.

[0015]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above objects, and as a result, found that the following silver halide light-sensitive materials can achieve the above objects.

That is, in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing a silver halide emulsion on one side of a reflective support having resin coating layers on both sides of a base paper, At least one hydrophilic colloid layer containing a white pigment is provided between the support and the silver halide emulsion layer, and any one of the above formulas [I], [Chemical formula 1] to [VIII], [Chemical formula 5] A silver halide color photographic light-sensitive material comprising at least one kind of photographic cyan coupler represented by the above formula in at least one of the silver halide emulsion layers.

The present invention will be described in detail below.

First, the general formulas [I] to [VII] according to the present invention are described.
The cyan coupler represented by [I] will be described. Each of these couplers can be synthesized by a known method.

The pyrazoloazole type cyan coupler having at least one electrophotographic attractive group at a substitutable position excluding the active site of the pyrazoloazole ring represented by the general formula [I] according to the present invention is specifically described. explain.

The pyrazoloazole type cyan coupler is
It is a cyan coupler having a condensed ring in which an azole ring (including one in which a benzene ring or the like is condensed) is condensed to a pyrazole ring, that is, a pyrazoloazole ring.

The pyrazoloazole ring becomes a cyan coupler which forms a cyan dye by color development by having at least one electron-withdrawing group at a substitutable position excluding its active site.

Other optional substituents may be present at other substitutable positions of the pyrazoloazole ring except the active site. The active site of the pyrazoloazole ring means a position at which a hydrogen or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent formed as a result of color development is bonded.

The electron-withdrawing group of the present invention means that a pyrazoloazole type cyan coupler reacts with an oxidized product of a developing agent,
It means a substituent having an electron withdrawing force of such strength that it forms a dye having an absorption maximum between 580 and 700 nm when dissolved in methanol and measured. The electron-withdrawing groups may each independently have the above-mentioned electron-withdrawing force, or may jointly have the above-mentioned electron-withdrawing force.

The pyrazoloazole type cyan coupler of the present invention is represented by the following general formula [I].

[0025]

[Chemical 6]

[In the formula, R ₁₁ represents a hydrogen atom or a monovalent substituent, and R ₁₂ represents a monovalent substituent. R ₁₂ represents a monovalent substituent. m represents the number of substituents R ₁₂ . When m is 0, R ₁₁ represents an electron-withdrawing group, and when m is 1 or 2,
At least one of R ₁₁ and R ₁₂ represents an electron-withdrawing group. When m is 2 or more, plural R ₁₂ may be the same or different.

Z ₁₁ represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle which may be condensed with a benzene ring or the like.

X ₁₁ represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent.

The electron-withdrawing group according to the present invention preferably has a substituent constant δp defined by Hammett of +0.
20 or more substituents, specifically, sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, carbamoyl, acyl, acyloxy, oxycarbonyl, carboxyl, cyano, nitro, halogenated alkoxy, halogenated aryloxy, pyrrolyl, Each group such as tetrazolyl, a halogen atom and the like can be mentioned.

Examples of the sulfonyl group include alkylsulfonyl, arylsulfonyl, halogenated alkylsulfonyl and halogenated arylsulfonyl groups.

Examples of the sulfinyl group include groups such as alkylsulfinyl and arylsulfinyl.

Examples of the sulfonyloxy group include groups such as alkylsulfonyloxy and arylsulfonyloxy.

As the sulfamoyl group, N, N-dialkylsulfamoyl, N, N-diarylsulfamoyl, N-
Examples include groups such as alkyl-N-arylsulfamoyl.

Examples of the phosphoryl group include alkoxyphosphoryl, aryloxyphosphoryl, alkylphosphoryl and arylphosphoryl groups.

Examples of the carbamoyl group include N, N-dialkylcarbamoyl, N, N-diarylcarbamoyl and N-alkyl-N-arylcarbamoyl groups.

As the acyl group, alkylcarbonyl,
Examples include groups such as arylcarbonyl.

As the acyloxy group, alkylcarbonyloxy and the like are preferable.

Examples of the oxycarbonyl group include groups such as alkoxycarbonyl and aryloxycarbonyl.

The halogenated alkoxy group is preferably an α-halogenated alkoxy group.

As the halogenated aryloxy group, each group such as tetrafluoroaryloxy and pentafluoroaryloxy is preferable.

Examples of the pyrrolyl group include groups such as 1-pyrrolyl.

Examples of the tetrazolyl group include groups such as 1-tetrazolyl.

In addition to the above substituents, trifluoromethyl group, heptafluoro-iso-propyl group, nonylfluoro group
A -t-butyl group, a tetrafluoroaryl group, a pentafluoroaryl group and the like are also preferably used.

In the general formula [I], among the substituents represented by R ₁₁ or R ₁₂ , various substituents other than the electron-withdrawing group can be mentioned, and there is no particular limitation, but typical ones As, alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkenyl,
Alkynyl, heterocycle, alkoxy, aryloxy, heterocycleoxy, siloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclethio, Examples include thioureido, hydroxy and mercapto groups, spiro compound residues, bridged hydrocarbon compound residues and the like.

The alkyl group preferably has 1 to 32 carbon atoms, and 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 above alkyl groups and aryl groups.

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

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferred.

The ureido group is an alkylureido group,
Aryl ureido group, etc .; Sulfamoylamino group is alkylsulfamoylamino group, arylsulfamoylamino group, etc .; Heterocyclic group is preferably 5 to 7-membered, specifically, 2-furyl group , 2-thienyl group, 2-
Pyrimidinyl group, 2-benzothiazolyl group, etc .; As the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferable, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole -5-oxy group and the like; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,
4-diphenoxy-1,3,5-triazole-6-thio group, etc .; siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group, succinimide group, 3-heptadecylsuccinic group Acid imide group, phthalimido group, glutarimide group, etc .; Spiro [3,3] heptan-1-yl, etc. as spiro compound residue; Bicyclo [2,2,1] heptane-as bridged hydrocarbon compound residue 1-
Yl, tricyclo [3,1,1 ^{3, 7]} decane-1-yl, 7,7-dimethyl - bicyclo [2,2,1] heptane-1-yl, and the like.

These groups may further contain a substituent such as a long chain hydrocarbon group or a diffusion resistant group such as a polymer residue.

In the general formula [I], the group capable of splitting off upon reaction with the oxidant of the color developing agent represented by X ₁₁ is
For example, halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy,
Acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycles bonded by N atom Ring, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl,

[0055]

[Chemical 7]

(R ₁₁ ′ and R ₁₂ ′ have the same meanings as R ₁₁ and R ₁₂ above, Rg and Rh each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and Z ₁₁ ′ represents Z ₁₁ and Synonymous with each other), but is preferably a hydrogen atom or a halogen atom. Of these, particularly preferable ones represented by X ₁₁ are a hydrogen atom and an alkoxy, aryloxy, alkylthio, arylthio, or nitrogen-containing heterocyclic group bonded by an N atom.

In the general formula [I], examples of the nitrogen-containing heterocycle formed by Z ₁₁ include a pyrazole ring, an imidazole ring, a benzimidazole ring, a triazole ring, and a tetrazole ring.

More specifically, the compound represented by the general formula [I] is represented by the following general formulas [I-1] to [I-7].

[0059]

[Chemical 8]

[0060] In the general formula, at least one of [I-1] Medium R ₁ and R _3, (I-2) Medium R ₁ and R
_At least one of ₄ , at least one of R ₁ , R ₅ and R ₆ in [I-3], at least one of R ₁ , R ₇ and R ₈ in [I-4], R ₁ and R in [I-5]
_At least one of the _nine , R ₁ in [I-6], [I-
In 7], at least one of R ₁ and R ₁₀ is an electron-withdrawing group.

X ₁ has the same meaning as X ₁₁ in formula [I], and p represents an integer of 0 to 4. Y represents a hydrogen atom or a substituent, and a preferable substituent represented by Y is, for example, a compound which is released from the cyan coupler before the compound of the present invention reacts with an oxidized product of a developing agent, and is described in, for example, JP-A-2006-29187. 61-2
Coupling off due to a group capable of splitting off under alkaline conditions as described in 28444 etc. or reaction with an oxidized product of a developing agent as described in JP-A-56-133734 etc. A substituent can be mentioned. Preferred Y is a hydrogen atom.

In the general formulas [I-1] to [I-7], R _{1 to} R ₁₀ which are not electron-withdrawing groups represent a hydrogen atom or a substituent, and R ₁₀ represents an electron. The substituent which is not an attractive group is not particularly limited, and specifically, in the general formula [I], when R ₁₁ or R ₁₂ is other than an electron attractive group, the substituent represented by R ₁₁ or R ₁₂ is represented. What was mentioned as a base is mentioned.

Cyan couplers having an electron-withdrawing group according to the present invention are disclosed in Japanese Patent Application Nos. 62-47323, 62-53417 and 62-6.
No. 2162, No. 62-53418, No. 62-62163, No. 62-48895,
It can be easily synthesized according to the method described in each specification such as No. 62-99950.

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

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

To the cyan coupler of the present invention, the methods and techniques usually used in cyan dye-forming couplers can be similarly applied. Typically, the cyan coupler of the present invention is incorporated into a silver halide emulsion, and this emulsion is coated on a support to form a color light-sensitive material of the present invention.

Typical examples of the pyrazoloazole type cyan coupler represented by the general formula [I] according to the present invention are shown below.

[0068]

[Chemical 9]

[0069]

[Chemical 10]

[0070]

[Chemical 11]

[0071]

[Chemical 12]

[0072]

[Chemical 13]

[0073]

[Chemical 14]

[0074]

[Chemical 15]

[0075]

[Chemical 16]

[0076]

[Chemical 17]

The cyan coupler represented by the general formula [II] according to the present invention will be described.

[0078]

[Chemical 18]

[Wherein, R ₂₁ and Y ₂₁ represent a hydrogen atom or a substituent, and X ₂₁ represents a hydrogen atom or a substituent which is released upon reaction with an oxidized product of a color developing agent.

Z ₂₁ represents a group of non-metal atoms necessary for forming a nitrogen-containing hetero 6-membered ring by condensing with the pyrazole ring together with> NY ₂₁ and the 6-membered ring has a substituent. In addition to the pyrazole ring, it may be condensed with a benzene ring. The cyan coupler of the present invention is condensed with a pyrazole ring,
There is no particular limitation on the substituent represented by R ₂₁ which has a structure forming a hetero 6-membered ring, and typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, Examples of each group include cycloalkyl and the like. In addition to these, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl,
Carbamoyl, sulfamoyl, cyano, alkoxy,
Sulfonyloxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino,
Alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxy, mercapto, nitro, sulfonic acid, and other groups, and Examples also include spiro compound residues and bridged hydrocarbon compound residues.

The alkyl group represented by R ₂₁ preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R ₂₁ is preferably a phenyl group.

The acylamino group represented by R ₂₁ is
Examples thereof include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R ₂₁ include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl component and aryl component in the alkylthio group and arylthio group represented by R ₂₁ include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R ₂₁ has 2 to 32 carbon atoms, and the cycloalkyl group has 3 carbon atoms.
The alkenyl group may be linear or branched.

The cycloalkenyl group represented by R ₂₁ preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

The sulfonyl group represented by R ₂₁ 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, 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, arylsulfamoyl group Groups, etc .; acylcarbonyl groups such as alkylcarbonyloxy groups, arylcarbonyloxy groups, etc .; carbamoyloxy groups, such as alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc .; The de group alkylureido group,
Aryl ureido group, etc .; Sulfamoylamino group is alkylsulfamoylamino group, arylsulfamoylamino group, etc .; Heterocyclic group is preferably 5 to 7-membered, specifically, 2-furyl group , 2-thienyl group, 2-
Pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group, etc .;
Those having a 7-membered heterocycle are preferred, 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-diphenoxy-1,3,5-
Triazole-6-thio group etc .; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group as succinimide group,
3-heptadecyl succinimide group, phthalimide group, glutarimide group, etc .; Spiro compound residue is spiro
[3,3] heptan-1-yl, etc .; bridged hydrocarbon compound residues include bicyclo [2,2,1] heptan-1-yl, tricyclo [3,3]
1,1 ³ , ^7, ] Decan-1-yl, 7,7-dimethyl-bicyclo [2,2,1]
Heptan-1-yl and the like can be mentioned.

The above groups 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 ₂₁ which can be released by the reaction with the oxidation product of the color developing agent include halogen atom (chlorine atom, bromine atom, fluorine atom, 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,
Alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl,

[0091]

[Chemical 19]

(R ′ has the same meaning as R, Z ′ has the same meaning as Z ₂₁ , and Ra and Rb each represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group) and the like. To be

Preferred specific examples of the cyan coupler of the present invention are represented by the following general formula [II-a].

[0094]

[Chemical 20]

[Wherein Z ″ is condensed with the pyrazole ring to form a nitrogen-containing 6-membered ring containing at least one> N—Y ″ and at least one carbonyl group or at least one sulfonyl group. The 6-membered ring may have a substituent and may be condensed with a benzene ring in addition to the pyrazole ring.

R ″ and Y ″ represent a hydrogen atom or a substituent, and X ″ represents a hydrogen atom or a substituent which is released by the reaction with the oxidation product of the color developing agent.] The cyan coupler of the present invention will be described in more detail. To do.

In the general formula [II], the nitrogen-containing hetero 6-membered ring formed by Z ₂₁ is preferably 6π electron system or 8π
An electronic system containing at least one> N-Y-
At least one carbonyl group containing four nitrogen atoms and contained in the 6-membered ring represents a group such as> C = O or> C = S. Further, the at least one sulfonyl group contained in the 6-membered ring represents a group> S (= O) ₂ .

In the general formula [II], Y ₂₁ represents a hydrogen atom or a substituent, and the preferred substituent represented by Y ₂₁ is
For example, the compounds of the present invention, after reaction with oxidized developer, but in which desorbed from said compounds, for example Y ₂₁
The substituent represented by is a group capable of splitting off under alkaline conditions, as described in JP-A-61-228444, etc., or a group described in JP-A-56-133734, etc. Examples of the substituent include a substituent that is coupled / off by a reaction with an oxidized product of a developing agent, and preferably Y ₂₁ is a hydrogen atom.

Among the cyan couplers of the present invention, preferred specific examples include compounds represented by the following general formulas [B] to [N].

[0100]

[Chemical 21]

[0101]

[Chemical formula 22]

[Wherein R ₁ , R ₂ and R ₃ are represented by the general formula [II]
Has the same meaning as R ₂₁ in, X is synonymous with X ₂₁ to Orelle general formula [II], Y has the same meaning as Y ₂₁ in formula (II). In the general formulas [B], [G], and [L], n
Represents an integer of 0 to 4, and when n is an integer of 2 to 4, a plurality of R ₂ may be the same or different.

R ₂ and R ₃ in the general formulas [K], [M] and [N] have the same meaning as R ₂₁ in the general formula [II], provided that R ₂ is not a hydroxyl group.

Z ₂ ″ ″ represents an atomic group necessary for forming a heterocycle. Preferred as the groups represented by R ₂ and R ₃ are, for example, alkyl groups, aryl groups, carboxyl groups, oxycarbonyl groups, cyano groups, alkoxy groups, aryloxy groups, amino groups, amide groups and sulfonamide groups. Group, hydrogen atom, halogen atom and the like.

Examples of the cyan coupler of the present invention represented by the general formula [II] are shown below, but the present invention is not limited by these.

[0106]

[Chemical formula 23]

[0107]

[Chemical formula 24]

[0108]

[Chemical 25]

[0109]

[Chemical formula 26]

[0110]

[Chemical 27]

[0111]

[Chemical 28]

[0112]

[Chemical 29]

[0113]

[Chemical 30]

[0114]

[Chemical 31]

[0115]

[Chemical 32]

[0116]

[Chemical 33]

[0117]

[Chemical 34]

[0118]

[Chemical 35]

[0119]

[Chemical 36]

[0120]

[Chemical 37]

The cyan couplers represented by the general formulas [III] to [VI] according to the present invention will be described.

[0122]

[Chemical 38]

In each of the general formulas [III] to [VI],
The substituent represented by each of R ₃₁ , R ₃₂ and R ₃₃ is not particularly limited, but typically, each group such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like. 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, heterocyclethio, thioureido, carboxy, hydroxy, hydroxy, Each group of mercapto, nitro, sulfo, etc., as well as a spiro compound residue, a bridged hydrocarbon compound residue and the like can be mentioned.

Hereinafter, in each of the groups represented by R _{31 to} R ₃₃ , the alkyl group preferably has 1 to 32 carbon atoms, and 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 aryl component in the alkylthio group and arylthio group are the same as those listed above as the alkyl group and aryl group.

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

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferred. Alkylsulfonyl group, arylsulfonyl group, etc. as sulfonyl group; alkylsulfinyl group, arylsulfinyl group, etc. as sulfinyl group; alkylphosphonyl group, alkoxyphosphonyl group, aryloxyphosphonyl group, arylphosphonyl group as phosphonyl group Etc .; as the acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .;
The carbamoyl group is an alkylcarbamoyl group, an arylcarbamoyl group or the like; the sulfamoyl group is an alkylsulfamoyl group, an arylsulfamoyl group or the like;
An alkylcarbonyloxy group as the acyloxy group,
Arylcarbonyloxy group, etc .; Sulfonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, etc .; Carbamoyloxy group, alkylcarbamoyloxy group, arylcarbamoyloxy group, etc .; Ureido group, alkylureido group, arylureido group, etc. Etc .; as a sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc .; as a heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, 2-thienyl group Group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group, etc .; The heterocyclic oxy group is preferably one having a 5- to 7-membered heterocycle, for example, 3,4,5,6 -Tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-oxy group, etc .; as a heterocyclic thio group Are preferably 5- to 7-membered heterocyclic thio groups, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group; siloxy As the group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; as the imide group, succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc .; as spiro compound residue, spiro compound [3,3] heptan-1-yl, etc .; bridged hydrocarbon compound residues include bicyclo [2,2,1] heptan-1-yl, tricyclo [3,3,1,1]
³⁷ ] Decan-1-yl, 7,7-dimethyl-bicyclo [2,2,1]
Heptan-1-yl and the like can be mentioned.

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.

Of the substituents represented by R ₃₂ and R ₃₃ , an electron-withdrawing group having a Hammett's substitution constant σ p of 0.3 or more is preferable, and a typical example of such a substituent is a cyano group, a nitro group, Sulfonyl group (for example, octylsulfonyl group, phenylsulfonyl group, tolufluoromethylsulfonyl group, pentafluorophenylsulfonyl group, etc.),
β-carboxyvinyl group, sulfinyl group (eg t-butylsulfinyl group, tolylsulfinyl group, trifluoromethylsulfinyl group, pentafluorophenylsulfinyl group, etc.), β, β-dicyanovinyl group, halogenated alkyl group (eg trifluoromethyl Methyl group, perfluorooctyl group, ω-hydroperfluorododecyl group, etc.), formyl group, carboxy group, carbonyl group (eg acetyl group, pivaloyl group, benzoyl group, trifluoroacetyl group etc.), alkyl and aryloxycarbonyl groups (Eg, ethoxycarbonyl group, phenoxycarbonyl group, etc.), 1-tetrazolyl group, 5-chloro-1-tetrazolyl group, carbamoyl group (eg, dodecylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (eg, trifluoromethyl group) Rufamoiru group, phenyl sulfamoyl group, an ethyl sulfamoyl group and the like) and the like.

Of these substituents represented by R ₃₂ and R ₃₃ , particularly preferred are alkyl and aryloxycarbonyl groups.

In each of the general formulas [III] to [VI],
The substituent represented by EWG is Hammett's substituent constant σ _p
It is an electron-withdrawing group of 0.3 or more, and typical examples of such a substituent include a cyano group, a nitro group, a sulfonyl group (for example, an octylsulfonyl group, a phenylsulfonyl group, a tolfluoromethylsulfonyl group, a pentafluorophenylsulfonyl group. Group), β-carboxyvinyl group,
Sulfinyl group (for example, t-butylsulfinyl group, tolylsulfinyl group, trifluoromethylsulfinyl group, pentafluorophenylsulfinyl group, etc.), β,
β-dicyanovinyl group, halogenated alkyl group (eg trifluoromethyl group, perfluorooctyl group, ω-
Hydroperfluorododecyl group, etc.), formyl group, carboxyl group, carbonyl group (eg acetyl group, pivaloyl group, benzoyl group, trifluoroacetyl group etc.),
Alkyl and aryloxycarbonyl groups (eg ethoxycarbonyl group, phenoxycarbonyl group etc.), 1-tetrazolyl group, 5-chloro-1-tetrazolyl group, carbamoyl group (eg dodecylcarbamoyl group, phenylcarbamoyl group etc.), sulfamoyl group (eg Trifluoromethylsulfamoyl group, phenylsulfamoyl group, ethylsulfamoyl group, etc.) and the like.

Of the substituents represented by EWG, preferred is
A cyano group, a sulfonyl group, a sulfinyl group, and a halogenated alkyl group.

Examples of the group represented by X ₃₁ which can be split off by the reaction with the oxidation product of the color developing agent include halogen atom (chlorine atom, bromine atom, fluorine atom and the like), alkylene, alkoxy, aryloxy, heterocyclic oxy, Acyloxy, sulfonyloxy, alkoxycarbonyloxy,
Aryloxy carbonyl, alkyl oxalyl oxy, alkoxy oxalyl oxy, alkyl thio, aryl thio, heterocyclic thio, alkyloxy thiocarbonyl thio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by N atom, alkyloxy carbonylamino, aryloxy Examples thereof include carbonylamino and carboxyl groups. The group represented by X ₃₁ is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or a nitrogen-containing heterocycle bonded by an N atom.

Y ₃₁ represents a hydrogen atom or a substituent, and a preferred substituent is that which is eliminated after reacting with an oxidized product of a developing agent. For example, as the substituent represented by Y ₃₁ , JP-A-61 is used. -228444 and the like, under alkaline conditions, by coupling with a group capable of splitting off and a developing agent oxidant as described in JP-A-56-133734 and the like, coupling. Examples of the substituent include a substituent that turns off, and Y ₃₁ is preferably a hydrogen atom.

Typical examples of the photographic cyan couplers represented by each of formulas [III] to [VI] are shown below.

[0139]

[Chemical Formula 39]

[0140]

[Chemical 40]

[0141]

[Chemical 41]

[0142]

[Chemical 42]

[0143]

[Chemical 43]

Next, the cyan coupler of the general formula [VII] according to the present invention will be described.

[0145]

[Chemical 44]

[Wherein A represents a 1-naphthol type cyan coupler in which a ballast group is bonded at a position other than the 4-position, and the substituent (B) is bonded to the 2-position of A]. R ₇₁ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an amino group or an aryl group, R _{72 is} a group capable of substituting the Benzen ring, and R ₇₃ and R ₇₄ Represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group or an aryloxy group, 1 represents an integer of 0 to 4, and m represents an integer of 0 to 4, respectively. The cyan coupler used in the present invention is preferably represented by the following general formula [VII ′] or [VII ″].

[0147]

[Chemical formula 45]

[Wherein R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an amino group or an aryl group;
² is a group capable of substituting on the benzene ring, R ³ and R ⁴ are hydrogen atoms, alkyl groups, aryl groups, halogen atoms, alkoxy groups or aryloxy groups, and R ₅ is a group capable of substituting on the naphthalene ring. Ball is a ballast group, X is a hydrogen atom or a coupling-off group, 1 is an integer of 0 to 4,
m represents an integer of 0 to 4, respectively. ]

[0149]

[Chemical formula 46]

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and Bal are
l, l and X have the same definitions as in the general formula [VII '], and each represents an integer of 0 to 3, and p represents an integer of 0 to 5, respectively. In the general formulas [VII ′] and [VII ″], R ¹ is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (hereinafter referred to as C number) (more preferably 1 to 3) (eg, methyl, ethyl, Isopropylchloromethyl, fluoromethyl, difluoromethylmethylmethoxymethyl, n-butyl), C
Number 2-8 (more preferably 2-4) alkenyl group (eg vinyl, propenyl, allyl), C number 2-8 (more preferably 2-4) alkynyl group (eg ethynyl, provalalkyl], C number 3- 8 (more preferably 3-5) cycloalkyl groups (eg cyclopropyl, 2-methyl-1)
-Methylcyclopropyl, 1-fluorocyclopropyl,
Cyclobutyl), an aralkyl group having a C number of 7 to 12 (preferably 7 to 10) (eg, benzyl, phenethyl), a C number of 1 to
8 (preferably 1 to 4) alkoxy group (eg methoxy, ethoxy) or C number 0 to 8 (preferably 0 to 4)
An amino group (for example, amino, methylamino, ethylamino, dimethylamino, pyrrolidyl) or a C number of 6 to 12
(Preferably 6-10) aryl groups (eg phenyl,
p-tolyl, p-methoxyphenyl, o-tolyl),
Particularly preferred is an alkyl group or a cycloalkyl group.

R in the general formulas [VII ′] and [VII ″]
³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group or an aryloxy group, preferably a hydrogen atom and an alkyl group having a C number of 1 to 24 (preferably 1 to 16). (For example, methyl, ethyl, isopropyl, n-butyl, n-hexadecyl), aryl having a C number of 6 to 24 (preferably 6 to 12) (for example, phenyl group), halogen atom (F, Cl, Br, I), C Number 1-24
It is preferably an alkoxy group (preferably 1 to 12) (eg methoxy) or an aryloxy group having a C number of 6 to 24 (preferably 6 to 12) (eg phenoxy), and particularly preferably a hydrogen atom or an alkyl group. When l is plural,

[0152]

[Chemical 47]

May be the same or different.

R in the general formulas [VII ′] and [VII ″]
² and R ⁵ are preferably halogen atoms (F, Cl, Br, I)
Alkyl group having 1 to 12 C (preferably 1 to 6) C (eg, methyl, isoprovir, t-butyl), cycloalkyl group having 3 to 12 C (preferably 3 to 6) C (eg cyclopropyl, cyclohexyl) , C number 1 to 12 (preferably 1 to
6) an alkoxy group (eg methoxy, n-butoxy),
An alkylthio group having a C number of 1 to 12 (preferably 1 to 6) (for example, methylthio, n-dodecylthio), an aryloxy group having a C number of 1 to 12 (preferably 1 to 10) (for example, phenoxy, pt-butylphenoxy), An arylthio group (for example, phenylthio) having a C number of 1 to 12 (preferably 1 to 10), C
Number 1 to 12 (preferably 1 to 6) alkylsulfonyl group (eg methylsulfonyl), C number 6 to 12 (preferably 6 to 10) arylsulfonyl group (eg p-trisulfonyl), C number 1 to 12 (Preferably 1 to 8) carbonamide group (eg, acetamide, benzamide), C number 1 to 12 (preferably 1 to 8) sulfonamide group (eg, methanesulfonamide, p-toluenesulfonamide), C number 1 To 12 (preferably 1 to 8) acyl groups (eg acetoxy, benzoyloxy), C 1 to 12 (preferably 1 to 8) acyloxy groups (eg acetoxy), C 2 to 12 (preferably 2) 10) Alkoxycarbonyl group (eg ethoxycarbonyl), C number 1 to 12
(Preferably 1 to 7) carbamoyl group (eg -N-methylcarbamoyl), C number 0 to 12 (preferably 0 to 8) sulfamoyl group [eg -N-ethylsulfamoyl), C number 1 to 12, (preferably 1-8) ureido groups (eg 3-methylureido, 3-phenylureido), C
Number 2 to 12 (preferably 2 to 10) alkoxycarbonylamino group (eg ethoxycarbonylamino), cyano group or nitro group, particularly preferably halogen atom, alkyl group, alkoxy group, acyl group, carbonamido group, A sulfonamide group, a carbamoyl group, a sulfamoyl group or a cyano group. Here, when m or o are plural, R ² may be the same or different, and when n or p is plural, R ⁵ may be the same or different. R ² may be substituted at positions 2 ′, 3 ′, 4 ′ and 5 ′ in the general formula [VII ′] or [VII ″], but positions 3 ′, 4 ′ and 5 ′ are preferred. R ⁵ is 3, ^5, 6, ^7, in the general formula [VII ′] or [VII ″],
8 may be substituted at any position, but 5, 6, or 7
Is preferred.

In the general formulas [VII ′] and [VII ″],
Ball represents a group having a size and shape sufficient to impart diffusion resistance to the coupler represented by the general formula [VII ′] or [VII ″], and preferably has a C number of 6 to 36 (more preferably 8 to 24). Alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, carbonamido group,
Sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, acyl group, acyloxy group, alkylsulnonyloxy group or alkoxycarbonyl group, particularly preferably alkyl group, alkoxy group, aryloxy group, alkylthio group. Is a group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a urereido group or an alkoxycarbonyl group. Ball is represented by the general formula [VII '] at the positions 3, 5, 6, 7, and 8 and in the general formula [VII]. VI
I ″] may be substituted at any position of 2 ′, 3 ′, 4 ′, 5 ′, but preferably at positions 5, 6, 7 in the general formula [VII ′] and the general formula [VII ″] ], 3 ', 4', 5 '.

In the general formulas [VII ′] and [VII ″], X represents a hydrogen atom or a coupling-off group which can be eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent, Preferably hydrogen atom, halogen atom (F, Cl, Br, I), sulfo group, thiocyanato group, C number 1
To 16 (preferably 1 to 8) alkoxy group, C number of 6 to 10
(Preferably 6 to 10) aryloxy group, C number of 1 to 16
(Preferably 1 to 8) alkylthio group, C number 6 to 36
(Preferably 6 to 24) arylthio group, C number of 2 to 16
(Preferably 2 to 12) heterocyclic oxy group, C number of 2 to 36
(Preferably 2 to 24) heterocyclic thio group, C number of 1 to 24
(Preferably 1 to 12) acyloxy group, C number of 1 to 24
(Preferably 1 to 12) sulfonyloxy group, C number of 2
24 (preferably 2-12) carbamoyloxy group, C number 1-36 (preferably 1-24) azolyl group, C number 4-36
It is an imide group (preferably 4 to 24) or a hydantoinyl group having a C number of 3 to 36 (preferably 3 to 16).

As X, a relatively electron-withdrawing group such as a halogen atom, a sulfo group, a thiocyanato group, a heterocyclic thio group, an azolyl group, or an imide group is used, and stains (dirt on a white background) due to light or heat are small. Is particularly preferable.

In the general formula [VII '] or [VII "], l is preferably 1 or 2, m, n, o, p
Is preferably 0 or 1. l is particularly preferably 1
And m, n, o and p are particularly preferably 0.

Specific examples of each substituent in the general formulas [VII '] and [VII "] are shown below.

[0160]

[Chemical 48]

[0161]

[Chemical 49]

[0162]

[Chemical 50]

Specific examples of the cyan coupler of the present invention are shown below, but the compounds of the present invention are not limited to these compounds.

[0164]

[Chemical 51]

[0165]

[Chemical 52]

Next, the cyan coupler represented by the general formula [VIII] will be described.

[0167]

[Chemical 53]

[In the formula, Y ₈₁ represents a non-metal atom group necessary for forming a 3- to 8-membered heterocyclic ring together with N, L ₈₁ represents an alkylene group, R ₈₁ represents an aryl group, and Z ₈₁ represents a hydrogen atom. Alternatively, each represents a coupling-off group. However, in the above heterocycle, the carponyl group is not directly bonded to N. ] In the following description,

[0169]

[Chemical 54]

The heterocyclic group represented by is represented by X ₈₁ for convenience. The heterocyclic group represented by X ₈₁ in the general formula [VIII] has 3 to 8 members (preferably 5 to 7 members) of 1 to 30 (preferably 1 to 24) total carbon atoms (hereinafter referred to as C number). ) Is a heterocyclic group which may further contain N, O, S, Se or Te in the ring, and may have a substituent (if substitutable) or may be condensed (condensable with a ring). Good) When X is a monocycle, examples are 1-pyrrolyl-1-imidazolyl-1-pyrazolyl, 1,2, З-triazol-1-yl-1,2,4-triazol-1-yl, 1,2,4- Triazol-4-yl, 1,2,3-triazol-1-yl, 1,2,3-4-tetrazol-1-yl, 1,2,3,
4-tetrazol-2-yl, 4-pyridon-1-yl and the like, and examples of the case where X is a condensed ring include indol-1-yl,
Examples include indazol-1-yl, benzimidazol-1-yl, penzotriazol-1-yl, penzotriazol-2-yl, carpazolyl, purin-1-yl, xanthin-1-yl and the like.

The heterocyclic group represented by X ₈₁ may be substituted, and examples of the substituent include a halogen atom, a nitro group, a cyano group, a carboxyl group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, Examples include an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfonyl group, an amino group, an alkoxycarbonyl group, an acyloxy group, a carponamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureido group and an alkoxycarbonylamino group.

X ₈₁ is preferably 1-imidazolyl, 1-pyrazolyl 1,2,4-triazol-1-yl, 1,2,3,4-tetrazol-1-yl, 1,2,3,4-tetrazole -2-yl, benzimidazol-1-yl, benzotriazol, 1-yl,
Benzotriazol-2-yl or 1,2,3-triazole-
1-yl, more preferably 1-pyrazolyl, 1,2,4-
Triazol-1-yl, 1,2,3,4-tetrazol-2-yl, penzotriazol-2-yl or 1,2,3-triazol-1-yl.

In the general formula [VIII], L ₈₁ is a C number of 1 to 30.
(Preferably 1 to 18), which may have a substituent (for example, a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarponyl group).

L ₈₁ is preferably the following general formula [VIII-1]
It is represented by.

[0175]

[Chemical 55]

In the general formula [VIII-1], R ² and R ³
Are each independently a hydrogen atom, an alkyl group, an aryl group,
An alkoxy group, an aryloxy group or an alkoxycarbonyl group, and m represents an integer of 1 to 6, respectively. However when m plural -CR ² (R ³⁾ - may be the same or different.

In the general formula [VIII-1], R ² and R ³
Is preferably a hydrogen atom, an alkyl group or an aryl group, and m is preferably an integer of 1 to 3, more preferably 1
Is.

In the general formula [VIII], R ₈₁ preferably represents an aryl group having a C number of 6 to 36, more preferably 6 to 15, and may be substituted with a substituent selected from the following substituent group A. It may be a condensed ring. Here, the substituent group A is a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, a nitro group, an amino group, an alkyl group,
Alkenyl group, alkynyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, alkoxycarponyl group, aryloxycarbonyl group, carvone It refers to a group of substituents consisting of an amide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureido group, an alkoxycarbonylamino group, a sulfamoylamino group, an alkoxysulfonyl group, an imide group and a heterocyclic group.
More preferred substituents are halogen atoms (F, C, B
r, I), cyano group, nitro group, acyl group (eg acetyl, benzoyl), alkyl group (eg methyl, t-butyl, trifluoromethyl, trichloromethyl), alkoxy group (eg methoxy, ethoxy, butoxy, trifluoro) Methoxy), alkylsulfonyl groups (eg methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl), arylsulfonyl groups (eg phenylsulfonyl, p-tolylsulfonyl, p-chlorophenylsulfonyl), alkoxycarbonyl groups (eg methoxycarbonyl, butoxycarbonyl). ), Sulfonamide groups (eg methanesulfonamide, trifluoromethanesulfonamide, toluenesulfonamide), carbamoyl groups (eg N, N-dimethylcarbamoyl, N-phenylcarbamoyl) ) Or a sulfamoyl group (eg, N, N-diethylsulfamoyl, N-phenylsulfamoyl).

R _8l is preferably a phenyl group having at least one substituent selected from a halogen atom, a cyano group, a sulfonamide group, an alkylsulfonyl group, an arylsulfonyl group and a trifluoromethyl group,
More preferably 4-cyanophenyl, 4-cyano-3-halogenophenyl, 3-cyano-4-halogenophenyl, 4-alkylsulfonylphenyl, 4-alkylsulfonyl-3-halogenophenyl, 4-alkylsulfonyl-3-alkoxy Phenyl, 3-alkoxy-4-alkylsulfonylphenyl, 3,4-dihalogenophenyl, 4-halogenophenyl, 3,
4,5-trihalogenophenyl, 3,4-dicyanophenyl, 3-
Cyano-4,5-dihalogenophenyl, 4-trifluoromethylphenyl or 3-sulfonamidophenyl, particularly preferably 4-cyanophenyl, 3-cyano-4-halogenophenyl, 4-cyano-3-halogenophenyl , 3,4-dicyanophenyl or 4-alkylsulfonylphenyl.

In the general formula [VIII], Z ₈₁ is a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter).
Represents Preferred examples of coupling-off group, a halogen ^{atom, -OR 4, -SR 4, -O} (CO) R 4, -OSO 2 R 4, -NH (C
O) R ⁴ , -NH (CO) SR ⁴ , -O (CO) OR ⁴ , -O (CO) NHR ⁴ , C number 6
To a arylazo group, a C number of 1 to 30, and a heterocyclic group bonded to a coupling active position (position to which Z is bonded) at a nitrogen atom (for example, succinimide, phthalimide, hydantoinyl, pyrazolyl, 2-benztria). Zolyl) and the like. Here, R ⁴ is an alkyl group having 1 to 36 C atoms,
It represents an alkenyl group having 2 to 36 C's, a cycloalkyl group having 3 to 36 C's, an aryl group having 3 to 36 C's or a heterocyclic group having 2 to 36 C's, and these groups are selected from the above-mentioned group A. It may be substituted with a substituent. Z ₈₁ is more preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group or an alkylthio group, and particularly preferably a hydrogen atom, a chlorine atom, a group represented by the following general formula [VIII-2] or the following general formula: It is a group represented by [VIII-3].

[0181]

[Chemical 56]

In the general formula [VIII-2], R ⁵ is a halogen atom, a cyano group, a nitro group, an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an arylsulfonyl group, a carbonamide group, a sulfonamide group, an alkoxy group. A carbonyl group, a carbamoyl group, a sulfamoyl group or a carboxyl group, and n represents an integer of 0-5. When n is plural, R ⁵ may be the same or different.

[0183]

[Chemical 57]

In the general formula [VIII-3], R ⁶ and R ⁷
Are each independently a hydrogen atom or a monovalent group, and T is -CO
-, - SO -, - SO 2 - or - (PO) R ⁹ - represents a. However, R ⁸ and R ⁹ are each a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an alkenyloxy group,
In the aryloxy group or amino group, p represents an integer of 1 to 6. Here when p is more -C (R ⁶⁾ R ⁷ - may be the same or different.

In the general formula [VIII-2], R ⁵ is preferably a halogen atom, an alkyl group (eg methyl, t-butyl, t-octyl, pentadecyl), an alkoxy group (eg methoxy, n-butoxy, n-octyl). Oxy, benzyloxy, methoxyethoxy), a carbonamide group (eg acetamide, 3-carboxypropanamide) or a sulfonamide group (eg methanesulfonamide, toluenesulfonamide, p-dodecyloxybenzenesulfonamide), particularly preferably It is an alkyl or alkoxy group. n is preferably an integer of 0 to 2, more preferably 0 or 1.

In the general formula [VIII-3], R ⁶ and /
Or, when R ⁷ represents a monovalent group, it is preferably an alkyl group (eg, methyl, ethyl, butyl, ethoxycarbonylmethyl, benzyl, isodecyl, n-dodecyl), an aryl group (eg, phenyl, 4-chlorophenyl, 4-methoxy). Phenyl), an acyl group (eg, acetyl, decanoyl, benzoyl, pivaloyl) or a carbamoyl group (eg, N-phenylrucarbamoyl-Nphenylcarbamoyl), and R ⁶ and R ⁷ are more preferably a hydrogen element, an alkyl group or an aryl group. Is.

In the general formula [VIII-3], T is preferably --CO-- or --SO _2- , and more preferably --CO.
− In the general formula [VIII-3], R ⁸ is preferably an alkyl group, an alkoxy group, an alkenyloxy group, an aryloxy group or a substituted or unsubstituted amino group.

In the general formula [VIII-3], p preferably represents an integer of 1 to 3, more preferably l.

Specific examples of the substituent in the general formula [VIII] are shown below as X _81, that is, the group represented by "Chemical formula 54".

[0190]

[Chemical 58]

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

[0192]

[Chemical 59]

In order to incorporate the cyan coupler of the present invention into an emulsion, a conventionally known method may be used. For example, the boiling point of tricresyl phosphate, dibutyl phthalate, etc. is 17
After dissolving the cyan coupler of the present invention alone or in combination in a high-boiling organic solvent having a boiling point of 5 ° C. or higher or butyl acetate, a low-boiling solvent such as butyl propionate alone or in a mixed solution thereof as necessary, The silver halide emulsion to be used in the present invention can be prepared by mixing with a gelatin aqueous solution containing a surfactant and then emulsifying with a high-speed rotating mixer or a colloid mill and then adding to a silver halide.
As gelatin used for dispersing the coupler, alkali-treated ossein gelatin having a jelly strength of 250 gr or more is preferable.

The white pigment used in the hydrophilic colloid layer containing the white pigment according to the present invention is, for example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin. For example, titanium dioxide is preferable for various reasons. The white pigment is dispersed in a water-soluble binder of a hydrophilic colloid such as gelatin that allows the treatment liquid to penetrate, and is applied as a hydrophilic colloid layer containing the white pigment. The coating amount of the white pigment is preferably in the range of 1 g / m ² to 50 g / m ² , and more preferably 2 g / m ² to 20 g / m ² .

The hydrophilic colloid layer containing the white pigment according to the present invention can be provided between the support and the silver halide emulsion layer closest to the support. Between the support and the silver halide emulsion layer closest to the support, in addition to the white pigment-containing hydrophilic colloid layer, if necessary, an undercoat layer on the support, or an intermediate layer or the like at an arbitrary position. A non-photosensitive hydrophilic colloid layer can be provided.

To the hydrophilic colloid layer containing the white pigment according to the present invention, in addition to the white pigment, a coloring agent such as yellow, gray, blue and black colloidal silver, an inorganic colored pigment, an organic colored pigment and a dye is added. You can do it.

A colorant-containing hydrophilic colloid layer can be provided between the hydrophilic colloid layer containing the white pigment according to the present invention and the support. As the colorant, various known filter dyes can be used in addition to yellow, gray, blue, and black colloidal silver. As such a light-absorbing substance, it is possible to use a substance that absorbs only light in the entire visible spectrum region, or a substance that selectively absorbs light in a certain part of the region as necessary. You can choose. The transmittance of the colorant-containing hydrophilic colloid layer is preferably 50% or less, particularly preferably 30% or less.

The halogen composition of the silver halide grains according to the present invention may be any of silver chloride, silver bromide and silver iodide, or may be a mixed composition of any of these. Examples thereof include silver chlorobromide, silver iodobromide and silver chloroiodobromide. In particular, when rapid development is required in the case of a color print photosensitive material, silver chlorobromide having a silver chloride content of 95 mol% or more is preferably used.

Heavy metal ions can be contained in the silver halide emulsion according to the present invention. Heavy metal ions used include iron, iridium, platinum, palladium,
Examples include Group 8-10 metals such as nickel, rhodium, osmium, ruthenium, and cobalt, Group 12 transition metals such as cadmium, zinc, and mercury, and ions of lead, rhenium, molybdenum, tungsten, and chromium. . Of these, transition metal ions of iron, iridium, platinum, ruthenium and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of salt or complex salt.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. Further, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589
Issue, Japanese Patent Publication No. 55-42737 and The Journal of Photographic Science (J.Photogr.Sci.) 21, 39
(1973) etc., the octahedron,
Particles having a tetradecahedral shape, a dodecahedron shape, or the like can be prepared and used. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes.

The grain size of the silver halide grain according to the present invention is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm, more preferably 0.2. The range is to 1.0 μm.

The above-mentioned particle size can be measured by various methods generally used in this technical field. A representative method is Loveland's "Particle Size Analysis Method" (ASTM Symposium on Light Microscopy, pages 94-122, (1955)) or "Theory of Photographic Processes, Third Edition" (Mies and Co-authored by James,
The method described in Chapter 2, Macmillan, (1966)) can be mentioned.

This particle size can be measured 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 expressed as a diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.

As the apparatus and method for preparing the silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making 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 halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but the one obtained by the simultaneous mixing method. Is preferred. As one form of the simultaneous mixing method, the pAg controlled double jet method described in JP-A-54-48521 may be used.

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

The coating amount of silver halide color photographic light-sensitive material used in the present invention is 0.9 g / m 2 because of suitability for rapid processing.
² or less is desirable, preferably 0.7 g / m ² or less, and particularly preferably 0.6 g / m ² or less.

For the silver halide emulsion according to the present invention, a sensitization method using a sulfur compound, a sensitization method using a gold compound, and a sensitization method using both a sulfur compound and a gold compound can be used.

Examples of the sulfur sensitizer applied to the silver halide emulsion according to the present invention include thiosulfate, allylthiocarbamidourea, allylisothiocyanate, cystine, p-toluenethiosulfonic acid, rhodanine, and inorganic sulfur. Can be mentioned.

As the gold sensitizer applied to the silver halide emulsion according to the present invention, various gold complexes other than chloroauric acid, gold sulfide and the like and the above gold compounds can be preferably used.

The silver halide emulsion according to the present invention is intended to prevent fog occurring during the process of preparing a silver halide photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fog occurring during development. Antifoggant known in
Stabilizers can be used. As an example of a compound that can be used for such a purpose, JP-A-2-146036 discloses.
The compound represented by the general formula (II) described in the lower column of the page can be mentioned, and specific compounds thereof include (IIa-1) to (IIa-) described on page 8 of the publication.
8), compounds of (IIb-1) to (IIb-7) and 1-
(3-methoxyphenyl) -5-mercaptotetrazole, 1-
Examples thereof include compounds such as (4-ethoxyphenyl) -5-mercaptotetrazole. These compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, the end of the chemical sensitization step, and a coating solution preparation step depending on the purpose.

The support used in the present invention is a paper support based on paper and having resin layers on both sides, and the resin layer on the side coated with the silver halide emulsion layer contains a white pigment. It is a paper support.

The base paper used in the paper support of the present invention can be selected from the raw materials generally used for photographic printing paper. Examples thereof include natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, and various raw materials for laminated paper. Generally, natural pulp mainly composed of softwood pulp, hardwood pulp, mixed pulp of softwood pulp and hardwood pulp, etc. can be widely applied. Any type of paper such as neutral paper and acid paper may be used.

The thickness of the paper is preferably 40 μm to 250 μm.

Further, the support may contain additives such as a sizing agent, a fixing agent, a tension enhancer, a denaturant, an antistatic agent, a dye and an antifoggant, which are generally used in papermaking, Further, a surface sizing agent, a surface tension agent, an antistatic agent, or the like may be appropriately applied to the surface.

As a method of applying a resin coating layer on the support used in the present invention, a method of laminating a polyolefin resin or a polyethylene terephthalate resin is known.

The olefin resin mainly used for lamination can be selected from ethylene, α-olefins and a mixture of at least two kinds thereof. Among them, the widely used polyolefin resin is low density polyethylene, high density polyethylene or a mixture thereof.

In general, a resin laminate can be formed by melt-extruding a resin composition on a support and coating it. In order to carry out this melt extrusion coating method, usually, a resin composition is melt extrusion coated in a form of a single layer or a plurality of layers from a slit die of an extruder on a running support.

Usually, the melt extrusion temperature is preferably 200 to 250 ° C.

The thickness of the resin coating layer is not particularly limited and is usually 15 to 60 μm.

Examples of the white pigment used in the resin coating layer of the support used in the present invention include rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, and the like.
Barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used, but titanium dioxide is particularly preferable.

Titanium dioxide may or may not be surface-treated with aluminum hydroxide, alcohol, a surfactant or the like. The amount of these white pigments is 3 to 25% by weight, preferably 5 to 20% by weight, based on the resin in the resin coating layer on the side of the reflective support on which the photographic emulsion is coated.

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

As useful sensitizing dyes, cyanine dyes,
Examples include merocyanine dyes and complex merocyanine dyes.

As the coupler used in the silver halide color photographic light-sensitive material according to the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by a coupling reaction with an oxidant of a color developing agent is used. Any compound that can be formed can be used, but as a typical example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm. What is known as is typical.

As the yellow coupler, various acylacetanilide type couplers and the like can be used.

As the magenta dye-forming coupler, 5-pyrazolone type couplers, pyrazolone benzimidazole type couplers, pyrazoloazole type couplers, open chain acylacetonitrile type couplers and the like can be used.

The yellow coupler which can be preferably used in the silver halide color photographic light-sensitive material of the present invention is a coupler represented by formula (Y-I) described on page 8 of JP-A-4-114154. Can be mentioned. Specific compounds are described in YC- on pages 9 to 11 of the same specification.
1 to YC-9 can be mentioned. Among them, YC described on page 11 of the same specification
-8 and YC-9 are preferable because they can reproduce a preferable yellow color, but the present invention is not limited thereto.

As magenta couplers which can be preferably used in the silver halide color photographic light-sensitive material according to the present invention, the general formulas (MI) and (M-II) described on page 12 of JP-A-4-114154 can be used. ) And a coupler represented by Specific compounds include those described as MC-1 to MC-11 on pages 13 to 16 of the same specification. Among them, the couplers represented by formula (M-I) are particularly preferable for enhancing the effect of the present invention, and specific compounds are described as MC-8 to MC-11 described on pages 15 to 16 of the same specification. However, the present invention is not limited to this.

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

In place of the method using a high-boiling point organic solvent, the coupler and the water-insoluble and organic solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. It is also possible to employ a method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder. Examples of the water-insoluble organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

For the purpose of shifting the absorption wavelength of the color forming dye, the compound (d-11) described on page 33 of JP-A-4-114154 and the compound (A'- on page 35 of the specification).
Compounds such as 1) can be used. Besides, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

In the silver halide color photographic light-sensitive material of the present invention, gelatin is used as a binder, and if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, Hydrophilic colloids such as sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymeric substances such as homopolymers or copolymers can also be used in combination with gelatin.

The gelatin used in the silver halide color photographic light-sensitive material of the present invention may be lime-processed gelatin or acid-processed gelatin, and may be cow bone, cow skin, pig skin or the like. Gelatin produced as a raw material may be used, but lime-processed gelatin made from cow bone or pig skin is preferable.

In the present invention, the photosensitive silver halide from the silver halide emulsion layer closest to the support on the side coated with the silver halide emulsion layer to the hydrophilic colloid layer farthest from the support. From the viewpoint of suitability for rapid processing and sensitivity, the total amount of gelatin contained in the emulsion layer and the non-photosensitive hydrophilic colloid layer is preferably 7.5 g or less per 1 m ^{2 of the} silver halide color photographic light-sensitive material of the present invention, and more preferably. It is 4 g or more and less than 7 g.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide color photographic light-sensitive material according to the present invention include
For the purpose of preventing spoilage of hydrophilic colloid such as gelatin, a fungicide represented by phenol is generally used.

In the photographic emulsion layer and other hydrophilic colloid layers of the silver halide color photographic light-sensitive material according to the present invention, a hardener which crosslinks binder (or protective colloid) molecules to enhance film strength is used alone or in combination. By doing so, the dura is cured.

To the silver halide color photographic light-sensitive material according to the present invention, various photographic additives can be added in addition to the above-mentioned compounds.

As such examples, for example, ultraviolet absorbers (for example, benzophenone compounds, benzotriazole compounds, etc.), development accelerators (for example, 1-aryl-3-pyrazolidone compounds, etc.), water-soluble anti-irradiation dyes. (For example, azo compound, styryl compound, oxonol compound, etc.), film physical property improving agent (liquid paraffin, polyalkylene glycol, etc.), color turbidity preventing agent (diffusion-resistant hydroquinone compound, etc.), color image stabilizer (for example, Hydroquinone derivatives, gallic acid derivatives, etc.), water-soluble or oil-soluble optical brighteners, and ground color tone adjusting agents.

In addition to these, competitive couplers, fogging agents, development inhibitor releasing couplers (so-called DIRs)
A coupler), a development inhibitor releasing compound and the like can be added.

In the silver halide color photographic light-sensitive material of the present invention, when the silver halide emulsion layer and the hydrophilic colloid layer used in the present invention are coated on the support used in the present invention, the coating property is improved. A thickening agent may be used for the purpose. As a coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are useful.

To form a photographic image using the silver halide color photographic light-sensitive material of the present invention, the image recorded on the negative is optically formed on the silver halide photographic light-sensitive material to be printed. You can image it and bake it,
After converting the image into digital information, CRT the image.
An image may be formed on a (cathode ray tube), and this image may be formed on the silver halide photographic light-sensitive material to be printed and printed, or scanning is performed by changing the intensity of laser light based on digital information. You may bake it.

The silver halide color photographic light-sensitive material of the present invention can form an image by being subjected to color development processing known in the art.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds may be mentioned as examples of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4-amino-3-methyl-N-ethyl-N- (β-butoxyethyl) aniline CD-5) 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) Aniline CD-6) 4-Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfone Amide CD-8) N, N-Dimethyl-p-phenylenediamine CD-9) 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10) 4-Amino-3-methyl-N- Ethyl-N- (β-ethoxyethyl) aniline CD-11) 4-Amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) Diphosphoric color developing agent is usually per liter of the developer 1 × 10 ^-2
It is used in the range of from 2 × 10 ^-1 mol, and from the viewpoint of rapid processing, it is preferably used in the range of from 1.5 × 10 ^-2 to 2 × 10 ^-1 mol per liter of the color developing solution. The color developing agent may be used alone or in combination with other known p-phenylenediamine derivatives.

The color developer according to the present invention may contain the following developer components in addition to the above components. As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, silicates, etc. may be used alone or in combination to prevent precipitation. , P
It can be used in combination within a range that maintains the H stabilizing effect. Further, disodium hydrogen phosphate, for the purpose of preparation or for the purpose of increasing ionic strength,
Various salts such as dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate and borate can be used.

Inorganic and organic antifoggants can be added, if necessary.

For the purpose of suppressing development, halide salt ions are often used, but chloride ions are mainly used to complete development in a very short time, and potassium chloride, sodium chloride and the like are used. Used. The amount of chloride ion is approximately 3.0 × 10 ^-2 per liter of color developing solution.
It is at least mol, preferably 4.0 × 10 ^{-2 to} 5.0 × 10 ^-1 mol. Bromide ions can be used within a range that does not impair the effects of the present invention, but have a large effect of suppressing development, and are approximately 1.0 × 10 ⁻³ mol or less, preferably 5.0 × 10 ⁻⁴ mol, per liter of color developing solution. The following is desirable.

If necessary, a development accelerator can be used. As a development accelerator, US Pat.
Various pyridinium compounds represented by 48604, 3671247 and JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, US Patents No. 2533990, 253
1832, 2950970, 2577127 and JP-B-44-9504
Polyethylene glycol and its derivatives, nonionic compounds such as polythioethers described in JP-B-44-950
Organic solvents, organic amines, ethanolamines, ethylenediamines, diethanolamines, triethanolamines, etc. described in JP-A-9 are included. Further, phenethyl alcohol described in U.S. Pat. No. 2,304,925 and acetylene glycol, methyl ethyl ketone, cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines and the like can be mentioned.

Further, in the color developing solution, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other Japanese Patent Publication Nos. 47-33378 and 44-9509 are described. The compound can be used as an organic solvent to increase the solubility of the developing agent.

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol sulfate, phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N,
N ', N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount is usually 1
0.01 to 1.0 g is used per liter.

Each component of the above color developing solution can be prepared by sequentially adding and stirring to a fixed amount of water. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. Further, more generally, a color developing solution is prepared by adding a plurality of components, each of which can coexist stably, in a concentrated aqueous solution or in a small container prepared in advance in a solid state into water and stirring. You can also

In processing the silver halide color photographic light-sensitive material of the present invention, the color developer is used at an arbitrary pH.
Although it can be used in the range, it is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0, from the viewpoint of rapid processing.

The processing temperature for color development according to the present invention is 15 ° C.
As described above, the temperature is preferably 45 ° C or lower, and particularly preferably 20 ° C or higher and 45 ° C or lower.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is within 1 minute. Further, it is preferable to perform the treatment within 50 seconds.

When the silver halide photographic light-sensitive material of the present invention is subjected to a running process while continuously replenishing the color developing solution, the overflow of the color developing solution is reduced,
In order to reduce environmental damage due to waste liquid, the replenishing amount of the color developing solution is preferably 20 to 150 ml per 1 m ² of the light-sensitive material. Further more preferably the waste by substantially overflow replenishment amount that does not occur, 20 per light-sensitive material 1 m ² as the specific replenishing amount
More preferably, it is 60 ml. Under such conditions, the performance of the silver halide photographic light-sensitive material is likely to change, and the silver halide photographic light-sensitive material according to the present invention can be particularly advantageously used under such conditions.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a washing process is performed. Further, as a substitute for the water washing treatment, a stabilizing treatment may be performed. As a development processing apparatus used for the development processing of the silver halide photographic light-sensitive material of the present invention, even if it is a roller transport type that conveys the light-sensitive material sandwiched between rollers arranged in a processing tank,
The endless belt method may be used in which the photosensitive material is fixed to the belt and conveyed, but a method of forming a processing tank in a slit shape and supplying the processing liquid to the processing tank and conveying the photosensitive material is also used. A spray method for atomizing, a web method by contact with a carrier impregnated with a treatment liquid, a method with a viscous treatment liquid, and the like can also be used.

[0261]

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 therein was laminated to prepare a reflective support. Each layer having the constitution shown below was coated on this reflective support to prepare a multilayer silver halide photographic light-sensitive material, Sample 101. The coating liquid was prepared as follows.

Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.67 g, stain inhibitor (HQ-1) 0.67
g and 60.67 g of high boiling organic solvent (DNP) were dissolved by adding 60 ml of ethyl acetate, and this solution was dissolved in 15% surfactant (S
U-1) A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of 10% gelatin aqueous solution containing 9.5 ml using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions, and 6.7 ml of a 5% aqueous solution of an anti-irradiation dye AI-3 was added, and the compounds shown in Table 3 were added. Was added to prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, as a hardening agent, (HH-1) was used for the second and fourth layers, and (HH-) for the seventh layer.
2) was added. As a coating aid, a surfactant (SU
-2) and (SU-3) were added to adjust the surface tension.
Further, phenol was added to each layer so that the total amount was 0.04 g / m ² .

The layer structure is as shown in the table below.

[0265]

[Table 1]

[0266]

[Table 2]

Additives used in each layer are as follows.

HH-1: tetrakis (vinylsulfonylmethyl) methane HH-2: 2,4-dichloro-6-hydroxy-S-triazine sodium SU-1: sodium tri-i-propylnaphthalene sulfonate SU-2: sulfo Succinic acid di (2-ethylhexyl) ester sodium SU-3: sulfosuccinic acid di (2,2,3,3,4,4,5,5, -octafluoropentyl) ester sodium DOP: dioctyl phthalate DNP: dinonyl Phthalate DIDP: Di-i-decyl phthalate PVP: Polyvinylpyrrolidone HBS-1: 1-dodecyl-4- (p-toluenesulfonamide) benzene HBS-2: Tri (2-ethylhexyl) phosphate and tricresyl phosphate 2: 1 (Volume ratio) HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2-hexadecyl-5-methylhydroquinone FF-1: 5-chloro-2-methylisothiazolin-3-one

[0269]

[Chemical 60]

[0270]

[Chemical formula 61]

[0271]

[Chemical formula 62]

(Preparation of Blue-Sensitive Silver Halide Emulsion) In 1000 ml of a 2% gelatin aqueous solution kept at 40 ° C., the following (Solution A) and (Solution B) were taken for 30 minutes while controlling pAg = 6.5 and pH = 3.0. At the same time, and then add the following (C solution) and (D solution) to pA
Simultaneous addition was carried out over 180 minutes while controlling g = 7.3 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the 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 was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 2.10 g K ₂ IrCl ₆ 2 × 10 ^-8 mol / mol _{AgX K 4 Fe (CN) 6} 1 × 10 -5 mol / mol AgX water to make 600ml (D solution) after 600ml completion of the addition by the addition of silver nitrate 300g water, Kao Atlas Co. Demol N Desalination was performed using a 5% aqueous solution of magnesium sulfate and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.85 μm, coefficient of variation (S / R) = 0.07, and silver chloride content of 99.5 mol%. A monodisperse cubic emulsion EMP-1 of 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-3 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 method of green-sensitive silver halide emulsion) (solution A) and (B
(Liquid) and the addition time of (C liquid) and (D liquid) are changed in the same manner as EMP-1, except that the average particle size is 0.43 μm.
A monodisperse cubic emulsion EMP-2 having m, a coefficient of variation (S / R) = 0.07 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 120 ° 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 (red Method for preparing sensitive silver halide emulsion) (solution A) and (B)
The average particle size is 0.50 μm in the same manner as EMP-1 except that the addition time of (solution) and the addition time of (solution C) and (solution D) are changed.
A monodisperse cubic emulsion EMP-3 having m, coefficient of variation (S / R) = 0.08, and silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-3:
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-R) was obtained.

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-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0280]

[Chemical formula 63]

The sample thus obtained was designated as Sample 101.
Next, the C coupler in the fifth layer of Sample 101 was replaced with the compound shown in Table 3 (the amount of coupler added was the same molar amount as EXC-1) to prepare Samples 102 to 109.

Further, as in Samples 101 to 109, Sample 11
0 to 118 were prepared, but S-1 layer and S-2 layer having the following constitution were applied between the support and the first layer.

S-2 Layer Gelatin 0.5 g / m ² (Intermediate Layer) S-1 Gelatin 1.5 g / m ² (White Pigment Layer) Anatase Titanium Dioxide 3.0 g / m ² Using the sample thus prepared The following evaluation was performed.

<Evaluation of Color Reproduction by Print> Each sample was exposed through a color negative and developed to prepare a color print, which was presented to 10 test subjects.
Visual evaluation from the viewpoint of the color reproducibility of the image, 1 point for inferior ones, 3 points for ordinary ones, and 5 points for excellent ones. The average value was used for evaluation. The following four scenes were used as the scenes.

(Scene 1) Portrait of a woman in a red sweater (Scene 2) Scenery of an amusement park (Scene 3) Scenery of a mountain (Scene 4) Group photo <Evaluation of sharpness> A resolution test chart is attached to each sample. After baking with red light and carrying out the development processing step A below, the obtained cyan image is microdensitometer PDM-5D.
The concentration was measured by (manufactured by Konica Corporation), and the value represented by the following formula was defined as the sharpness.

Sharpness (%) = (Dmax-Dmin of 5 lines / mm dense line print image) / (Dmax-Dmin in large area) where Dmax: maximum density Dmin: minimum density This value is large. The better the sharpness is.

(Processing step A) Processing step Processing temperature time Color development 35.0 ± 0.3 ° C. 45 seconds Bleach fixing 35.0 ± 0.5 ° C. 45 seconds Stability 30-34 ° C. 90 seconds Dry 60-80 ° C. 60 seconds Composition of developing solution Is shown below.

Color developing solution Pure water 800 ml Tritylenediamine 2 g Diethylene glycol 10 g Potassium bromide 0.01 g Potassium chloride 3.5 g Potassium sulfite 0.25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline Sulfate 6.0g N, N-diethylhydroxylamine 6.8g Triethanolamine 10.0g Diethylenetriaminepentaacetic acid sodium salt 2.0g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 2.0g Potassium carbonate 30g Add water Adjust the total volume to 1 liter and adjust the pH to 10.10.

Bleach-fixing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 5-Amino-1,3,4-thiadiazole-2-thiol 2.0 g Ammonium sulfite (40 % Aqueous solution) 27.5 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 6.5 with potassium carbonate or glacial acetic acid.

Stabilizer Orthophenylphenol 1.0 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP ) 2.0 g 1-Hydroxyethylidene-1,1-disulfonic acid 1.8 g BiCl ₃ (45% aqueous solution) 0.65 g MgSO4 · 7H ₂ O 0.2 g PVP (polyvinylrollidone) 1.0 g Ammonia water (25% ammonium hydroxide aqueous solution) 2.5g Nitriloacetic acid trisodium salt 1.5g Add water to make the total volume 1 liter and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

The results obtained are shown in Table 3.

[0292]

[Table 3]

As shown in Table 3, the S-1 layer and the S-
It can be seen that 2 coating improves color reproducibility and sharpness.
Further, it is understood that the cyan coupler according to the present invention improves color reproducibility and slightly improves sharpness.

On the other hand, it can be seen that the silver halide light-sensitive sample according to the present invention exerts a synergistic effect, and has excellent color reproducibility and sharpness. Especially scene (2)
It is concluded that the high-saturation color is contained in a large amount, and the combination of the present invention reproduces the high-saturation color with a faithful hue.

Example 2 The C coupler of the fifth layer of Samples 102 and 111 of Example 1 was A-3.
Replace with the compound shown in (the amount of coupler added is EXC-
Samples 201 and 202 were prepared.

Then, the C coupler-dispersed gelatin of Sample 202 was replaced with only the use of alkali-treated ossein gelatin having a jelly strength of 270 gr (the amount of coupler added was an equimolar amount to EXC). It was created.

Camera [Konica FT-1 MOTOR Konica Corporation
A color Macbeth chart [made by ColorChecker Macbeth] was photographed on a negative film under a daylight light source. Next, color negative development processing [CNK-4 Konica
Co., Ltd.] was performed to obtain a negative image. This negative image is sample 10
Konica Color Printer CL-P2000 [manufactured by Konica Corporation] was applied to Nos. 1, 201 to 203 to obtain print samples 211 to 214, respectively.
The printer conditions during printing were set for each sample so that the gray portion [Neutral 5] of the reflection density 0.7 of the color chart was reproduced on the print.

Next, the yellow, magenta, cyan, blue, green, and red parts of the color chart, and the yellow, magenta, cyan, blue, and green parts of the color charts of the print samples 211 to 214. , And the red part are reflected spectrophotometers [high-speed spectrophotometric color difference meter CMS
-1200, manufactured by Murakami Color Research Laboratory Co., Ltd.] to obtain the respective spectral reflectances, and a chromaticity diagram under a 2 degree visual field C light source on the (L *, a *, b *) display system. (A *, b *) is displayed.

The results are shown in FIG.

In FIG. 1, the black circles show the values of the yellow, magenta, cyan, blue, green and red parts of the color chart. Subscripts Y, M, C, B, G, and R
Indicates that the measured values are in the yellow, magenta, cyan, blue, green, and red portions, respectively. In addition, ◯ is the print sample 211 (comparison), Δ is the print sample 212 (comparison), ◎ is the print sample 213 (present invention),
□ indicates the values of the yellow, magenta, cyan, blue, green, and red portions of the color chart of the print sample 214 (invention).

As is apparent from FIG. 1, the comparative sample 211 is not preferable in terms of color reproducibility in both saturation and hue as compared with the chromaticity method of the original color chart. In the comparative sample 212, both the saturation and the hue are close to the chromaticity point of the original color chart, and the color reproducibility is improved, but it is still insufficient. It can be seen that the sample 213 of the present invention is closer to the chromaticity point of the original color chart in both saturation and hue, and shows more faithful color reproducibility.

In particular, cyan and blue are desirable because they approach the original, respectively.

Further, since the sample 214 of the present invention showed more faithful color reproducibility, it was proved that the above-mentioned gelatin is the preferred embodiment.

Example 3 From the 1st layer to the 7th layer except that the S-1 layer and S-2 layer of the sample 111 of Example 1 were changed to the S-1 layer and S-2 layer shown below.
Sample 301 was prepared in the same manner as Sample 111 for all layers.

In the same manner, S-1 of sample 115 of Example 1
Sample 302 was prepared by changing the layers and the S-2 layer to the S-1 layer and the S-2 layer shown below.

S-2 layer gelatin 0.8 g / m ² (intermediate layer) S-1 layer gelatin 1.5 g / m ² (white pigment layer) anatase type titanium dioxide 3.0 g / m ² black colloidal silver 1.0 g / m ² sample 301 and 302 were evaluated in the same manner as in Example 1, and the results obtained are shown in Table 4 below.

[0307]

[Table 4]

As is clear from Table 4, Samples 301 and 302 according to the present invention have excellent color reproducibility and sharpness.

Example 4 The S-1 layer and S-2 layer of the sample 111 of Example 1 were changed to the S-1 layer and S-2 layer shown below, and further, between the S-1 and the support. A sample 401 was prepared in the same manner as the sample 111 except that the S-0 layer was applied to the first layer to the seventh layer.

S-2 layer gelatin 0.5 g / m ² (intermediate layer) S-1 layer gelatin 2.0 g / m ² (white pigment layer) anatase titanium dioxide 4.0 g / m ² S-0 layer gelatin 0.8 g / m ² (Colored layer) Black colloidal silver 1.2 g / m ² Sample 401 was evaluated in the same manner as in Example 1, and Example 1 was obtained.
It was confirmed that the silver halide color light-sensitive material of the present invention had excellent color reproducibility and sharpness by reproducing the same results as in Example 1.

Example 5 Sample 50 prepared in the same manner as in Example 3 except that 10% by weight of a styrene / acrylic acid copolymer (hollow fine particles having an average particle size of 0.1 micron) was added to the SS-1 layer.
Created 1, 502. When the obtained sample was tested in the same manner as in Example 1, it was found that the effect of the present invention was reproduced and the sharpness was slightly improved.

Example 6 Samples 701 to 718 were carried out in the same manner as in Example 1 except that the support used in the sample of Example 1 was changed to the support shown below.
It was created.

<Adjustment of reflective support B> L for photographic printing paper
50% by weight of BKP (sulfate bleached hardwood pulp) and NBSP
(Sulfate bleached softwood pulp) 50% by weight white base paper (basis weight
Extrusion coating of a polyethylene composition (density 0.95 g / cc, MI 8.0 g / 10 min) was performed on one surface of 175 g / m ² , thickness 180 μm) to form a back laminate layer of 25 g / m ² .
A sheet-like substrate was manufactured.

Next, 93 parts by weight of a polyethylene composition (density 0.92 g / cc, melt index (MI) 5.0 g / 10 minutes) on the surface not back laminated,
Add 7 parts by weight of titanium oxide white pigment (anatase type), knead and then melt extrusion laminate to 30 g / m ²
The water resistant resin layer of was coated on the surface of the sheet substrate. The surface of the cooling roller used for cooling the molten polyethylene was smooth.

When the obtained sample was evaluated in the same manner as in Example 1, Samples 713 to 714 related to the present invention were the same as those in Example 1, and the effects of the present invention were sufficiently obtained.

Example 7 In the same manner as in Example 1, a color light-sensitive material having the constitution shown below was prepared.

With respect to the obtained sample, color reproduction and sharpness evaluation were carried out in the same manner as in Example 1. The results are shown in Table 5.

Each layer having the following constitution was coated on a 110 μm-thick support in which polyethylene was laminated on one side of the paper support and polyethylene containing titanium oxide was laminated on the first layer side of the other side, to form a multilayer structure. A color photographic light-sensitive material was produced.

(Preparation of Emulsion EM-1) While controlling the aqueous solution containing ossein gelatin at 40 ° C., the aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (molar ratio KBr: NaCl = 95: 5). ) Is added at the same time by the control double jet method to obtain a particle size of 0.30
A μm cubic silver chlorobromide core emulsion was obtained. At that time, pH and pAg were controlled so as to obtain a cubic particle shape. An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (molar ratio KBr: NaCl = 40: 60) were simultaneously added to the obtained core emulsion by the control double jet method to obtain average grains. Diameter 0.42 μm
The shell was formed until At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

After washing with water to remove the water-soluble salt, gelatin was added to obtain an emulsion EM-1. The breadth of distribution of this emulsion EM-1 was 8%.

(Preparation of Emulsion EM-2) While controlling the aqueous solution containing ossein gelatin at 40 ° C., the aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (molar ratio KBr: NaCl = 95: 5). ) Is added at the same time by the control double jet method to obtain a particle size of 0.18
A μm cubic silver chlorobromide core emulsion was obtained. At that time, pH and pAg were controlled so as to obtain a cubic particle shape. An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (molar ratio KBr: NaCl = 40: 60) were simultaneously added to the obtained core emulsion by the control double jet method to obtain average grains. Diameter 0.25 μm
The shell was formed until At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

After washing with water to remove the water-soluble salt, gelatin was added to obtain an emulsion EM-2. The breadth of distribution of this emulsion EM-2 was 8%.

(Preparation of Blue Sensitive Emulsion EM-B) EM-1
After sensitizing dye DD-1 to sensitize the dye, 600 mg of T-1 was added per mol of silver to prepare a blue-sensitive emulsion EM-B.

(Preparation of Green Sensitive Emulsion EM-G) A green sensitive emulsion EM-G was prepared in the same manner as the blue sensitive emulsion except that the sensitizing dye DD-2 was added to EM-2 for color sensitization.

(Preparation of Red Sensitive Emulsion EM-R) Red sensitive emulsion EM-R was prepared in the same manner as blue sensitive emulsion except that sensitizing dyes DD-3 and DD-4 were added to EM-2 for color sensitization. It was made.

(Preparation of pan-sensitive emulsion EM-P) Same as the blue-sensitive emulsion except that sensitizing dyes DD-1, DD-2, DD-3 and DD-4 were added to EM-1 for color sensitization. To prepare a pan-sensitive emulsion EM-P.

T-1: 4-hydroxy-6-methyl-1,3,3a,
7-Tetrazaindene

[0328]

[Chemical 64]

EM-B, EM-G, EM-R, EM
-A color photographic light-sensitive material having the following constitution using P-
1 was produced. The first to ninth layers were coated on the front surface of the support in the following constitution, and the tenth layer was coated on the back surface side. still,
Sample 1-1 was prepared using SA-1 and SA-2 as coating aids and HH-1 and HH-2 as hardeners.

SA-1: sulfosuccinic acid di (2-ethylhexyl) ester sodium SA-2: sulfosuccinic acid di (2,2,3,3,4,4,5,5-octafluoropentyl) ester Sodium HH-1: Tetrakis (vinylsulfonylmethyl) methane HH-2: 2,4-dichloro-6-hydroxy-s-triazine / sodium layer composition Coating amount (g / m ² ) 9th layer gelatin 0.78 (UV ray Absorption layer) UV absorber (UV-1) 0.065 UV absorber (UV-2) 0.120 UV absorber (UV-3) 0.160 Solvent (SO-2) 0.1 Silica matting agent 0.03 Eighth layer Gelatin 1.43 (Blue sensitive layer) ) Blue-sensitive emulsion EM-B (coated silver amount) 0.4 Pan-sensitive emulsion EM-P (coated silver amount) 0.1 Yellow coupler (YC-2) 0.82 Anti-staining agent (AS-2) 0.025 Solvent (SO-1) 0.82 Inhibition Agent (ST-1, ST-2, T-1) Trace amount 7th Gelatin 0.54 (Intermediate layer) Anti-color mixing agent (AS-1, 3, 4, 5, 6 equivalents) 0.055 Solvent (SO-2) 0.072 6th layer Gelatin 0.42 (Yellow yellow colloidal silver 0.1 colloidal silver layer) Anti-color mixing agent (AS-1, 3, 4, 5, 6 equivalents) 0.04 Solvent (SO-2) 0.049 Polyvinylpyrrolidone (PVP) 0.047 Anti-irradiation dye (AI-6) 0.03 Fifth layer Gelatin 0.54 (Intermediate layer) Mixed color Inhibitor (AS-1, 3, 4, 5, 6 equivalents) 0.055 Solvent (SO-2) 0.072 4th layer Gelatin 1.43 (Green sensitive layer) Green sensitive emulsion EM-G (Coated silver amount) 0.40 General sensitive emulsion EM-P (Amount of coated silver) 0.10 Magenta coupler (MC-2) 0.25 Yellow coupler (YC-3) 0.06 Stain inhibitor (AS-2) 0.019 Solvent (SO-1) 0.31 Inhibitor (ST-1, ST- 2, T-1) Trace third layer gelatin 0.75 ( Intermediate layer) Color mixture inhibitor (AS-1, 3, 4, 5, 6 equivalents) 0.055 Solvent (SO-2) 0.072 Irradiation prevention dye (AI-4) 0.01 Irradiation prevention dye (AI-5) 0.01 Two-layer gelatin 1.38 (red sensitive layer) Red sensitive emulsion EM-R (coated silver amount) 0.30 General sensitive emulsion EM-P (coated silver amount) 0.06 Cyan coupler (EXC-2) 0.44 Solvent (SO-1) 0.31 Stain prevention Agent (AS-2) 0.015 Inhibitor (ST-1, ST-2, T-1) Trace amount 1st layer Gelatin 1.0 (White pigment layer) Anatase type titanium dioxide 3.0 10th layer Gelatin 6.00 (Back layer) Silica matting agent 0.65 The amount of coated silver is converted to silver.

SO-1: trioctyl phosphate SO-2: dioctyl phthalate AS-1: 2,4-di-t-octylhydroquinone AS-2: 2,4-di-t-butylhydroquinone ST-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole ST-2: N-benzyladenine

[0332]

[Chemical 65]

[0333]

[Chemical formula 66]

[0334]

[Chemical formula 67]

[0335]

[Chemical 68]

[0336]

[Chemical 69]

The conditions of the development processing and the prescription of the processing liquid are as follows. Processing Step-1 Temperature Time Immersion (Developer) 37 ° C 12 seconds Fog exposure-12 seconds (1 lux) Development 37 ° C 95 seconds Bleach-fixing 35 ° C 45 seconds Stabilization 25-30 ° C 90 seconds Dry 60-85 ° C 40 Second processing solution composition (color developer) Benzyl alcohol 15.0 ml Cerium sulfate 0.015 g Ethylene glycol
8.0 ml potassium sulfite
2.5 g Potassium bromide 0.6 g Sodium chloride 0.2 g Potassium carbonate 25.0 g T-1 0.1 g Hydroxylamine sulfate 5.0 g Diethylenetriamine sodium pentaacetate 2.0 g 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate Salt 4.5 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 15.0 ml Water is added to bring the total volume to 1 liter and the pH is adjusted to 10.15.

(Bleach-fixing solution) Diethylenetriamine pentaacetate ferric ammonium 90.0 g Diethylenetriamine pentaacetic acid 3.0 g Ammonium thiosulfate (70% aqueous solution) 180 ml Ammonium sulfite (40% aqueous solution) 27.5 ml 3-Mercapto-1,2,4-triazole Adjust the pH to 7.1 with 0.15 g potassium carbonate or glacial acetic acid and add water to bring the total volume to 1 liter.

(Stabilizing solution) o-Phenylphenol 0.3 g Potassium sulfite (50% aqueous solution) 12 ml Ethylene glycol 10 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.5 g Bismuth chloride 0.2 g Zinc sulfate heptahydrate 0.7 g Water Ammonium oxide (28% aqueous solution) 2.0 g Polyvinylpyrrolidone (K-17) 0.2 g Fluorescent brightener (4,4'-diaminostilbenedisulfonic acid derivative) 2.0 g Add water to bring the total volume to 1 liter and add ammonium hydroxide or Adjust the pH to 7.5 with sulfuric acid. The stabilization process is 2
A counter-current system with a tank configuration was adopted.

The formulation of the replenisher for running is shown below.

(Color development replenisher) Benzyl alcohol 18.5 ml Ceric sulfate 0.015 g Ethylene glycol 10.0 ml Potassium sulfite 2.5 g Potassium bromide 0.3 g Sodium chloride 0.2 g Potassium carbonate 25.0 g T-1 0.1 g Hydroxylamine sulfate 5.0 g Sodium diethylenetriaminepentaacetate 2.0g 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 5.4g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0g Potassium hydroxide 2.0 g Diethylene glycol 18.0 ml Add water to make the total volume 1 liter and adjust to pH 10.35.

(Bleach-fixing solution replenisher) The same as the above-mentioned bleach-fixing solution.

(Stabilizer Replenisher) The same as the above stabilizer.

The replenishing amount of the developer replenishing solution, the bleach-fixing solution and the stabilizing solution was 320 ml per 1 square meter of the light-sensitive material.

The results are shown below.

[0346]

[Table 5]

As is clear from Table 5, S-1 layer, S-
It can be seen that 2 coatings improve color reproducibility and sharpness, and that the cyan coupler according to the present invention also improves color reproducibility and sharpness. However, it is clear that the silver halide light-sensitive sample according to the present invention probably exerts a synergistic effect, and has excellent color reproducibility and sharpness.

[0348]

According to the present invention, a silver halide color photographic light-sensitive material having excellent color reproducibility and sharpness can be obtained.

[Brief description of drawings]

FIG. 1 is a chromaticity diagram showing the results of Example 2.

[Explanation of Symbols] Y A subscript indicating that the measured value is in the yellow portion. M is a subscript indicating that it is a measured value in the magenta color portion. C It is a subscript indicating that it is a measured value in the cyan color portion. B is a subscript indicating that it is a measured value in the blue portion. G It is a subscript indicating that it is a measured value in the green part. R is a subscript indicating that the measured value is in the red portion. a * Chromaticity diagram display system b * Chromaticity diagram display system

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing a silver halide emulsion on one side of a reflection support comprising resin coating layers on both sides of a base paper. A photographic cyan represented by any of the following general formulas [I] to [VIII], which has a hydrophilic colloid layer containing at least one white pigment between a support and the silver halide emulsion layer. A silver halide color photographic light-sensitive material comprising at least one coupler in at least one of the silver halide emulsion layers. [Chemical 1] [In the formula, R ₁₁ represents a hydrogen atom or a monovalent substituent,
₁₂ represents a monovalent substituent. m represents the number of substituents R ₁₂ .
When m is 0, R ₁₁ represents an electron withdrawing property, and when m is 1 or 2 or more, at least one of R ₁₁ and R ₁₂ represents an electron withdrawing group. When m is 2 or more, plural R ₁₂ may be the same or different. Z ₁₁ represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle which may be condensed with a benzene ring and the like. ] [Chemical 2] [In the formula, R ₂₁ and Y ₂₁ represent a hydrogen atom or a substituent,
X ₂₁ represents a hydrogen atom or a substituent which is released by the reaction with the oxidation product of the color developing agent. Z ₂₁ represents a group of non-metal atoms necessary for forming a nitrogen-containing hetero 6-membered ring by condensing with the pyrazole ring together with> N—Y ₂₁ —, and the 6-membered ring has a substituent. Alternatively, it may be condensed with a benzene ring in addition to the pyrazole ring. ] [Chemical 3] [In each of the general formulas [III] to [VI], R ₃₁ ,
R ₃₂ , R ₃₃ and Y ₃₁ each represent a hydrogen atom or a substituent, EWG represents an electron withdrawing property having a Hammett's substituent constant σ p of 0.3 or more, and X ₃₁ represents a hydrogen atom or an oxidant of a color developing agent. It represents a group which can be removed by a reaction. ] [Chemical 4] [In the formula, A is a ballast group bonded at a position other than the 4-position.
Represents a naphthol type cyan coupler, the substituent (B) is
It is attached to the 2-position of A. R ₇₁ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group,
An alanyl group, an alkoxy group, an amino group or an aryl group, R ₇₂ is a group capable of substituting on a benzene ring, R ₇₃ and R ₇₄
Is a hydrogen atom, an alkyl group, an aryl group, a halogen atom,
The alkoxy group or the aryloxy group, l represents an integer of 0 to 4, and m represents an integer of 0 to 4, respectively. ] [Chemical 5] [Wherein Y ₈₁ represents a non-metal atom group necessary for forming a 3- to 8-membered heterocycle together with N, and L ₈₁ represents an alkylene group, R ₈₁
Represents an aryl group, and Z ₈₁ represents a hydrogen atom or a coupling leaving group. However, in the heterocycle, the carbonyl group does not directly bond to N. ]