JPH0950101A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive material having excellent raw preservability, moisture dependence during exposure, color developing property, color reproducing property and stability against changes in processing conditions, by incorporating an each specified cyan coupler and a non-color developing compd. into a red-sensitive silver halide emulsion layer. SOLUTION: This photographic sensitive material has photographic structural layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a supporting body. The red-sensitive silver halide emulsion layer contains at least one kind of a cyan coupler expressed by formula I or formula II and at least one kind of a non-color developing compd. expressed by formula III. In the formula, each of R1 and R3 is a branched alkyl group or heterocyclic group, each of R2 and R4 is a substituent, each of X1 and X2 is hydrogen atom or a group which can be released by the reaction with the oxidizing group in a color developing agent, each of R11 and R12 is an alkyl group of >5 carbon number, each of R13 and R14 is a substituent, and each of n11 and n12 is an integer 0 to 3.

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, it is excellent in raw storability of the light-sensitive material, humidity dependence upon exposure, color development, color reproducibility, and processing variability. And a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material for direct viewing, such as color photographic paper, a combination of a yellow coupler, a magenta coupler and a cyan coupler is usually used as a color forming agent for forming a dye image. Used. These couplers are required to have basic properties such as color reproducibility, color developability and image storability in dye images to be obtained. In recent years, in particular, color reproduction is performed to faithfully reproduce the original color of the object. There is a growing demand from users to improve the quality.

To date, phenols or naphthols have been widely used as cyan image forming couplers.

However, the cyan image obtained from the conventionally used phenols and naphthols has a serious problem in color reproduction. That is, the sharpness of absorption on the short wave side is poor, and unnecessary absorption, that is, irregular absorption, is also present in the green region. As a result, it is unavoidable to correct irregular absorption due to masking or the like in the negative, and in the case of paper, there is no means for correction, and color reproducibility is considerably deteriorated at present.

For the purpose of improving color reproducibility, Japanese Patent Laid-Open No. Sho 64-64
-554, 63-250649, 63-250.
No. 650 and the like propose a pyrazoloazole type cyan coupler.

However, these couplers show good color reproducibility because electron-withdrawing groups and hydrogen-bonding groups are introduced in order to satisfy the absorption wavelength of the color-forming dye formed. However, the level of coupling activity was not sufficiently satisfactory, and color development and color reproducibility were not simultaneously satisfied.

Further, in recent years, the printing process and the developing process of the light-sensitive material for color photographing and printing have been shortened and accelerated, and the stability of the process is more and more required. .

In a photographic light-sensitive material for printing such as color photographic paper, it is known that photographic performance changes depending on environmental conditions during printing, especially humidity.
It was revealed that when a pyrazoloazole type cyan coupler was used, the change in photographic performance due to changes in humidity was remarkable. Furthermore, it was revealed that the use of pyrazoloazole type cyan couplers deteriorates the raw storability of the light-sensitive material.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to provide a silver halide color photograph which is excellent in raw storability of a light-sensitive material, humidity dependence upon exposure, color development, color reproducibility and processing variability. To provide a light-sensitive material.

[0010]

The above object of the present invention can be achieved by the following constitutions.

1) A photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer is provided on a support, and the red-sensitive silver halide emulsion layer. And at least one cyan coupler represented by the following general formula (1) or (2) and at least one non-color-forming compound represented by the following general formula [A-1]. A silver halide color photographic light-sensitive material.

[0012]

[Chemical 7]

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

[0014]

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[In the formula, R ₁₁ and R ₁₂ represent a secondary or tertiary alkyl group having 5 or more carbon atoms. R ₁₃ and R
₁₄ represents a substituent, and n ₁₁ and n ₁₂ represent an integer of 0 to 3. 2) It has a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support, and the red-sensitive silver halide emulsion layer has the above-mentioned structure. A halogen containing at least one cyan coupler represented by the general formula (1) or (2) and at least one non-color-forming compound represented by the following general formula [A-2]. Silver halide color photographic light-sensitive material.

[0016]

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[In the formula, R ₂₁ and R ₂₂ represent an alkyl group. R ₂₃ and R ₂₄ represent a substituent, and n ₂₁ and n ₂₂ are
Represents an integer from 0 to 3. 3) A photographic constitutional layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer is provided on a support, and the red-sensitive silver halide emulsion layer has the above-mentioned composition. At least one cyan coupler represented by the general formula (1) or (2) and at least one non-color-forming compound represented by the following general formula [A-3] are contained. Silver halide color photographic light-sensitive material.

[0018]

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[In the formula, R ₃₁ and R ₃₂ represent a secondary alkyl group. R ₃₃ and R ₃₄ represent a substituent, and R ₃₅ and R ₃₆
Represents a hydrogen atom or a substituent. n ₃₁ and n ₃₂ are 0
Represents an integer of 3 to 3. 4) A photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer is provided on a support, and the red-sensitive silver halide emulsion layer has the above-mentioned composition. At least one cyan coupler represented by the general formula (1) or (2) and at least one non-color-forming compound represented by the following general formula [A-4] are contained. Silver halide color photographic light-sensitive material.

[0020]

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[In the formula, R ₄₁ represents a substituent, and R ₄₂ represents
Represents an alkyl group. n ₄₁ represents an integer of 0 to 3,
₄₂ represents an integer of 0 to 6. 5) A photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer is provided on a support, and the above-mentioned red-sensitive silver halide emulsion layer has the above-mentioned structure. At least one cyan coupler represented by the general formula (1) or (2) and at least one non-color-forming compound represented by the following general formula [A-5] are contained. Silver halide color photographic light-sensitive material.

[0022]

[Chemical 12]

[In the formula, R ₅₁ represents an alkyl group, an alkenyl group or an aryl group. R ₅₂ and R ₅₃ represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. The present invention will be described in detail below. First, the cyan couplers represented by the general formulas (1) and (2) of the present invention will be described in detail.

In the general formulas (1) and (2), the branched alkyl group represented by R ₁ and R ₃ is i-
Examples thereof include a propyl group, a t-butyl group, a sec-butyl group, an i-butyl group and a t-octyl group.

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

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

As the heterocyclic group, 2-furyl group, 2-thienyl group, 2-imidazolyl group, 2-thiazolyl group, 3
-Isoxazolyl group, 3-pyridyl group, 2-pyridyl group, 2-pyrimidyl group, 3-pyrazolyl group, 2-benzothiazolyl group and the like can be mentioned.

When R ₁ and R _{3 each} represent a branched alkyl group or a heterocyclic group, these groups may have a substituent if necessary.

There are no particular restrictions on these substituents, but typical examples include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl groups, and the like. 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, hetero Examples include groups such as ring thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, and sulfo, as well as spiro compound residues and bridged hydrocarbon compound residues.

In the general formulas (1) and (2), R ₂
The substituent represented by and R ₄ is not particularly limited, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl groups. A halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy,
Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, sulfo and other groups, In addition, spiro compound residues, bridged hydrocarbon compound residues and the like are also included.

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

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

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

The sulfonyl group is an alkylsulfonyl group, an arylsulfonyl group or the like; the sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group or the like;
The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; The acyl group is an alkylcarbonyl group, an arylcarbonyl group, etc .; The carbamoyl group is an alkylcarbamoyl group, an arylcarbamoyl group. Etc .; as sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, etc .; as acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc .; as sulfonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, etc. A carbamoyloxy group as an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; a ureido group as an alkylureido group, an arylureido group, etc .; sulfamoylamino As alkylsulfamoyl group, an aryl sulfamoylamino group such as, is preferably a 5- to 7-membered as heterocyclic group, specifically 2-
Furyl, 2-thienyl, 2-pyrimidinyl, 2-
A benzothiazolyl group, a 1-pyrrolyl group, a 1-tetrazolyl group, etc .; a heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, 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-heptadecylsuccinimide group , Phthalimide group, glutarimide group, etc .; spiro [3.3] heptan-1-yl, etc. as spiro compound residue; bridged hydrocarbon compound Examples of the group 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 substituent represented by R ₂ and R ₄ is preferably an alkyl group or an aryl group, and particularly preferably an aryl group.

The above 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 ₁ and X ₂ which can be split off by the reaction with the oxidation product of the color developing agent are, for example, halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, and heterocyclic oxy. , Acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio,
Examples include acylamino, sulfonamide, nitrogen-containing heterocycle linked by an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl. X ₁ and X ₂ are preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a nitrogen-containing heterocyclic group bonded by an N atom and the like.

Among the cyan couplers represented by the general formulas (1) and (2), those represented by the general formula (1) are preferable.

Specific examples of the cyan coupler represented by the general formulas (1) and (2) are shown below, but the invention is not limited thereto.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

[Chemical 21]

[0053]

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[0054]

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[0055]

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[0056]

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Next, the compound represented by formula (A-1) of the present invention will be described.

2 having 5 or more carbon atoms represented by R ₁₁ and R ₁₂
Examples of the secondary or tertiary alkyl group include s-pentyl, t-pentyl, s-hexyl, t-hexyl,
Examples include groups such as 1,1-dimethylhexyl and 1,1-dimethyloctyl.

The substituents represented by R ₁₃ and R ₁₄ include
For example, alkyl, cycloalkyl, alkenyl, aryl, amide, sulfonamide, alkylthio, arylthio, halogen atom, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, Acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino,
Examples thereof include groups such as alkoxycarbonyl, aryloxycarbonyl and carboxy.

Next, the compound represented by formula (A-2) will be described.

Examples of the alkyl group represented by R ₂₁ and R ₂₂ include groups such as methyl, ethyl, t-butyl, hexyl, octyl, nonyl and dodecyl.

R ₂₃ and R ₂₄ represent the same groups as R ₁₃ and R _{14 in the} general formula [A-1].

Next, the compound represented by formula [A-3] will be described.

Examples of the secondary alkyl group represented by R ₃₁ and R ₃₂ include groups such as i-propyl, s-butyl, s-pentyl and s-hexyl groups.

The substituents represented by R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ are the same as R ₁₃ and R _{14 in the} general formula [A-1].

Next, the compound represented by formula [A-4] will be described.

R ₄₁ represents the same group as R ₁₃ and R _{14 in} the above general formula [A-1].

The alkyl group represented by R ₄₂ preferably has 1 to 32 carbon atoms, and may be linear or branched.

Next, the compound represented by the general formula [A-5] will be described.

The alkyl group represented by R ₅₁ , R ₅₂ and R ₅₃ preferably has 1 to 32 carbon atoms and may be linear or branched.

The alkenyl group represented by R ₅₁ , R ₅₂ and R ₅₃ preferably has 1 to 32 carbon atoms and may be linear or branched.

Examples of the aryl group represented by R ₅₁ , R ₅₂ and R ₅₃ include groups such as phenyl and naphthyl.

The general formulas [A-1] to [A- of the present invention will be described below.
Representative specific examples of the compound represented by 5] are shown below.

[0074]

[Chemical formula 26]

[0075]

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[0076]

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[0077]

[Chemical 29]

[0078]

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[0079]

[Chemical 31]

[0080]

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[0081]

[Chemical 33]

[0082]

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[0083]

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[0084]

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The high boiling point solvents represented by the general formulas [A-1] to [A-5] of the present invention can be used in combination of two or more kinds.

To emulsify and disperse in the hydrophilic protective colloid to obtain lipophilic fine particles, a dispersing aid such as a surfactant is used and a stirrer, homogenizer, colloid mill, flow jet mixer, ultrasonic device, etc. are used. Spread. A step of removing the low-boiling organic solvent at the same time as the dispersion may be included.

An aqueous gelatin solution is preferably used as the hydrophilic protective colloid.

The average particle size of the lipophilic fine particles is 0.04.
μm to 2 μm is preferred, but more preferably 0.06
μm to 0.4 μm. The particle diameter can be measured by Coulter Model N4 manufactured by Coulter, UK.

In the above, the mixing ratio of the coupler, the high boiling point solvent and the low boiling point solvent or the auxiliary solvent such as an organic solvent miscible with water is such that the solution in which the coupler and the high boiling point solvent are dissolved in the auxiliary solvent is a hydrophilic colloid. It may be selected so as to have a viscosity suitable for being easily dispersed therein. The ratio (weight ratio) of the high boiling point solvent to the coupler used is 1:20 to 5:
1, preferably 1:10 to 2: 1.

The photosensitive silver halide emulsion layer of the silver halide color photographic light-sensitive material of the present invention contains a silver halide emulsion.

The silver halide emulsion of the present invention includes silver chloride, silver bromide, silver iodide or mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodide and silver chloroiodobromide. Etc. can be applied. These silver halide emulsions are produced by a usual method, and an ammonia method, a neutral method, an acidic method, a halogen conversion method, a function addition method, a uniform precipitation method, and the like can be applied. The average diameter of the particles is not limited, but is preferably 0.01 μm to 5 μm. Two or more silver halide emulsions formed separately may be used as a mixture.

The silver halide emulsion used in the present invention is
Chemical sensitization can be performed using a usual method. Chemical sensitization includes a gold sensitization method using a gold complex salt, a reduction sensitization method using a reducing substance, a sulfur-containing compound capable of reacting with silver ions and a so-called sulfur sensitization method using active gelatin, A sensitization method using a salt of a noble metal belonging to Table VIII can be used.

The silver halide emulsion used in the present invention is
Spectral sensitization can be performed. The method can be carried out by using cyanine dyes such as monomethine cyanine, pentamethine cyanine, merocyanine and carbocyanine alone or in combination, or by combining them with a styryl dye or an aminostilbene compound.

The silver halide emulsion used in the present invention includes stabilizers, antifoggants, surfactants, defoamers, antistatic agents, film hardeners, film physical property improvers, brighteners and stain inhibitors. ,
Additives such as ultraviolet absorbers and irradiation inhibitors can be included. About these various additives, Research Disclosure volume 176,
No. All those described in 17643 (1978) can be used.

The support of the color photographic light-sensitive material of the present invention comprises
It can be appropriately selected according to the purpose. For example, a cellulose acetate film, a polyethylene terephthalate film, a polystyrene film, a polycarbonate film, or a laminate thereof, paper, baryta paper, α-
Paper, synthetic paper, glass, coated with olefin polymer,
There are metals, etc.

In the above color photographic light-sensitive material, it is advantageous to use gelatin as the binder or protective colloid, but other hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, and hydroxy. Cellulose derivatives such as ethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, etc. It is possible to mix and use various types of synthetic hydrophilic polymer substances.

The processing method of the silver halide photographic light-sensitive material of the present invention is not particularly limited, and any generally known processing method can be applied. For example, as a typical example thereof, after color development, a bleach-fixing treatment is carried out, and if necessary, further washing with water and / or a stabilizing treatment is carried out.
Bleaching and fixing are performed separately, and further washed with water and / or
Alternatively, any method of stabilizing treatment may be used, but the silver halide color photographic light-sensitive material of the present invention is rapidly treated in the steps of color development, bleach-fixing and washing (or stabilizing). Suitable to be done.

[0098]

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

Example 1 On a support having polyethylene laminated on one side of a paper support and polyethylene containing titanium oxide on the other side, a polyethylene layer containing titanium oxide was added to each layer having the following constitution. Samples 1 to 20 of multilayer silver halide color photographic light-sensitive material were prepared by coating on the side of. The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST
-2) 6.67 g, additive (HQ-1) 0.67 g, irradiation prevention dye (AI-3) 0.335 g, high boiling point organic solvent (DNP) 6.67 g and ethyl acetate 60 m
1 and dissolved, and this solution was added to a 20% surfactant (SU-
1) 220 ml of 10% gelatin aqueous solution containing 7 ml
The mixture was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a first layer coating solution.

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

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

[0103]

[Table 1]

[0104]

[Table 2]

[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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(Method for Preparing Blue-Sensitive Silver Halide Emulsion) 4
The following (solution A) and (solution B) were pAg = 6.5 and pH = 3 in 1000 ml of a 2% aqueous gelatin solution kept at 0 ° C.
The solution was added simultaneously over 30 minutes while controlling to 0, and the following (Solution C) and (Solution D) were further pAg = 7.3 and pH = 5.
5 and simultaneously added over 180 minutes. The pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide. For control of pAg, a control solution having the following composition was used. The composition of the control solution is a mixed halide salt aqueous solution composed of sodium chloride and potassium sulfide. The ratio of chloride ion to bromide ion is 99.8: 0.2. When mixing the liquids, the molar ratio was 0.1 mol / l, and when mixing the liquids C and D, the molar ratio was 1 mol / l.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to make up to 200 ml.

(Solution B) Silver nitrate 10 g Water was added to make up to 200 ml.

(Liquid C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to make a final volume of 600 ml.

(Solution D) 300 g of silver nitrate Water was added to make 600 ml.

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
a Desalting was performed using a 5% aqueous solution and a 2.0% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to have an average particle diameter of 0.85 μm, a variation coefficient of 0.07, and a silver chloride content of 99.5 mol. % Of a monodispersed cubic emulsion EMP-1.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (preparation method of green-sensitive silver halide emulsion) (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) in the same manner as in EMP-1 except that the average particle diameter was 0.4.
A monodispersed cubic emulsion EMP-2 having a size of 3 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained. EMP-2 was chemically ripened at 55 ° C. for 120 minutes using the following compound to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (Preparation method of red-sensitive silver halide emulsion) (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) were changed in the same manner as in EMP-1 except that the average particle diameter was 0.5.
A monodispersed cubic emulsion EMP-3 having a thickness of 0 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained. EMP-3 was chemically ripened at 60 ° C. for 90 minutes using the following compounds to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX The coefficient of variation is the number obtained by dividing the standard deviation of the particle size by the average particle size.

[0122]

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The obtained samples were evaluated by the following methods.

<Evaluation of Relative Sensitivity> Each sample was subjected to gradation exposure for sensitometry for 0.5 seconds through a red filter, and then developed in the following steps. An optical densitometer (PDA-65 manufactured by Konica Corporation) was used for the obtained sample.
Type) to measure the density, sensitivity and maximum density (Dma
x) was determined.

<Evaluation of storability> For each sample, after coating, in an environment of 25 ° C. and 60% (relative humidity),
After storage for 1 day and 3 months, exposure and treatment were performed in the same manner as above, and the sensitivities of both were compared. In the sensitivity comparison, the sensitivity of the sample one day after application was set to 100 and the sensitivity of the sample after storage for 3 months was represented by relative sensitivity.

<Evaluation of Sensitivity Change by Humidity Change during Exposure> The ambient temperature during exposure was kept constant at 25 ° C., the relative humidity around was changed to 15% and 80%, and the sensitivity was compared. The sensitivity variation was tested by changing the ambient humidity.
For comparison of sensitivity, the sensitivity when relative humidity was 15% was set to 100, and the sensitivity at relative humidity of 80% was expressed by relative sensitivity.

The processing conditions are as follows.

Treatment process Temperature Time Color development 35.0 ± 0.3 ° C. 45 seconds Bleach fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Dry 60-80 ° C. 60 seconds Color development Developer solution Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1. 0 g Catechol-3,5-disulfonic acid disodium salt 1.0 g Diethylene glycol 10 g N-Ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate (CD-3) 4.5 g Fluorescence enhancement Whitening agent (4,4'-diaminostilbene sulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.10.

Bleach-fixing solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water was added to bring the total volume to 1 liter and carbonic acid. Adjust the pH to 5.7 with potassium or glacial acetic acid.

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

The same procedure as above was carried out except that the obtained sample was exposed to light in the same manner as described above, and then the amount of CD-3 as a color developing agent in the color developing solution in the processing step was changed to 3.5 g / l. Processing was carried out by the process, and the maximum density (Dmax ') of the red-sensitive photosensitive layer was measured.

The color reproducibility of each of Samples 1 to 20 was evaluated by the following method.

First, a color negative film (Konica Color LV-400: manufactured by Konica Corporation) and a camera (Konica F)
T-1 MOTOR: manufactured by Konica Corporation) was used to photograph a Macbeth color checker. Subsequently, color negative development processing (CNK-4: manufactured by Konica Corporation) is performed, and the obtained negative image is processed by Konica Color Printer CL-
Using P2000 (manufactured by Konica Corporation)
o. Prints were made on each of Nos. 1 to 20 to a size of 82 mm × 117 mm, and practical prints were obtained in the same manner as described above. Printer conditions at the time of printing were set for each sample so that the gray on the color checker became gray on the print.

The color reproducibility of the obtained practical prints was visually evaluated.

The results are summarized in Table 3.

[0136]

[Table 3]

[0137]

Embedded image

As is clear from Table 3, Sample No. 1 using the cyan coupler outside the present invention and HBS outside the present invention.
1 and No. 1 No. 2 is not sufficient in terms of sensitivity, maximum density, raw storability, humidity dependency during exposure, process variability, and color reproducibility. Further, cyan couplers other than the present invention and HBs of the present invention
Sample No. using S. 3 and No. 3 4 is the highest concentration,
Although a slight improvement in color reproducibility is recognized, it cannot be said that the raw storability and the humidity dependency during exposure are sufficient.

On the other hand, Sample No. 1 using the cyan coupler of the present invention and HBS other than the present invention. In No. 5, although a slight effect in color development and raw storability is recognized, it cannot be said that processing variability and color reproducibility are sufficient.

On the other hand, Sample No. 6 to sample N
o. No. 20 has a high sensitivity, a high maximum density, a good raw storability, and a very good humidity dependency at the time of exposure, processing variability, and color reproducibility.

Example 2 A sample was prepared in the same manner as in Example 1 except that the HBS of the fifth layer was changed as shown in Table 4, and the same evaluation as in Example 1 was performed. It was The results are also shown in Table 4.

[0142]

[Table 4]

As is clear from Table 4, Sample No. 1 using the cyan coupler outside the present invention and the HBS outside the present invention.
1 and No. 1 No. 2 is not sufficient in terms of sensitivity, maximum density, raw storability, humidity dependency during exposure, process variability, and color reproducibility. Further, cyan couplers other than the present invention and HBs of the present invention
Sample No. using S. 23 and No. 23. No. 24 shows some improvement in maximum density and color reproducibility,
It is hard to say that the humidity dependency during exposure is sufficient.

On the other hand, Sample No. 1 using the cyan coupler of the present invention and HBS other than the present invention. In No. 5, although a slight effect is observed on the color developability and the raw storability, it cannot be said that the processing variability and the color reproducibility are sufficient.

On the other hand, the sample No. of the present invention. 26-Sample No. No. 40 has a high sensitivity, a high maximum density, a good raw storability, and a very good humidity dependency at the time of exposure, processing variability, and color reproducibility.

Example 3 A sample was prepared in the same manner as in Example 1 except that the HBS of the fifth layer was changed as shown in Table 5, and the same evaluation as in Example 1 was performed. It was The results are shown in Table 5.

[0147]

[Table 5]

As is clear from Table 5, Sample No. 1 using the cyan coupler outside the present invention and HBS outside the present invention.
1 and No. 1 No. 2 is not sufficient in terms of sensitivity, maximum density, raw storability, humidity dependency during exposure, process variability, and color reproducibility. Further, cyan couplers other than the present invention and HBs of the present invention
Sample No. using S. 43 and No. 43. In No. 44, the maximum density and color reproducibility are slightly improved, but the raw preservation property,
It is hard to say that the humidity dependency during exposure is sufficient.

On the other hand, Sample No. 1 using the cyan coupler of the present invention and HBS other than the present invention. In No. 5, although a slight effect is observed on the color developability and the raw storability, it cannot be said that the processing variability and the color reproducibility are sufficient.

On the other hand, the sample No. 46-Sample No. No. 60 has high sensitivity, high maximum density, good raw storability, and very good humidity dependency at the time of exposure, process variability, and color reproducibility.

Example 4 A sample was prepared in the same manner as in Example 1 except that the HBS of the fifth layer was changed as shown in Table 6, and the same evaluation as in Example 1 was performed. It was Table 6 also shows the results.

[0152]

[Table 6]

As is clear from Table 6, Sample No. 1 using the cyan coupler outside the present invention and the HBS outside the present invention.
1 and No. 1 No. 2 is not sufficient in terms of sensitivity, maximum density, raw storability, humidity dependency during exposure, process variability, and color reproducibility. Further, cyan couplers other than the present invention and HBs of the present invention
Sample No. using S. 63 and No. No. 64 shows a slight improvement in the maximum density and color reproducibility, but the raw storability,
It is hard to say that the humidity dependency during exposure is sufficient.

On the other hand, Sample No. 1 using the cyan coupler of the present invention and HBS other than the present invention. In No. 5, although a slight effect is observed on the color developability and the raw storability, it cannot be said that the processing variability and the color reproducibility are sufficient.

On the other hand, Sample No. 66-Sample No. No. 80 has high sensitivity, high maximum density, good raw storability, and very good humidity dependency during exposure, process variability, and color reproducibility.

Example 5 A sample was prepared in the same manner as in Example 1 except that the HBS of the fifth layer was changed as shown in Table 7, and the same evaluation as in Example 1 was performed. It was The results are also shown in Table 7.

[0157]

[Table 7]

As is clear from Table 7, Sample No. 1 using the cyan coupler outside the present invention and HBS outside the present invention.
1 and No. 1 No. 2 is not sufficient in terms of sensitivity, maximum density, raw storability, humidity dependency during exposure, process variability, and color reproducibility. Further, cyan couplers other than the present invention and HBs of the present invention
Sample No. using S. 83 and No. No. 84 has some improvement in maximum density and color reproducibility,
It is hard to say that the humidity dependency during exposure is sufficient.

On the other hand, Sample No. 1 using the cyan coupler of the present invention and HBS other than the present invention. In No. 5, although a slight effect is observed on the color developability and the raw storability, it cannot be said that the processing variability and the color reproducibility are sufficient.

On the other hand, the sample No. 86-Sample No. No. 100 has high sensitivity, high maximum density, good raw storability, and very good humidity dependency during exposure, process variability, and color reproducibility.

[0161]

According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material which is excellent in raw storability, humidity dependence upon exposure, color development, color reproducibility and processing variability. .

Claims (5)

[Claims] 1. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer is represented by the following general formula (1) or general formula (2). At least one cyan coupler and the following general formula [A-
[1] A silver halide color photographic light-sensitive material containing at least one non-color-forming compound represented by the formula [1]. Embedded image [In the formula, R ₁ and R ₃ each represent a branched alkyl group, a substituted alkyl group, a substituted aryl group or a heterocyclic group, R ₂ and R ₄ each represent a substituent, and X ₁ and X ₂ each represent a hydrogen atom. Alternatively, it represents a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ] [Chemical 2] [In the formula, R ₁₁ and R ₁₂ represent a secondary or tertiary alkyl group having 5 or more carbon atoms. R ₁₃ and R ₁₄ represent a substituent, and n ₁₁ and n ₁₂ represent an integer of 0 to 3. ] 2. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer is represented by the above general formula (1) or general formula (2). At least one cyan coupler and the following general formula [A-
[2] A silver halide color photographic light-sensitive material containing at least one non-color forming compound represented by the above [2]. Embedded image [In the formula, R ₂₁ and R ₂₂ represent an alkyl group. R ₂₃ and R ₂₄ represent a substituent, and n ₂₁ and n ₂₂ represent an integer of 0 to 3. ] 3. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer is represented by the above general formula (1) or general formula (2). At least one cyan coupler and the following general formula [A-
[3] A silver halide color photographic light-sensitive material containing at least one non-color-forming compound represented by the formula [3]. Embedded image [In the formula, R ₃₁ and R ₃₂ represent a secondary alkyl group. R ₃₃
And R ₃₄ represent a substituent, and R ₃₅ and R ₃₆ represent a hydrogen atom or a substituent. n ₃₁ and n ₃₂ represent an integer of 0 to 3. ] 4. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer is represented by the above general formula (1) or general formula (2). At least one cyan coupler and the following general formula [A-
[4] A silver halide color photographic light-sensitive material containing at least one non-color-forming compound represented by the formula [4]. Embedded image [In the formula, R ₄₁ represents a substituent, and R ₄₂ represents an alkyl group. n ₄₁ represents an integer of 0 to 3, and n ₄₂ represents an integer of 0 to 6. ] 5. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer is represented by the above general formula (1) or general formula (2). At least one cyan coupler and the following general formula [A-
[5] A silver halide color photographic light-sensitive material containing at least one non-color-forming compound represented by the formula [5]. [Chemical 6] [In the formula, R ₅₁ represents an alkyl group, an alkenyl group or an aryl group. R ₅₂ and R ₅₃ represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. ]