JP3503008B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] This invention relates to silver halide color photography.
Regarding photosensitive materials, for more information,
Excellent humidity dependency, color development and color reproducibility
Silver halide color photographic materials with excellent mobility
You. [0002] 2. Description of the Related Art Silver halide photographs used for direct viewing
For photosensitive materials such as color photographic paper, dye images
Yellow couplers, mazes
When a combination of an intermediate coupler and a cyan coupler is used
It is. For these couplers, the resulting dye image
Characteristics such as color reproducibility, color development and image storability
Function is required, especially in recent years,
Is the request for color reproducibility improvement to be reproduced on the user side?
Is rising. [0003] As a cyan image forming coupler,
Phenols or naphthols are often used in
I have. However, conventionally used phenols
Reproduction of cyan images obtained from phenols and naphthols
There is a big problem. It is bad on the short wave side of absorption
And also have unnecessary or irregular absorption in the green region
It is. This allows the negative to be masked
Correction of irregular absorption must be performed, and in the case of paper
Has no means of correction and considerably deteriorates color reproducibility
is the current situation. For the purpose of improving color reproducibility, Japanese Patent Application Laid-Open
-554, 63-250649, 63-250
No. 650 and others offer pyrazoloazole-type cyan couplers.
Is being planned. [0006] However, these couplers
In order to satisfy the absorption wavelength of the coloring dye that is also formed
Has an electron-withdrawing group and a hydrogen-bonding group
High color reproducibility but high coupling activity
Is not at a level that is satisfactory enough,
Not satisfied at the same time. In recent years, for color photography and printing
For photosensitive materials, the printing process and the development process
Process has become faster and more stable
Is increasingly required. [0008] Photographs for printing such as color photographic paper
For photosensitive materials, environmental conditions during printing, especially
It is known that photographic performance changes with humidity,
The use of pyrazoloazole type cyan couplers
It is clear that the change in photographic performance due to the change in degree is remarkable
Became. Furthermore, pyrazoloazole type cyan couplers
It is clear that the use of
It became clear. [0009] SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive device.
Raw storability of materials, humidity dependence during exposure, color development, color reproduction
Silver halide color with excellent processability and process variability
-To provide photographic light-sensitive materials. [0010] The above object of the present invention is as follows.
This is achieved by the above configuration. 1) Blue-sensitive silver halide emulsion on a support
Layer, green-sensitive silver halide emulsion layer, and red-sensitive halide
Having a photographic constituent layer including a silver emulsion layer,
The silver emulsion layer is represented by the following general formula (1) or (2).
And at least one cyan coupler represented by the following general formula
[A-3At least one non-color-forming compound represented by
Silver halide color photographic feeling characterized by containing
Light material. [0012] Embedded image [Wherein, R₁And R_ThreeIs a branched alkyl
Group, substituted alkyl group, substituted aryl group or heterocyclic group
Represents, R_TwoAnd R_FourRepresents a substituent, and X₁And X_Two
Reacts with a hydrogen atom or an oxidized form of a color developing agent, respectively.
Represents a group capable of leaving more. ] [0014] [0015] [0016] [0017] [0018] Embedded image[Wherein, R₃₁And R₃₂Is a secondary alkyl
Represents a group. R₃₃And R₃₄Represents a substituent, and R₃₅And R
₃₆Represents a hydrogen atom or a substituent. n₃₁And n₃₂Is
Represents an integer of 0 to 3. ] [0020] [0021] [0022] [0023] In the general formulas (1) and (2),
And R₁And R_ThreeAs the branched alkyl group represented by
Propyl group, t-butyl group, sec-butyl group, i-butyl
Examples thereof include a tyl group and a t-octyl group. The alkyl component of the substituted alkyl group includes
It may be a straight-chain, branched or cyclic alkyl group,
Group, ethyl group, butyl group, i-propyl group, t-butyl
Group, sec-butyl group, i-butyl group, t-octyl
And cyclohexyl groups. The aryl component of the substituted aryl group includes
Examples include a phenyl group. Examples of the heterocyclic group include a 2-furyl group and a 2-thio group.
Enyl group, 2-imidazolyl group, 2-thiazolyl group, 3
-Isoxazolyl group, 3-pyridyl group, 2-pyridyl
Group, 2-pyrimidyl group, 3-pyrazolyl group, 2-benzo
And a thiazolyl group. R₁And R_ThreeIs a branched alkyl group or hetero
When a ring group is represented, these groups may have a substituent, if necessary.
May have. There are no particular restrictions on these substituents.
But typically, alkyl, aryl, anilino,
Ruamino, sulfonamide, alkylthio, arylthio
O, alkenyl, cycloalkyl, etc.
But also a halogen atom, cycloalkenyl,
Quinyl, heterocycle, sulfonyl, sulfinyl, phosphoni
, Acyl, carbamoyl, sulfamoyl, cyano,
Alkoxy, aryloxy, heterocyclic oxy, siloxy
Si, acyloxy, sulfonyloxy, carbamoylo
Xy, amino, alkylamino, imide, ureido,
Rufamoylamino, alkoxycarbonylamino, a
Reeloxycarbonylamino, alkoxycarbonyl
, Aryloxycarbonyl, heterocyclic thio, thioure
Id, carboxyl, hydroxyl, mercapto, nit
B, sulfo, etc., spiro compound residue, bridge
Hydrocarbon compound residues are also included. In the general formulas (1) and (2), R_Two
And R_FourThe substituent represented by is not particularly limited.
Representatively, alkyl, aryl, anilino, acylamido
No, sulfonamide, alkylthio, arylthio, a
Examples include groups such as alkenyl and cycloalkyl.
Other than halogen atoms, cycloalkenyl, alkynyl
, Heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, carbamoyl, sulfamoyl, cyano, al
Coxy, aryloxy, heterocyclic oxy, siloxy, a
Siloxy, sulfonyloxy, carbamoyloxy,
Amino, alkylamino, imide, ureido, sulfa
Moylamino, alkoxycarbonylamino, aryl
Oxycarbonylamino, alkoxycarbonyl, ant
Oxycarbonyl, heterocyclic thio, thioureido,
Ruboxyl, hydroxyl, mercapto, nitro, sulf
Each group such as e, spiro compound residue, bridged hydrocarbon
Compound residues are also included. The above R₁, R_ThreeA branched alkyl represented by
Group, substituted alkyl group, substituted aryl group or heterocyclic group
And R and_Two, R_FourThe substituent represented by
As the alkyl group, those having 1 to 32 carbon atoms are preferable.
It may be linear or branched. As the aryl group, a phenyl group is preferred.
No. As the acylamino group, alkylcarbo
Nylamino group, arylcarbonylamino group and the like.
It is. As the sulfonamide group, alkylsulfone
Honylamino group, arylsulfonylamino group and the like.
Can be In the alkylthio group and the arylthio group
As the alkyl component and the aryl component, the above R_Two, R_FourIn table
Examples of the substituent include an alkyl group and an aryl group.
It is. As the alkenyl group, those having 2 to 32 carbon atoms are used.
And a cycloalkyl group having 3 to 12 carbon atoms,
5 to 7 are preferable, and the alkenyl group is linear or branched.
May be. The cycloalkenyl group may have 3 to 3 carbon atoms.
12, especially 5-7 are preferred. As the sulfonyl group, alkylsulfonyl
Group, arylsulfonyl group, etc .;
Alkylsulfinyl group, arylsulfinyl group and the like;
Examples of the phosphonyl group include an alkylphosphonyl group and an alkoxy group.
Cyphosphonyl group, aryloxyphosphonyl group, aryl
Ruphosphonyl group, etc .; acyl group is alkyl carbonyl
Group, arylcarbonyl group, etc .; as carbamoyl group
Is an alkylcarbamoyl group or an arylcarbamoyl group
Etc .; as the sulfamoyl group, alkylsulfamoyl
Group, arylsulfamoyl group, etc .;
Is an alkylcarbonyloxy group, an arylcarbonyl
An oxy group and the like;
Ruphonyloxy group, arylsulfonyloxy group, etc .;
As the rubamoyloxy group, alkylcarbamoyloxy
Si group, arylcarbamoyloxy group, etc .; ureido group
An alkylureido group, an arylureido group, etc .;
As the sulfamoylamino group, alkyl sulfamoyl
Amino group, arylsulfamoylamino group, etc .; heterocyclic ring
The group is preferably a 5- to 7-membered group.
Furyl, 2-thienyl, 2-pyrimidinyl, 2-
Benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl
A 5- to 7-membered heterocyclic ring as a heterocyclic oxy group;
Preferably, for example, 3,4,5,6-tetrahi
Dropranyl-2-oxy group, 1-phenyltetrazo
A 5-5-oxy group or the like; a 5- to 7-membered heterocyclic thio group
Is preferred, for example, 2-pyridylthio
Group, 2-benzothiazolylthio group, 2,4-diphenoxy
C-1,3,5-triazole-6-thio group and the like;
Examples of the silyl group include trimethylsiloxy and triethylsiloxy.
Si group, dimethylbutylsiloxy group, etc .;
Succinimide group, 3-heptadecyl succinimide
Group, phthalimide group, glutarimide group, etc .; spiro compound
Spiro [3.3] heptan-1-yl
Etc .; as a bridged hydrocarbon compound residue, bicyclo [2.
2.1] Heptan-1-yl, tricyclo [3.3.
1.1³⁷] Decan-1-yl, 7,7-dimethyl-bis
Black [2.2.1] heptane-1-yl and the like.
You. R_TwoAnd R_FourThe substituent represented by
A kill group and an aryl group are preferred, and an aryl group is particularly preferred.
New The above-mentioned groups may further include a long-chain hydrocarbon group and
It may have a substituent such as a non-diffusible group such as a mer residue. X₁And X_TwoOxidized color developing agent represented by
Examples of the group capable of leaving by the reaction with
Atoms (chlorine, bromine, fluorine, etc.) and alkoxy
Si, aryloxy, heterocyclic oxy, acyloxy,
Rufonyloxy, alkoxycarbonyloxy, aryl
Ruoxycarbonyl, alkyl oxalyloxy, al
Coxyoxalyloxy, alkylthio, arylthio
E, heterocyclic thio, alkyloxythiocarbonylthio,
Acylamino, sulfonamide, nitrogen-containing nitrogen-bonded
Elementary heterocycle, alkyloxycarbonylamino, aryl
Each group such as oxycarbonylamino and carboxyl is mentioned.
Can be X₁And X_TwoIs preferably a hydrogen atom, a halogen
Atom, alkoxy group, aryloxy group, alkylthio
Group, arylthio group, nitrogen-containing heterocyclic group linked by N atom
And so on. The shear represented by the general formulas (1) and (2)
Of the couplers, preferably represented by the general formula (1)
Things. In the following, formulas (1) and (2) are used.
Specific examples of cyan couplers are shown below.
The invention is not limited to this. [0044] Embedded image[0045] Embedded image[0046] Embedded image[0047] Embedded image[0048] Embedded image[0049] Embedded image[0050] Embedded image[0051] Embedded image[0052] Embedded image[0053] Embedded image[0054] Embedded image[0055] Embedded image[0056] Embedded image[0057] [0058] [0059] [0060] [0061] [0062] Next, the compound represented by the general formula [A-3]
explain about. R₃₁And R₃₂And a secondary alkyl group represented by
For example, i-propyl, s-butyl, s-pen
Groups such as tyl and s-hexyl groups. R₃₃, R₃₄, R₃₅And R₃₆The position represented by
Substitute groupAre, for example, alkyl, cycloalkyl, al
Kenyl, aryl, amide, sulfonamide, alkyl
Thio, arylthio, halogen atom, heterocycle, sulfoni
, Sulfinyl, phosphonyl, acyl, carbamoy
, Sulfamoyl, cyano, alkoxy, arylo
Xy, heterocyclic oxy, siloxy, acyloxy, carba
Moyloxy, amino, alkylamino, imide, uree
Id, sulfamoylamino, alkoxycarbonyla
Mino, alkoxycarbonylamino, aryloxyca
Rubonylamino, alkoxycarbonyl, aryloxy
Groups such as cicarbonyl and carboxy. [0066] [0067] [0068] [0069] [0070] [0071] [0072] The general formula [A-3]
Typical examples of the compounds to be used are shown below. [0074] [0075] [0076] [0077] Embedded image[0078] Embedded image[0079] Embedded image[0080] [0081] [0082] [0083] [0084] The general formula [A-3]
Two or more boiling solvents can be used in combination.
You. Emulsified and dispersed in hydrophilic protective colloid
To obtain fine particles, use a dispersing aid such as a surfactant.
, Stirrer, homogenizer, colloid mill, frog
Disperse by jet mixer, ultrasonic device, etc. dispersion
At the same time, a process for removing low boiling organic solvents may be included.
No. As the hydrophilic protective colloid, gelatin aqueous solution
Liquid is preferably used. The average particle size of the lipophilic fine particles is 0.04
μm to 2 μm is preferred, more preferably 0.06
μm to 0.4 μm. Particle size is from Coulter, UK
It can be measured with a Coulter model N4 or the like. In the above, the coupler, high boiling point solvent and
And low-boiling solvents or auxiliary solvents such as water-miscible organic solvents
The mixing ratio of couplers and high-boiling solvents is
The resulting solution is easily dispersed in the hydrophilic colloid
The viscosity should be selected so as to be suitable for High boiling point solution used
The ratio (weight ratio) of the medium to the coupler is 1:20 to 5:
1, preferably 1:10 to 2: 1. The silver halide color photographic light-sensitive material of the present invention
The photosensitive silver halide emulsion layer contains a silver halide emulsion.
Have. The silver halide emulsion of the present invention includes
Silver, silver bromide, silver iodide or mixed silver halide, for example
Apply silver chlorobromide, silver bromoiodide, silver chloroiodide, silver chloroiodobromide, etc.
Can be These silver halide emulsions
Manufactured by the ammonia method, neutral
Method, acid method, halogen conversion method, function addition method,
A single precipitation method or the like can be applied. Any average particle diameter
However, 0.01 μm to 5 μm is preferable. Formed separately
Two or more silver halide emulsions 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. Chemistry
For sensitization, a gold sensitization method using a gold complex salt and a reducing substance are used.
Reduction sensitization, sulfur-containing compounds that can react with silver ions
And so-called sulfur sensitization method using active gelatin, and periodic table
Using a sensitization method using a salt of a noble metal belonging to Group VIII
Can be The silver halide emulsion used in the present invention is
Spectral sensitization can be performed. As a method,
Methine cyanine, pentamethine cyanine, merocyanine
Cyanine dyes such as
May be used in combination or with styryl dyes or
This can be done in combination with a minostilbene compound, etc.
Can be. For the silver halide emulsion used in the present invention,
Is a stabilizer, antifoggant, surfactant, defoamer,
Inhibitor, hardener, film property improver, whitening agent, stain inhibitor,
Contains additives such as UV absorbers and irradiation inhibitors
You can have. About these various additives
Research Disclosure Volume 176,
No. 17643 (1978)
Are all available. 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, cell
Loose acetate film, polyethylene terephthalate
Film, polystyrene film, polycarbonate
Film, or a laminate thereof, paper, baryta paper, α-
Paper, synthetic paper, glass, coated with olefin polymer,
There are metals and the like. In the above color photographic light-sensitive material,
Gelatin should be used
Advantageously, but other hydrophilic colloids, such as Zera
Tin derivatives, graft polymers of gelatin and other polymers
-, Hydroxyethyl cellulose, carboxymethyl cellulose
Cellulos such as cellulose and cellulose sulfates
Base derivative, polyvinyl alcohol, polyvinyl alcohol
Acetal, poly-N-vinylpyrrolidone, poly
Acrylic acid, polymethacrylic acid, polyacrylamide, etc.
Synthetic hydrophilic polymers such as mono- or copolymers
Substances and the like can be mixed and used. Processing of the silver halide photographic light-sensitive material of the present invention
There is no particular limitation on the method,
Any processing method can be applied. For example, the typical one
After color development, perform bleach-fixing and, if necessary,
Water washing and / or stabilizing treatment, after color development,
Bleaching and fixing are performed separately, and if necessary, washing and / or
Or a method that performs stable processing, whichever method is used
The silver halide color photographic light-sensitive material of the present invention may be used.
The materials are processed for color development, bleach-fixing, washing (or stabilization).
Suitable for rapid processing. [0098] EXAMPLES Specific examples of the present invention will be described below.
Embodiments of the invention are not limited to this. Embodiment 1 Laminate polyethylene on one side of the paper support and
Laminate polyethylene containing titanium oxide on one side
Each layer of the following composition is placed on the support
Coating on the side of polyethylene layer containing
Sample 1 of silver color photographic light-sensitive material2, 5, 43-60
Produced. The coating solution was prepared as follows. First layer coating solution Yellow coupler (Y-1) 26.7 g, dye image stable
Agent (ST-1) 10.0 g, dye image stabilizer (ST
-2) 6.67 g, additive (HQ-1) 0.67 g, a
0.335 g of anti-radiation dye (AI-3), high
Ethyl acetate 60m in 6.67g of boiling point organic solvent (DNP)
1 and dissolved, and this solution is added with a 20% surfactant (SU-
1) 220 ml of 10% gelatin aqueous solution containing 7 ml
Emulsified and dispersed using an ultrasonic homogenizer
A coupler dispersion was prepared. This dispersion was prepared under the following conditions.
Blue-sensitive silver halide emulsion (containing 8.68 g of silver)
) To prepare a first layer coating solution. The coating solutions for the second to seventh layers are also the same as those for the first layer.
Was prepared in the same manner as described above. As a hardening agent, (H) was added to the second and fourth layers.
-1) and (H-2) were added to the seventh layer. Coating aid and
And then add surfactants (SU-2) and (SU-3)
Then, the surface tension was adjusted. In addition, silver halide photographic materials
The amount added in the ingredients is 1 m unless otherwise specified.^TwoGram per
Indicates a number. [0103] [Table 1][0104] [Table 2] [0105] Embedded image[0106] Embedded image [0107] Embedded image[0108] Embedded image[0109] Embedded image[0110] Embedded image[0111] Embedded image (Method for Preparing Blue-Sensitive Silver Halide Emulsion) 4
Place in 1000 ml of 2% aqueous gelatin solution kept at 0 ° C.
The above (solution A) and (solution B) were pAg = 6.5 and pH = 3.
0, and simultaneously added over 30 minutes.
(Solution C) and (Solution D) were pAg = 7.3, pH = 5.
5 and simultaneously added over 180 minutes. pH control
Control using an aqueous solution of sulfuric acid or sodium hydroxide.
Was. For control of pAg, a control solution having the following composition was used. control
The composition of the liquid is a mixture of sodium chloride and potassium sulfide.
Aqueous halide salt solution, chloride ion and bromide
The ion ratio is 99.8: 0.2, and the concentration of the control solution is
Is 0.1 mol / litre when mixing solution A and solution B
When mixing C, D and D
Was. [0113] (A liquid)   3.42 g of sodium chloride   Potassium bromide 0.03g   200 ml with water Finished. [0114] (B liquid)   Silver nitrate 10g   200 ml with water Finished. [0115] (Liquid C)   Sodium chloride 102.7g   1.0 g of potassium bromide   600 ml with water Finished. [0116] (D liquid)   Silver nitrate 300g   600 ml with water Finished. After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
aUse 5% aqueous solution and 2.0% aqueous solution of magnesium sulfate
After desalting, mix with gelatin aqueous solution and average
Particle size 0.85μm, coefficient of variation 0.07, silver chloride content
99.5 mol% of a monodispersed cubic emulsion EMP-1 was obtained. The following compound was added to the above emulsion EMP-1.
Perform chemical ripening at 50 ° C for 90 minutes to obtain a blue-sensitive halogen
Thus, a silver halide emulsion (Em-B) was obtained. [0119]   Sodium thiosulfate 0.8mg / mol AgX   Chloroauric acid 0.5mg / mol AgX   Stabilizer STAB-1 6 × 10^-FourMol / mol AgX   Sensitizing dye BS-1 4 × 10^-FourMol / mol AgX   Sensitizing dye BS-2 1 × 10^-FourMol / mol AgX (Preparation Method of Green-Sensitive Silver Halide Emulsion)
Solution (C) and (C solution) and (D)
Except for changing, the same as EMP-1,
3 μm, coefficient of variation 0.08, silver chloride content 99.5 mol
% Of a monodispersed cubic emulsion EMP-2. EMP-2
On the other hand, chemical aging was performed at 55 ° C for 120 minutes using the following compounds.
Then, a green-sensitive silver halide emulsion (Em-G) was obtained. [0120]   Sodium thiosulfate 1.5mg / mol AgX   Chloroauric acid 1.0mg / mol AgX   Stabilizer STAB-1 6 × 10^-FourMol / mol AgX   Sensitizing dye GS-1 4 × 10^-FourMol / mol AgX (Method for Preparing Red-Sensitive Silver Halide Emulsion) (A Solution) and (B)
Solution (C) and (C solution) and (D)
Except for further changes, in the same manner as EMP-1,
0 μm, coefficient of variation 0.08, silver chloride content 99.5 mol
% Of a monodispersed cubic emulsion EMP-3 was obtained. EMP-3
On the other hand, chemical ripening was performed at 60 ° C for 90 minutes using the following compounds.
A red-sensitive silver halide emulsion (Em-R) was obtained. [0121]   Sodium thiosulfate 1.8mg / mol AgX   Chloroauric acid 2.0mg / mol AgX   Stabilizer STAB-1 6 × 10^-FourMol / mol AgX   Sensitizing dye RS-1 1 × 10^-FourMol / mol AgX The coefficient of variation is a value obtained by dividing the standard deviation of the particle size by the average particle size.
It is. [0122] Embedded imageThe obtained sample was evaluated by the following method.
Value. <Evaluation of Relative Sensitivity> For each sample,
0.5 seconds for sensitometry through filter
After exposure, development processing of the following steps was performed. Obtained
The sample obtained was used as an optical densitometer (PDA-65 manufactured by Konica Corporation).
), And the sensitivity and maximum density (Dma
x) was determined. <Evaluation of storage stability>
After application, in an environment of 25 ° C. and 60% (relative humidity),
After storage for one day and three months, exposure and processing are performed as described above.
The sensitivities of the two were compared. Sensitivity comparison is performed one day after application.
The sensitivity of the sample after storage for 3 months is 100
Expressed as sensitivity. <Evaluation of sensitivity fluctuation due to humidity change during exposure>
Value> Keep the ambient temperature during exposure constant at 25 ° C, and
Change the humidity between 15% and 80%, compare the sensitivity,
A test for sensitivity fluctuation due to a change in ambient humidity during light was performed.
The comparison of the sensitivity is 100 when the relative humidity is 15%.
The sensitivity at a relative humidity of 80% was expressed as a relative sensitivity. The processing conditions are as follows. [0128] Processing process Temperature Time Color development 35.0 ± 0.3 ° C 45 seconds Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds Stabilization 30-34 ° C 90 seconds Drying 60-80 ° C 60 seconds Color developer   800ml pure water   Triethanolamine 10g   N, N-diethylhydroxylamine 5g   Potassium bromide 0.02g   Potassium chloride 2g   0.3 g of potassium sulfite   1.0 g of 1-hydroxyethylidene-1,1-diphosphonic acid   1.0 g of ethylenediaminetetraacetic acid   Catechol-3,5-disulfonic acid disodium salt 1.0 g   10 g of diethylene glycol   N-ethyl-N-β-methanesulfonamide   4.5 g of ethyl-3-methyl-4-aminoaniline sulfate (CD-3)   Fluorescent whitening agent (4,4'-diaminostilbene sulfonic acid derivative) 1.0 g   Potassium carbonate 27g   Add water to bring the total volume to 1 liter and adjust to pH = 10.10. [0129] Bleaching fixer   Ferric ammonium ethylenediaminetetraacetate dihydrate 60g   3 g of ethylenediaminetetraacetic acid   Ammonium thiosulfate (70% aqueous solution) 100ml   Ammonium sulfite (40% aqueous solution) 27.5ml   Add water to make the total volume 1 liter, and adjust the pH to 5.7 with potassium carbonate or glacial acetic acid. adjust. [0130] Stabilizing liquid   0.2 g of 5-chloro-2-methyl-4-isothiazolin-3-one   1,2-benzisothiazolin-3-one 0.3 g   1.0 g of ethylene glycol   1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g   1.0 g of sodium o-phenylphenol   1.0 g of ethylenediaminetetraacetic acid   Ammonium hydroxide (20% aqueous solution) 3.0 g   Fluorescent brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.5 g   Add water to make the total volume 1 liter, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide. adjust. Further, the obtained sample was treated in the same manner as described above.
After exposure, color development of the color developer of the above-mentioned processing step
The same except that the amount of the main drug, CD-3, was 3.5 g / l.
Processing by the same process as above, the maximum density of the red-sensitive layer
(Dmax ') was measured. The sample 12, 5, 43-60
Was evaluated for color reproducibility by the following method. First, a color negative film (Konica Color)
LV-400: Konica Corporation) and camera (Konica F
T-1 MOTOR: manufactured by Konica Corporation)
I photographed a color checker manufactured by Beth. Next, color
Perform negative development (CNK-4: Konica Corporation)
Konica Color Printer CL-
Using P2000 (manufactured by Konica Corporation)
o. Pudding in the size of 82mm x 117mm in 1-20
Then, a practical print was obtained in the same manner as described above. Print
When printing, the gray conditions on the color checker
Make settings for each sample so that it is gray on the print.
Was. Color reproducibility of the obtained practical print
Was visually evaluated. The results are tabulated5Are shown together. [0136] [0137] Embedded image[0138] [0139] [0140] [0141] [0142] [0143] [0144] [0145] [0146] [0147] [Table 5] As is clear from Table 5, a system outside the present invention was used.
Sample No. using an uncoupler and HBS outside the present invention.
1 and No. 1 2 is sensitivity, maximum density, raw preservability, at the time of exposure
Humidity dependence, processing variability, and color reproducibility are not sufficient.
hard. Further, the cyan coupler outside the present invention and the HB of the present invention
No. S using sample No. 43 and No. 44 is the highest density
Although slight improvements in degree and color reproducibility are observed,
It is hard to say that the humidity dependency at the time of exposure is sufficient. On the other hand, the cyan coupler of the present invention and the
Sample No. using HBS 5 for color development and raw storage
Although some effects are observed, both processing variability and color reproducibility
Not enough. On the other hand, Sample No. 46 ~ sample
No. 60 has high sensitivity, maximum concentration, and raw preservability
Is good, humidity dependence during exposure, process variability,
It is very good in terms of its actuality. [0151] [0152] [0153] [0154] [0155] [0156] [0157] [0158] [0159] [0160] [0161] According to the present invention, raw preservability, humidity at the time of exposure
Excellent dependence, color development, color reproducibility, and processing variability
Providing excellent silver halide color photographic materials
Was completed.

Claims (1)

(57) Claims: 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 (2). At least one of cyan couplers and the following general formula [A-
3 ) A silver halide color photographic light-sensitive material comprising at least one non-color-forming compound represented by the following formula: Embedded image [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 represent a hydrogen atom Or a group capable of leaving by reaction with an oxidized form of a color developing agent. [Chemical formula 4] [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 are integers from 0 to 3
Represents ]