JP3491215B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] This invention relates to silver halide color photography.
For photosensitive materials, specifically, low fog and high color density
Halo with excellent color reproducibility and rapid processing
It relates to a silver genide color photographic light-sensitive material. [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
The process has been shortened and speeded up, and rapid processing is possible
Are increasingly demanding. However, halogenation satisfying this requirement
The fact is that silver photographic light-sensitive materials have not been found yet. [0009] SUMMARY OF THE INVENTION The object of the present invention is to
Low color, high color density, excellent color reproducibility, and quick
Silver halide color photographic materials capable of high-speed processing
To provide. [0010] SUMMARY OF THE INVENTION The object of the present invention is to
Blue-sensitive silver halide emulsion layer on support, green-sensitive halide
A photographic structure including a silver emulsion layer and a red-sensitive silver halide emulsion layer
A red-sensitive silver halide emulsion layer having the following general formula:
(1)soContaining at least one of the cyan couplers represented by
And the green-sensitive silver halide emulsion layer has the following general formula:
At least one of the magenta couplers represented by [MI]
Silver halide color photography characterized by containing seeds
Achieved by photosensitive material. [0011] [Chemical formula 3] [Wherein R₁ IsBranched alkyl group, substituted alkyl
A kill group, a substituted aryl group or a heterocyclic group;_Two Is
X represents a substituent₁ IsShow hydrogen or chlorine atom
You. ] [0013] Embedded image [Wherein R represents a hydrogen atom or a substituent.
And Z is a nonmetallic atom necessary to form a nitrogen-containing heterocyclic ring.
Represents a group, and the ring formed by Z may have a substituent
Good. X is a hydrogen atom or an antioxidant of a color developing agent
Represents a group capable of leaving upon reaction. Hereinafter, the present invention
It will be described in detail. First, the general formula (1) of the present invention)soShea represented
The coupler will be described in detail. The general formula (1))Where R ₁ ofRepresent
Examples of the branched alkyl group include i-propyl group, t-butyl
Group, sec-butyl group, i-butyl group, t-octyl group
And the like. 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. R ₁ IsA branched alkyl or heterocyclic group
When represented, these groups may have a substituent, if necessary.
Is also good. 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. The general formula (1))Where R _Two ofReplace
The group is not particularly limited, but typically, alkyl,
Aryl, anilino, acylamino, sulfonamide,
Alkylthio, arylthio, alkenyl, cycloal
And other groups such as a halogen atom and a halogen atom.
And cycloalkenyl, alkynyl, heterocycle, sulfoni
, Sulfinyl, phosphonyl, acyl, carbamoy
, Sulfamoyl, cyano, alkoxy, arylo
Xy, heterocyclic oxy, siloxy, acyloxy, sulfo
Nyloxy, carbamoyloxy, amino, alkyla
Mino, imide, ureido, sulfamoylamino, al
Coxycarbonylamino, aryloxycarbonyla
Mino, alkoxycarbonyl, aryloxycarboni
, Heterocyclic thio, thioureido, carboxyl, hydro
Each group such as xyl, mercapto, nitro, sulfo, etc.
Also include spiro compound residues, bridged hydrocarbon compound residues, etc.
Can be These groups are further substituted by the above substituents.
You may. The above, R ₁ soBranched alkyl represented
Group, substituted alkyl group, substituted aryl group or heterocyclic group
And R and _Two soIn the substituents represented,
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, _Two soExpressed
Alkyl and aryl groups in the substituents
No. As the alkenyl group, one having 2 to 32 carbon atoms is 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 _Two ofAs the substituent represented, alkyl
Groups and aryl groups are preferred, and aryl groups are particularly preferred.
No. The above groups further include a long-chain hydrocarbon group and
It may have a substituent such as a non-diffusible group such as a mer residue. X ₁ IsIt is a hydrogen atom or a chlorine atom. [0033] The general formula (1))soCyan represented
Specific exemplary compounds of the coupler are shown, but the present invention
However, the present invention is not limited to this. [0035] Embedded image [0036] Embedded image[0037] Embedded image[0038] Embedded image[0039] [Chemical formula 9] [0040] Embedded image[0041] Embedded image[0042] [Chemical formula 12] [0043] [Chemical formula 13] [0044] Embedded image[0045] Embedded image[0046] [0047] Next, the present invention is represented by the general formula [MI].
The magenta coupler will be described. In the general formula [MI]
The substituent represented by R 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, sulfamoyl, cyano, alkoxy, aryl
Ruoxy, heterocyclic oxy, siloxy, acyloxy,
Rubamoyloxy, amino, alkylamino, imide,
Ureido, sulfamoylamino, alkoxycarboni
Ruamino, aryloxycarbonylamino, alkoxy
Cycarbonyl, aryloxycarbonyl, heterocyclic thio
, And spiro compound residues, bridged hydrocarbon compounds
Product residue and the like. The alkyl group represented by R has the number of carbon atoms
It is preferably from 1 to 32, and may be linear or branched. The aryl group represented by R is phenyl
Preferred is a phenyl group. The acylamino group represented by R includes a
Alkylcarbonylamino group, arylcarbonylamino
And the like. As the sulfonamide group represented by R,
Alkylsulfonylamino group, arylsulfonylamino
And the like. An alkylthio group or an arylthio group represented by R
The alkyl component and the aryl component in the O group are represented by the above R.
Alkyl group and aryl group. The alkenyl group represented by R includes carbon
A cycloalkyl group having 3 to 32 carbon atoms,
To 12, particularly preferably 5 to 7, and the alkenyl group is preferably
It may be linear or branched. As the cycloalkenyl group represented by R
Preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. As the sulfonyl group represented by R, alkyl
Rusulfonyl group, arylsulfonyl group, etc .; Sulfini
Alkylsulfinyl, arylsulfinyl
Finyl group, etc .;
Group, alkoxyphosphonyl group, aryloxyphospho
Acyl group, arylphosphonyl group, etc .;
Alkylcarbonyl group, arylcarbonyl group, etc .;
Moyl groups include alkylcarbamoyl groups and arylca
Rubamoyl group, etc .; sulfamoyl groups include alkyls
Rufamoyl group, arylsulfamoyl group, aryl
Sulfamoyl group, etc .; alkyl as acyloxy group
Carbonyloxy group, arylcarbonyloxy group and the like;
As the ureido group, an alkylureido group, an aryluree
Sulfamoylamino groups include alkyls
Rufamoylamino group, arylsulfamoylamino
A heterocyclic group is preferably a 5- to 7-membered heterocyclic group;
Physically, 2-furyl, 2-thienyl, 2-pyrimidi
And a heterocyclic oxy group.
Are preferably those having a 5- to 7-membered heterocyclic ring.
3,4,5,6-tetrahydropyranyl-2-oxy
Group, 1-phenyltetrazol-5-oxy group, etc .;
As the ring thio group, a 5- to 7-membered heterocyclic thio group is preferable.
For example, 2-pyridylthio group, 2-benzothiazolyl
Thio group, 2,4-diphenoxy-1,3,5-triazo
Thiol group, etc .;
Roxy group, triethylsiloxy group, dimethylbutylsilo
Succinimide group, 3-hepc as imide group
Tadecyl succinimide group, phthalimide group, glutar
An imide group or the like; a spiro compound residue such as spiro [3.
3] heptane-1-yl and the like; a bridged hydrocarbon compound residue
Bicyclo [2.2.1] heptan-1-yl,
Licyclo [3.3.1.1^3.7Decane-1-yl,
7,7-dimethyl-bicyclo [2.2.1] heptane-
1-yl and the like. For the reaction of the color developing agent represented by X with the oxidized form,
Examples of the more removable group include a halogen atom (chlorine
Atom, bromine atom, fluorine atom etc.) and alkoxy, aryl
Ruoxy, heterocyclic oxy, acyloxy, sulfonylo
Xy, alkoxycarbonyloxy, aryloxyca
Rubonyl, alkyloxalyloxy, alkoxyoxy
Zalyloxy, alkylthio, arylthio, heterocyclicthio
E, alkyloxythiocarbonylthio, acylamido
, A sulfonamide, a nitrogen-containing heterocycle linked by an N atom,
Alkyloxycarbonylamino, aryloxycar
Bonylamino, carboxyl, [0058] Embedded image (R₁′ Has the same meaning as R above, and Z ′
Synonymous with the notation Z,_Two'And R_Three'Is a hydrogen atom, ally
Represents an alkyl group, an alkyl group or a heterocyclic group. ) Etc.
But preferably with a halogen atom, especially a chlorine atom
is there. The nitrogen-containing complex formed by Z or Z '
As the prime ring, a pyrazole ring, an imidazole ring, a tria ring
A sol ring or a tetrazole ring;
The substituents which may be mentioned are those described for R above.
No. Hereinafter, the compound according to the general formula [MI] of the present invention will be described.
The typical specific examples of the compounds are shown. [0062] Embedded image[0063] Embedded image[0064] Embedded image[0065] Embedded image[0066] Embedded image[0067] Embedded image[0068] Embedded image[0069] Embedded image[0070] Embedded image[0071] Embedded image[0072] Embedded image[0073] Embedded image[0074] Embedded image The cyan coupler or magenta according to the present invention
In order to incorporate a coupler into the photographic light-sensitive material of the present invention,
For ordinary cyan coupler or magenta coupler
Any known technique can be applied. Dissolve coupler with high boiling point
If necessary, dissolve the solvent in combination with a low boiling point solvent
Dispersed in the form of particles and added to the silver halide emulsion of the present invention.
Preferably. At this time, if necessary, hydroquinone
Derivatives, UV absorbers, anti-fading agents, etc. can be used together
can not use. The photographic light-sensitive material of the present invention is a full-color light-sensitive
When used as a material, the cyan cap according to the present invention
Color and magenta couplers and yellow couplers
It is. Yellow couplers are known without particular limitation.
Can be used. As the yellow coupler, for example,
Tomethylene-based couplers can be used. The silver halide emulsion in the present invention is probably
Either a dispersed emulsion or a monodispersed emulsion may be used.
Dispersed emulsions are preferred. The preferred monodisperse emulsion in the present invention is
Included within a particle size range of ± 20% around the amount average particle size d
The weight of silver halide is not less than 70% of the total weight of silver halide
And more than 80%
Those that account for 90% or more are particularly preferred. Grain form of silver halide used in the present invention
Shapes are regular crystals such as cubes, octahedrons, and tetradecahedrons
Having an irregular crystal form such as a sphere or a plate
Some have crystal defects such as twin planes
Or a composite form thereof may be used. The crystal structure is uniform
Also, the inside and outside are made of different halogen compositions.
Or a layered structure. Also, Epitaki
Silver halides with different compositions are joined by a char junction.
May be used.
It may be bonded to a compound other than silver logenide. Also
A mixture of particles of different crystal forms may be used. In the present invention, a tabular halogenated
When using a silver halide emulsion containing silver grains,
Tabular silver halide grains having a diameter / thickness ratio of 2 to 8 are
In the projected area, more than 70% of all particles exist
And a flat plate having a diameter / thickness ratio of 3 to 7.
Silver halide grains account for 70% of all grains in projected area
It is preferable that they are present in the above ratio. Adsorbability on the surface of silver halide grains
The substance can be added at any temperature,
Preferably added at 80 ° C, for the purpose of enhancing adsorptivity
In this case, the addition is preferably performed within the range of 50 to 80 ° C.
The pH and pAg values can be arbitrarily set, but the chemical sensitization
At the time of performing, it is preferable that the pH is 6-9 and the pAg is 8-9.
New Adsorbability on the surface of silver halide grains
Although any substance can be used,
Emulsion preparation of dyes, antifoggants, photographic performance stabilizers, etc.
It is preferable to use substances required in the process. When a photographic performance stabilizer is used,
The addition amount is 500 to 3,000 per mole of silver halide.
mg, more preferably 1,000 to 2,500 mg.
Good. When a sensitizing dye is used,
Is from 500 to 2,000 mg per mole of silver halide
Preferably, 600-1,000 mg is more preferable. Examples of the photographic performance stabilizer include Research
・ Disclosure (RD) No. 308119, No.
No. 998, VI, ibid. 17643, pp. 24-25, ibid.
No. 18716, p. 649
Can be Research sensitizing dyes include research and
Disclosure (RD) No. 308119, ninth
Page 96 VI-AA, B, C, D, H, I, J, N
o. No. 17643, pp. 23-24, ibid. 1871
6, Listed on pages 648-649
Can be. The silver halide photographic light-sensitive material of the present invention includes
Can contain various photographic additives. An example
For example, antifoggant, development accelerator, development retarder, bleach acceleration
Agents, stabilizers, UV absorbers, color stain inhibitors, fluorescent whitening
Agent, color image anti-fading agent, antistatic agent, hardener, surface activity
Agents, plasticizers, wetting agents and the like can be used. (RD1
No. 7643 can be referred to. ) Further coupling with competitive couplers and oxidized developing agents
Development accelerator, bleach accelerator, developer, halogen
Silver halide solvents, toning agents, hardeners, fogging agents, antifogging agents,
Photographers such as chemical sensitizers, spectral sensitizers, and desensitizers
Use compounds that release useful fragments
Wear. Support of the silver halide photographic light-sensitive material of the present invention
The body is made of, for example, baryta paper, polyethylene coated paper, polyp.
Propylene synthetic paper, glass plate, cellulose acetate, cellulose
Lurose nitrate, polyethylene terephthalate, etc.
Polyester film, polyamide film, polycarbonate
-Carbonate film, polystyrene film, etc.
In the case of a transparent support, a reflective layer may be used in combination. These supports depend on the purpose of use of the light-sensitive material.
Selected as appropriate. Emulsion layer used in the present invention and its emulsion layer
Dip coating, air doc
Various coating methods such as tar coating, curtain coating, hopper coating
Method can be used. U.S. Pat. No. 2,781,7
No. 91, 2, 941, 898
A simultaneous coating method of more than two layers can be used. In the present invention, the coating position of each emulsion layer is determined.
Although it can be determined as desired, the blue sensitivity
Silver halide emulsion layer, green-sensitive silver halide emulsion layer, red-sensitive
The arrangement of the silver halide emulsion layers is preferred. In the light-sensitive material of the present invention, depending on the purpose,
Providing an intermediate layer of an appropriate thickness is optional, and
Filter layer, anti-curl layer, protective layer, anti-halation
Various layers such as a component layer are appropriately combined and used as constituent layers.
Can be These constituent layers are hydrophilic as binders.
Colloids can be used, and gelatin is preferred
You can. Further, in the layer, it is mentioned in the description of the emulsion layer.
And various photographic additives. Photographic feeling using the silver halide emulsion of the present invention
There is no particular limitation on the processing method of the optical material, which is generally known.
All known treatment methods can be applied. For example
As a typical example, bleach-fix processing is performed after color development.
If necessary, further wash and / or stabilize
Method and color development, bleaching and fixing are performed separately.
Any method of further washing with water and / or stabilizing treatment
The silver halide of the present invention
For color photographic light-sensitive materials, color development, bleach-fixing,
Or stabilization) process.
You. [0093] 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 a silver color photographic light-sensitive material was prepared. The coating liquid is below
Prepared as described. 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
0.33 g of anti-radiation dye (AI-3), high boiling
Ethyl acetate 60ml in 6.67g of point organic solvent (DNP)
And dissolve the solution, and add this solution to 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. [0098] [Table 1] [0099] [Table 2][0100] Embedded image[0101] Embedded image [0102] Embedded image [0103] Embedded image[0104] Embedded image[0105] Embedded image[0106] 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. [0108] (A liquid)   3.42 g of sodium chloride   Potassium bromide 0.03g   200 ml with water Finished. [0109] (B liquid)   Silver nitrate 10g   200 ml with water Finished. [0110] (Liquid C)   Sodium chloride 102.7g   1.0 g of potassium bromide   600 ml with water Finished. [0111] (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. [0114]   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. [0115]   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. [0116]   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. [0117] Embedded imageNext, in the sample 1, the cyan cap of the fifth layer was formed.
The couplers C-1 and C-2 are shown in Table 3
(Equivalent to the total number of moles of comparative couplers C-1 and C-2)
Table 3 shows the magenta coupler MM-1 of the third layer.
Puller (addition amount is the same as the number of moles of the comparative coupler MM-1)
Volume)), except that samples 2 to 22 were prepared in exactly the same manner.
Produced. The obtained sample was subjected to a wedge by a conventional method.
After exposure, development processing is performed to prevent fog of the red-sensitive layer.
(Fog) and the maximum concentration (Dmax) were measured. Further, the obtained sample was subjected to c
After giving the edge exposure, the processing time of the processing step is reduced to 30
Developed in the same process except for seconds,
The fog (Fog) and maximum density (Dmax ') of the optical layer
It was measured. The following samples 1 to 22 were used.
The color reproducibility was evaluated by the method. First, the color negative
Film (Konica Color LV-400: Konica Corporation)
(Made by Konica FT-1 MOTOR: Konica Corporation)
Using a Macbeth color checker
Shadowed. Subsequently, color negative development processing (CNK-4:
Nika Co., Ltd.) and the resulting negative image
Printer CL-P2000 (Konica Corporation)
Sample no. 82mm x 11 for 1-22
Print to a size of 7 mm,
Got lint. The printer conditions for printing are
-Make the gray on the checker gray on the print
Settings were made for each sample. The color reproducibility of the obtained practical prints
Was visually evaluated. The results are summarized in Table 3. The processing conditions are as follows. [0125] 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 bring the pH to 10.10
adjust. [0126] 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 add potassium carbonate or ice
Adjust to pH = 5.7 with acetic acid. [0127] 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 add sulfuric acid or potassium hydroxide.
Adjust the pH to 7.0 with water. [0128] [Table 3] [0129] Embedded imageAs is evident from Table 3, the shear outside the present invention was used.
Coupler and a magenta coupler outside the present invention were used.
Sample No. No. 1 to No. 1 3 is high fog and coloring
Color reproduction and rapid processing
You. Further, the cyan coupler of the present invention and magenta other than the present invention
The sample no. 4 is fog and coloring
Although slight improvement is observed in terms of color reproducibility, color reproducibility is not sufficient.
It's hard to say. On the other hand, the cyan coupler and the book
Sample No. using the magenta coupler of the present invention. 5 is mosquito
High speed, insufficient rapid processing, and sufficient color reproducibility
It's hard to say. On the other hand, the sample No. 6-trial
Charge No. No. 22 has low fog and good color developability
Yes, rapid processing and color reproducibility are very good. [0131] According to the present invention, fog is low and color density is low.
, High color reproducibility, and rapid processing
Can provide silver halide color photographic light-sensitive material
Was.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 7/38

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 contains at least one cyan coupler represented by the following general formula (1 ). A silver halide color photographic light-sensitive material, characterized in that the green-sensitive silver halide emulsion layer contains at least one magenta coupler represented by the following formula [MI]. Embedded image Wherein, R ₁ represents branched alkyl group, a substituted alkyl group, a substituted aryl group or a heterocyclic group, R ₂ represents a substituent, X ₁ is a hydrogen atom or a chlorine atom. [Chemical formula 2] [Wherein, R represents a hydrogen atom or a substituent, Z represents a group of non-metallic atoms necessary to form a nitrogen-containing heterocyclic ring,
The ring formed by may have a substituent. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. ]