JPH03215851A - Silver halide color photosensitive material having improved gradation characteristic - Google Patents

Abstract

PURPOSE:To provide the silver halide color photosensitive material having the gentle gradation from a high exposing area to a low exposing area and excellent development processing stability by specifying the spectral reflection density on a photosensitive layer side surface. CONSTITUTION:The photosensitive material contg. at least one kind of monodisperse silver halides and having 1.0 to 1.4 reflection density at 450nm in the spectral reflection density on the photosensitive layer side surface, 0.8 to 1.2 reflection density at 550nm or 0.6 to 1.0 reflection density at 650nm is used in the silver halide color photosensitive material contg. colloidal silver, colored couplers and water-soluble dyes on a base. Yellow colloidal silver and black colloidal silver are particularly useful as the kind of the colloidal silver and the coating amt. thereof is preferably 0.01 to 1.0g/m<2> yellow colloidal silver in terms of metal silver and 0.02 to 1.0g/m<2> black colloidal silver. Colored magenta couplers and colored cyan couplers are useful as the colored couplers.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color light-sensitive material, and more particularly to a silver halide color light-sensitive material with improved gradation.

[Prior art]

General-use negative color photography light-sensitive materials are loaded into cameras and used to photograph various subjects under various conditions. In order to be able to record images even if the exposure is slightly off from the appropriate exposure, or to record more image information,
It is designed to have a wide latitude. That is, by using two or more types of silver halide emulsions having the same color sensitivity but different sensitivities, image information from a high exposure area to a low exposure area can be recorded.

In recent years, monodisperse silver halide emulsions have come to be used. This makes the structure, size, and characteristics of silver halide grains uniform, and eliminates unnecessary grains to save silver, increase sensitivity, improve exposure characteristics, improve development processing characteristics, and improve image quality. This technology plays a part in the technological progress of silver halide photosensitive materials.

However, when producing the negative color photosensitive material, the characteristic curve from the high exposure area to the low exposure area (the horizontal axis is -1ogE, E: exposure amount, and the vertical axis is the image density D) must be smooth. On the other hand, the monodisperse emulsion has a large slope of the characteristic curve due to its uniformity, and it is difficult to combine two or more types of monodisperse silver halide emulsions with the same dispersion but different degrees of dispersion. It is difficult to obtain the smooth characteristic curve.

In the past, attempts have been made to overcome this difficulty by making the chemical sensitization and spectral sensitization of monodisperse emulsions nonuniform, using large amounts of development inhibitors, and mixing many monodisperse emulsions. However, it had the disadvantage of poor stability during development.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a silver halide color light-sensitive material which has smooth gradation from a high exposure area to a low exposure area and has low development processing stability.

[Structure of the invention]

The present invention was achieved as follows. That is, in a silver halide color photosensitive material containing colloidal silver, a colored coupler, and a water-soluble dye on a support, the photosensitive material contains at least one type of monodisperse silver halide,
And the spectral reflection density of the photosensitive layer side surface is 450
Reflection density in nm is 1.0 to 1.4, or 550
Reflection density in nm is 0.8-1.2, or 650
This is a silver halide color photosensitive material characterized by a reflection density in nm of 0.6 to 1.0.

As the colloidal silver used in the present invention, any known colloidal silver used in ordinary silver halide color luminescent materials can be used. As for the types of colloidal silver, yellow colloidal silver and black colloidal silver are particularly useful, and the coating amount of yellow colloidal silver is 0.01 to 1.0 g/m in terms of metallic silver.
”, preferably 0.02 to 0.5 g/m2, particularly preferably 0.05 to 0.3 g/m2, black colloidal silver 0.02 to I.Og/m2, preferably 0.04 to 0
．． 5 g/m2, particularly preferably 0.08-0.4 g/m2
It is m2. The layer to which colloidal silver is added is preferably a non-photosensitive layer that does not contain photosensitive silver halide.

The colored coupler used in the present invention has spectral absorption characteristics in the visible region even in an unreacted state, and any known color coupler used in ordinary silver halide color light-absorbing materials can be used. Particularly useful are colored magenta couplers and colored cyan couplers.

The colored magenta coupler according to the present invention is preferably represented by the following general formula.

General formula (T) Cp-N=N-R, where Cp represents a magenta coupler residue (however, the azo group is bonded to the active site of the magenta coupler),
R represents an aryl group (including one having a substituent).

The magenta coupler residue represented by Cp is preferably a coupler residue derived from a 5-virazolone magenta coupler or a virazolotriazole magenta coupler, and particularly preferred is represented by the following general formula CI1).

General formula [■] R2 In the formula, R2 represents an aryol group, R3 represents an acylamino group, anilino group, a ureido group, or a carbamoyl group, and each R2. R3 includes those each having a substituent.

The aryl group represented by R2 is preferably a phenyl group. Examples of substituents for the ryoryl group represented by R2 include halogen atoms (e.g., fluorine, chlorine, bromine, etc.), alkyl groups (e.g., methyl, ethyl, etc.), alkoxy groups (
For example, methoxy, ethoxy, etc.), aryloxy groups (
(e.g., phenyloxy, naphthyloxy, etc.), acylamino groups (e.g., penzamide, α-(2,4-di-t-amylphenoxy)butylamide, etc.), sulfonylamino groups (e.g., benzenesulfonamide, n-hexadecanesulfonamide, etc.) ), sulfamoyl groups (e.g., methylsulfamoyl, phenylsulfamoyl, etc.), carhamoyl groups (e.g., n-butylcarhamoyl, phenylcarhamoyl, etc.), sulfonyl groups (e.g., methylsulfonyl, n-dodecyl), sulfonyl, hensensulfonyl, etc.), an acyloxy group, an ester group, a carbogicyl group, a sulfo group, a cyano group, a nitro group, and the like.

Furthermore, specific examples of R2 include phenyl, 24.6-
}IJ chlorphenyl, pentachlorphenyl, pentafluorophenyl, 2,4.6-trimethylphenyl,
2-chloro-4,6-dimedylphenyl, 2,6-dichloro-4-methylphenyl, 24-dichloro-6-methylphenyl, 24-dichloro-6-methoxyphenyl, 2
, 6-dichloro-4methoxyphenyl, 2,6-dichloro-4-[α(2,4-di-L-amylphenoxy)acetamido]phenyl, and the like.

Examples of the acylamino group represented by R3 include bihaloylamino, n-tetradecanamide, α-(3-pentadecylphenoxy)butyramide, 3-[α-
(2,4-di-t-amylphenoxy)acetamide]
Examples include henzamide, penzamide, 3-acetamide henzamide, 3-(3-n dodecylsuccinimide) penzamide, 3(4-n-dodecyloxybenzenesulfonamide) penzamide, and the like.

Examples of the anilino group represented by R3 include anilino, 2-chloroanilino, 2,4-dichloroanilino, 2
．． 4-dichloro-5-methoxyanilino, 4-cyanoanilino, 2-chloro-5-[α(24-di-t-amylphenoxy)butylamido]anilino, 2-chloro-5
-(3-octadecenylsuccinimide)anilino, 2
-Chlor-5-n-tetradecanamide anilino, 2-chloro-5-[α-(3-t-butyl-4-hydroxyphenoxy)tetradecanamide]anilino, 2-chloro-5-n-hexadecanesulfonamide anilino etc.

Examples of the ureido group represented by R3 include methylureido, phenylureido, 3-[α(2,4-di-
Examples include t-amylphenoxy)butylamide] phenylureide.

The carbamoyl group represented by R3 is, for example, n-
Tetradecylcarbamoyl, phenylcarbamoyl, 3
-[α-(2,4-di-t-amylphenoxy)acetamido]phenylcarhamoyl and the like.

The aryl group represented by R+ is preferably a phenyl group or a naphthyl group.

Examples of substituents for the aryl group represented by R1 include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group,
Examples include hydroxy group, acyloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, sulfonamide group, carbamoyl group, and sulfamoyl group.

Particularly preferred substituents are an alkyl group, a hydroxyl group, an alkoxy group, and an acylamino group.

Next, colored mazene 9 represented by the general formula CHI) Here are some specific examples of evening couplers: This limits It's not something you can do.

CM1C! CM 2 Cβ 10 CM 3 CM 4 1 ECM 5 CM 6 1 2 CM 7 CM 8 CI! ．． 1 3 CM 9 r ρ C2 CM 1 0 ■ 4 CM 1 1 CM 1 2 rI7 C! CM 13 CI2 Shi! 1 5 CM 14 nff CP. CM 15 C7! U CM 16 C! 16 CM 17 CA CM 1 8 ■ 7 CM 19 CM 20 1 8 CM 21 r ρ C! CM-22 CM 23 1 9 CM 24 The colored magenta coupler according to the present invention is disclosed in Japanese Patent Application Laid-Open No.
-123625, 49-131448, 52
- No. 42121, No. 52-102723, No. 54
It can be synthesized according to the methods described in U.S. Pat. No. 52532, U.S. Pat.

Although the colored magenta coupler according to the present invention can be added to any layer, it is preferably added to at least one of the green-sensitive layers. The amount added is 0.001 to 0.1 mol, preferably 0.001 to 0.1 mol, per 1 mol of silver halide in the added layer.
005 to 0.05 mol, particularly preferably 0.01 to 0.05 mol.
03 mole.

20 The colored cyan coupler according to the present invention has the following general formula CI
A compound represented by II) is preferred.

General formula (III) COUP (J}i-N = N - RS In the formula, COUP represents a cyan coupler residue, * represents a camping site of the cyan coupler, J represents a divalent linking group, m represents O or 1, and R represents an aryl group.

The cyan coupler residue represented by COUP includes a phenol coupler and a naphthol coupler residue, and a naphthol coupler residue is particularly preferred.

A preferable divalent linking group represented by J can be represented by the following general formula [IV].

General formula (IV) 21 ? Middle Y is -o-. -s-, -o-c0 1l Represents O-C-O-.

In the formula, R6 represents an alkylene group having 1 to 4 carbon atoms or an arylene group, R7 represents an alkylene group having 1 to 4 carbon atoms, and the alkylene groups of R6 and R7 are an alkyl group, a carboxy group, a hydroxy group, or a sulfonate group. May be substituted with groups.

R9 Z is -c-, -o- -s- --soRI
G so2- , -so■NH - , -CONH-
, -CooNHC(1- ,-NHSO■1,
Represents -OCO-, Rq, R+. represents an alkyl group or an aryl group.

R8 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, a cyano group, a nitro group, a sulfonyl group,
Represents an alkoxy group, aryloxy group, carboxy group, sulfo group, halogen atom, carponamide group, sulfonamide group, carbamoyl group, 22 alkoxycarbonyl group, or sulfamoyl group.

p represents O or a positive integer, q represents 0 or 1, and r represents an integer from 1 to 4. When p is 2 or more, R
6 and Z may be the same or different. When r is 2 or more, R8 may be the same or different.

The aryl group represented by R5 is preferably a phenyl group or a naphthyl group when m=o.

The phenyl group and naphthyl group can have a substituent, and the substituent includes a halogen atom, an alkyl group,
Alkoxy group, aryloxy group, hydroxy group, acyloxy group, carpoxyl group, alkoxycarbonyl group, aryloxycarbonyl group, mercapto group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acylamino group, These include a sulfonamide group, a carbamoyl group, and a sulfamoyl group.

When x=1, the aryl group represented by R is preferably a naphthol group represented by the following general formula (V).

General formula [■] In the formula, Rl+ is a linear or branched alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a probyl group,
isoprobyl group, butyl group, S-butyl group, t-butyl group, etc.), and M is a photographically inactive cation, such as a hydrogen atom, an alkali metal cation such as sodium atom or potassium atom, or ammonium atom. , methylammonium, ethylammonium, diethylammonium,
Represents triethylammonium, ethanolammonium, diethanolammonium, pyridinium, piperidium, anilinium, toluidinium, p-nitroanilinium, anisidium, etc.

Next, representative colored 24 represented by the general formula CI[I] A specific example of a coupler is shown below. Although limited to this It's not.

CC 1 CC 2 25 CC 3 0H CC 4 26 CC 6 27 CC 7 CC 8 28 CC 9 OH CC 10 CC 1 1 29 CC 12 0H CC 13 CC 1 4 30 The above compounds are described in JP-A-50-123341, Same 55
No. 65957, No. 56-94347, Special Publication No. 1973
, No. 11304, No. 44-32461, No. 4B-1
No. 7899, No. 53-34733, U.S. Patent No. 3,
It can be synthesized by the method described in No. 034,892, British Patent No. 1,084,480, etc.

Although the colored cyan coupler according to the present invention can be added to any layer, it is preferably added to at least one of the red-sensitive layers. The amount of addition is 1 silver halide in the addition layer.
per mole, 0.001 to 0.1 mole, preferably 0.0
02 to 0.05 mol, particularly preferably 0.005 to 0.05 mol.
03 mole.

As the water-soluble dye used in the present invention, known dyes used in ordinary silver halide color light-sensitive materials can be used. Among these, oxonol-based, merocyanine-based, hengelidene-based, anthraquinone-based, cyanine-based, styryl-based, Ab-based, hemioxonol-based and the like are preferred, and those having acidic groups such as sulfonic acid groups and carboxylic acid groups are particularly preferred. Furthermore, in the present invention, the maximum absorption wavelength of the water-soluble dye in an aqueous solution is 420 nm to 480 nm.
1 or 520 nm to 580 nm, or 600 nm
Those within the range of nm to 680 nm are preferred.

Specific examples of water-soluble dyes useful in the present invention are shown below, but the invention is not limited thereto.

[Dye-1] l{ [Dye 2] CI{3 32 [Dye 3] H H [Dye 4] [Dye 5] 33 [Dye 6] [Dye 7] HOOC C C CH CH CH CH C-COOH [Dye 8 ] H. C C C CH CH CH CH C C CH3 34 [Dye 9] HOOC-C-C CH CH = Cl{ CH= =CH-C-C COOH [Dye 1 0] SOJ 35 [Dye 1 1] [Dye 1 2] [Dye 1 3] δU3κ SU3K 36 [Dye 1 4] In the present invention, a water-soluble dye can be added to any layer. The amount of water-soluble dye added varies depending on the molecular extinction coefficient, molecular weight, solubility, etc. of the dye used, but is usually 0.1 to 1000 mg/m2, preferably 0.
．． It is used in a range of 5 to 500 mg/m2.

In the present invention, the spectral reflection density of the surface of the photosensitive layer obtained mainly from colloidal silver, colored couplers, and water-soluble dyes contained in the silver halide color light-sensitive material has a reflection density of 1.0 to 1 at 450 nm. .4, or the reflection density at 550 nm is 0.8 to 1.2, or the reflection density at 650 nm is 0.6 to 1.0, preferably the reflection density at 450 nm is 1.0 to 1.2. or the reflection density at 550 nm is 0.8 to 1.0, or the reflection density at 650 nm is 0.6 to 0.8, particularly preferably the reflection density at 450 nm is 1.0 to 1.2, and 5
Reflection density at 50 nm is 0.8 to 1.0 and 65
The reflection density at 0 nm is 0.6 to 0.8.

In the present invention, an ordinary spectral reflection densitometer can be used to measure the spectral reflection density of the surface of the photosensitive layer side of the silver halide color photosensitive material. However, in order to prevent slight blackening, use a spectral reflection densitometer in which the measurement light irradiated onto the sample surface is pre-spectralized measurement light, such as the Hitachi self-recording spectrophotometer U-3210. It is preferable.

In the present invention, a monodisperse silver halide emulsion is one in which the weight of silver halide contained within a grain size range of ±20% around the average grain size is 70% or more of the total weight of silver halide. It is preferably 8o38% or more, more preferably 90% or more.

Here, the average particle size d is the frequency n of particles with particle size d,
The particle diameter d is defined as when the product rzXd13 of and d,3 is maximum. (3 significant figures, minimum digit is 4 to 5
The particle size referred to here is the diameter when the projected image of the particle is converted into a circular image with the same area.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print. (The number of particles to be measured is assumed to be 1000 or more indiscriminately.

) Preferred highly monodisperse emulsions of the present invention have a distribution width defined by 20% or less, more preferably 15% or less, particularly preferably 12% or less.

Here, the particle size measurement method shall follow the measurement method described above,
The average particle size is a simple average.

39 A monodisperse emulsion can be obtained by adding a water-soluble silver salt solution and a water-soluble halide solution to a gelatin solution containing seed particles by the double gelation method under control of pllg and pH. When determining the addition rate, please refer to Japanese Patent Application Laid-Open No.
- No. 48521 and No. 58-49938 can be referred to.

A method for obtaining a more advanced monodisperse emulsion is disclosed in Japanese Patent Application Laid-Open No. 1983-
The growth method in the presence of a tetrazaindene compound disclosed in Japanese Patent No. 122935 can be applied.

The monodispersed emulsion of the present invention can be of any composition, such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc., but silver iodobromide is preferred, and silver iodobromide is particularly preferred. Preferably, the silver oxide content is 1 mol % or more and 10 mol % or less.

The monodisperse emulsion of the present invention is preferably a so-called core/shell type grain consisting of an internal core and a surface shell, with the core/shell having a higher silver iodide content in the core than in the shell. A type 40 iodobromide silver emulsion is preferred.

The core/shell type emulsion used in the present invention is
177535, No. 60-138538, No. 59-
No. 52238, No. 60-143331, No. 60
It can be manufactured by known methods disclosed in Japanese Patent No. 35726 and No. 60-258536.

The monodisperse emulsion of the present invention may have normal crystals or twin crystals.

The average particle size of the monodisperse emulsion of the present invention is 0.08 μm to 5 μm
, preferably 0.2 μm to 3 μm, particularly preferably 0.2 μm to 3 μm.
It is 3 μm to 1 μm.

The monodispersed emulsion of the present invention can be prepared in the process of forming and/or growing grains by using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (
Metal ions can be added using at least one selected from iron salts (including complex salts) and iron salts (including complex salts) to contain these metal elements inside the particles and/or on the particle surfaces. By placing it in a reducing atmosphere,
Reduction sensitizing nuclei can be added to the interior of the particles and/or to the surface of the particles.

The monodispersed emulsion of the present invention may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The silver halide emulsion used in the light-sensitive material of the present invention can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

The present invention is preferably used for color negative light-sensitive materials. It is particularly preferably used in color negative light-sensitive materials each having at least one blue-sensitive layer, one green-sensitive layer, and one red-sensitive layer on a support.

A coupler is used in the emulsion layer of a light-sensitive material for color photography.

42 Furthermore, by casopring with a competing coupler and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, an antifogging agent,
Compounds that release photographically useful fragments such as chemical sensitizers, spectral intensifiers, and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, an antiirradiation layer, and the like.

These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

Formalin scavengers, fluorescent brighteners, masotho agents, lubricants, image stabilizers, surfactants, color cast prevention agents, development accelerators, development retardants, and bleach accelerators can be added to the luminescent material. .

The total silver coating amount of silver halide and colloidal silver in the silver halide color light-sensitive material of the present invention is 4.5 in terms of metallic silver.
g/m” or more, preferably 5.0 to 7.5 g
/m2, particularly preferably 5.0 to 6.0 g/m2.

43 The dry film thickness of all coating layers provided on the support of the silver halide color light-sensitive material of the present invention is 25 μm or less, preferably 22 μm or less, particularly preferably 10 μm or more.
It is less than μm.

As the support, polycarbonate 1 film, polyethylene teleph clay 1 film, cellulose triacetate film, etc. can be used.

To obtain a dye image using the luminescent material of the present invention, after exposure,
Commonly known color photographic processing can be performed.

Example 1 Each layer having the composition shown below was sequentially formed on a triacetylcellulose film support from the support side to prepare multilayer color photographic element sample No. 101 was created. However, unless otherwise specified, the coating amount is expressed in terms of weight per 1 mZ.

1st layer; antihalation layer Dry film thickness 2.0 μm Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Colored coupler (CC-1) 0.02 g44 High boiling point solvent (Oiβ-1) 0.20
g(Oi R-2) 0.20
g Gelatin 1.6g 2nd layer;
Intermediate layer Dry thickness 1.0 μm Gelatin 1.3 g Third layer; Low sensitivity red-sensitive emulsion layer Dry thickness 2.3 μm Silver iodobromide emulsion (
Em-1) 0.4 g (Em-2)
0.4 g Sensitizing dye (S-1) 3
．． 2xlO-' (mol/1 mol of silver)〃(S-2) 3
．． 2X10-' (. )〃(S-3)
0.2X10-' ( ) Cyan coupler (C-1) 0.50 g (C-2
) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-
1) 0.006 gDIR compound (D
-2) 0.01 g additive (S
C-1) 0.003g high boiling point solvent (
Oiβ-1) 0.55 g gelatin
1.0g 4th layer; High sensitivity red-sensitive emulsion layer Dry film thickness 1.5μm45 Silver iodobromide emulsion (Em-3>0.9
g Sensitizing dye (S-1) 1.7X10-' (mol/1 mole of silver) (S-2) 1.6X10-' (
)// (S-3) 0.1X10-' (
// ) Cyan coupler (C-2)
0.23 g colored cyan coupler (C
C-1) 0.03 gDIR compound (D-2)
0.02 g high boiling point solvent (01β-1
) 0.25 g additive (SC-1
) 0.003 g gelatin
1.0g 5th layer; middle layer dry film thickness 0.
6 μm gelatin 0.8 g 6th layer; low sensitivity green-sensitive emulsion layer dry film thickness 3.5 μm silver iodobromide emulsion (Em-1) 0.6 g (Em
-2) 0.4 g sensitizing dye (S-4
) 6.7X10-' (mol/1 mol of silver)〃(S-5
) 0.8X10-' ( ) Magenta coupler (M-1). 0.17 g〃(
M-2). 0.43 g Colored magenta coupler (CM-1) 0.10 g46 DIR compound (D-3) 0.02 g
High boiling point solvent (Oiβ-2) 0.7
g additive (SC-1) 0.00
3 g gelatin 1.0 g 7th
Layer: High-sensitivity green-sensitive emulsion layer Dry film thickness 1.3 μm Silver iodobromide emulsion (Em-3) 0.9 g Sensitizing dye (S-6) 1.1xlO-' (mol/silver 1 mol)
(S-7) 2. OX10-' ( )
(S-8) 0.3X10-' ( )
Magenta coupler (M-1) 0.03 g
(M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling point solvent (Oi 7!-2) 0.35 g Additive (SC -1) 0.003 g
Gelatin 1.0 g 8th layer; Yellow filter layer Dry film thickness 0, 8 μm Yellow colloidal silver 0.1 g Additives (l
{S-1) 0.07 g (HS-2)
0.07 g47 Additive (SC-2) High boiling point solvent (Oiβ-2) Seratin 9th layer; low sensitivity blue-sensitive emulsion layer Iodobromide recording emulsion (Em-1) (Em-2) Sensitizing dye (S -9) 5.8X10-' Yellow coupler
(Y-1) (Y-2) DIR compound (D~1) (D-2) High boiling point solvent (Oi II-2) Additive (SC-1) Gelatin 10th layer; High sensitivity blue-sensitive emulsion layer Silver bromide emulsion (Em-4) Sensitizing dye (S-10) 3X10-' (S-11)
1.2xlO-' Yellow coupler = (Y-1) (Y-2) 0.12 g 0.15 g 1.0 g Dry film thickness 2.3 μm 0.25 g 0.4 g (mol/llil 1 mol) 0.6 g 0.32 go. 003g 0.006g 0.18g 0.004g 1.3g Dry film thickness 140μm O,5g (monole/1 strip 1 monole) (mol/1 mole of silver) 0.18 g 0.10 g 48 DTR compound (D -4) 0.002
gHigh boiling point solvent (Oi℃-2) 0.05
g additive (SC-1) 0.0
02 g Gelatin 1.1 g 11th layer; 1st protective layer Dry film thickness 1.0 μm Silver iodobromide emulsion (Em-5) 0.3 g UV absorber (IJV-1) 0.07 g (ROV
-2) 0.10
g High boiling point solvent (Oi (1 -1) 0
．． 07 g (Oi A-3) 0.07
g-formalin scavenger (Hs-1>0.2
g(}Is-2) 0.1 g Gelatin 0.8 g 12th layer;
2nd protective layer: dry film thickness 0.5 μm surfactant (30-
1) 0.004 g (SU-2)
0.02 g Alkali-soluble capping agent (average particle size 2 μm) 0.13 g polymethyl methacrylate (average particle size 3 μm) 0.02 g49 Cyan dye (No. 9) 0.0
05 g Magenta dye (positive 7) 0. Old g slip agent (Kei AX-1) 0.04
g Gelatin 0.58 In addition to the above composition, each layer also contains coating aid S [l-4, dispersion aid SO-3, hardener H-1, H-2, H-3, stabilizer ST1, preservative DI-1, antifoggant total-1, 8F
-2 was added as appropriate.

The emulsions used in the above samples are as follows.

Em-1 to Em-4 are all core/shell type monodispersed emulsions with high internal iodine content.

Mark E-1 = average AgT content 7.5 mol%, octahedron 0
．． 55μm Em-2: Average 8g■Content 2.5mol%, octahedron 0
．． 36 μm Em-3: Average AgI content 8.0 mol%, octahedron 0
．． 84 μm Em-4: Average Agl content 8.5 mol%, octahedron 0
．． 95 μm Em-5: Average AgI content 2.0 mol%, octahedron 5
0 0.08 μm Each of the above emulsions was added after being chemically sensitized and spectrally sensitized depending on the purpose.

Sample No. The compounds used in 101 are shown below.

S-1 S-2 S 3 51 S 4 S 5 C2H5 C2HS S 6 52 S 7 S 8 S 9 53 S 10 S 1 1 C ■ 54 C 2 M 1 M 2 Cp C! 55 Y 1 Y 2 吋r ρ 56 CC 1 0H CM 1 Cρ Cl 57 D 1 0H D 2 0H 58 D 3 D 4 0H 0H 59 UV 1 0H UV 2 C2H5 HS 1 U HS 2 60 H 1 H 2 ((C }12 ?I{SO2CH2)3CCH2SO■(CHZ)2)
2N (CHz) ZSO3K H 3 (CH2 C}I ?O■CR.)20 Su 1 H NaO. S-C COOCR2 (CF2CF2)3H C-COOCHZ (CF2CFZ)3HH2 Su 2 61 Su 3 (Alkanol XC) Su 4 H Na03S-C COOC. ll CH2 COOC8}117 SC 1 0H SC 2 62 WAX 1 (Average molecular weight: 30.000) Oil 1 0 1 7! 2 Oil 3 63 ST 1 0H AF 1 AF 2 DI ■ Next, dye No. 7, lt. Sample No. 9 and Floor 1 were prepared in the same manner except that the amounts added (g/mz) were changed as shown in Table 1. 102-105 were produced. However, Dye Tooth 1 was added to the 11th layer.

64 Sample No. The spectral reflection densities of the photosensitive layer side surfaces of Nos. 101 to 105 were measured using a Hitachi self-recording spectrophotometer U-3210, and the reflection densities at each wavelength of the obtained data are shown in Table 1-2.

Table 1 65 Table 2 The sample prepared in this way was exposed to 50CM using white light.
After performing sensitometric exposure to give an exposure amount of S, the following development treatment was performed.

Processing process (38℃) Color development bleaching water washing fixing washing stabilizing drying The composition of the processing solution used in each processing process is as follows:
seconds 6 minutes 30 seconds 3 minutes 15 seconds 6 minutes 30 seconds 3 minutes 15 seconds 1 minute 30.66 seconds

<Color developer> 4-amino-3-methyl-N Ethyl N-(β-hydroxy Ethyl (aniline, sulfate) Anhydrous sodium sulfite Hydroxylamine 1/2 sulfate Anhydrous potassium carbonate potassium iodide sodium bromide Nitriloacetic acid trisodium salt (monohydrate salt) potassium hydroxide Add water to make 1e.

Bleaching solution> Ethylenediaminetetraacetic acid iron ammonium salt Ethylenediamine 4-acetic acid diammonium ammonium chlorobromide 4.75 g 4.25 g 2.0 g 37.5 g 0.003g 1.3g 2.5g 1.0g 100 g 10.0 g 150.0 g 67 Glacial acetic acid 10 mI Add 2 water to make 1 p, and adjust the pH to -6.0 using aqueous ammonia.

<Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 liter,
Adjust pH=6.0 using acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 mβ
Konida Sox (Konica Co., Ltd.'!) 7.5
Add mβ water to make 1β.

For each sample obtained through the development process, the transmission density was measured using a densitometer model 310 manufactured by Chi-rite Co., Ltd. using a Status M filter, and a D-(-1ogE) characteristic curve was created. Regarding each characteristic curvature of blue light measurement density (B), green light measurement density (G), and red light measurement density (R) of each sample, (B) and (G
), from the point of concentration 1.0, Δ1ogE=1.
The slope (T1) is 68 with respect to the density point on the high exposure area side, and ΔlogE = 1 from the point of density 1.5.
．． 0 From the slope (γ2) to the density point on the high exposure area side, ΔIogE = 1.0 from the density point of 2.0. Data on the slope (γ3) with respect to the density point on the 0 high exposure region side, and Δ1ogE-1. Table 3 shows the data of the slopes (γ1), (γ2), and (γ3) for each density point in the 0 high exposure region side.

69 Table 3 In the results shown in Table 3, the comparative sample No. 101 prepared by combining monodispersed emulsions has undesirable undulations in the gradation from the high exposure region to the low exposure region of the characteristic curve. It can be seen that the composition of the present invention by adjusting the amount of water-soluble dye added has excellent smooth and linear gradation.

70 Example-2 Regarding sample holes 102 to 105 of Example-1, dye No.
．． Dye No. 7 instead of dye No. 13, dye No.
Dye No. 9 instead of dye No. Samples 202 to 205 were prepared by adjusting the addition amount so that the spectral reflection density on the surface of the photosensitive layer was as shown in Table 2, and the same evaluation as in Example 1 was performed. The same effect as 1 was obtained.

Example 3 A large amount of 2-mercaptobenzthiazole was added to each single-breakdown emulsion of Sample 101 of Example 1 to adjust the sensitivity and gradation, and each T value was approximately the same as Sample 105 of Table 3. A nearby sample hole 301 was prepared. For sample tooth 105 and positive 301, potassium iodide in the color developer of Example-1 was 0.009
When the development process was carried out in the same manner except that g/β was used, sample No. 301 exhibited gradation waviness, but sample tooth 105 maintained a smooth and linear gradation.

Example 4 Using sample patient 105 of Example 1, the following 71 runs were performed. Then sample IIk1.101
-105 were subjected to the same exposure as in Example-1, and then developed using a running liquid.

The process was continued until three times the capacity of the stabilization tank was filled with replenisher.

(The replenishment amount is the value per 1 m2 of photosensitive material.) However,
The stabilization process was carried out using a three-tank counter current, in which the final tank was replenished with the stabilizing liquid, and the overflow flowed into the previous tank.

Furthermore, part of the overflow of the stabilization tank following the fixing tank (
275 mβ/m2) was poured into the stabilization tank.

The composition of the color developing solution used is as follows.

Potassium carbonate 30 g Sodium bicarbonate 2.7 g 72 Potassium sulfite 2.8 g Sodium bromide 1.3 g Hydroxylamine sulfate 3.2 g Sodium chloride 0.6 g 4-Amino-3-methyl-N ethyl-I1-(β-hydroxylethyl ) Aniline sulfate 4.6g diethylenetriaminepentaacetic acid 3.0g potassium hydroxide
Add 1.3g water to make 1ρ, and use potassium hydroxide or 20% sulfuric acid to make p1110.01.
Adjust to.

The composition of the color developer replenisher used is as follows.

Potassium carbonate 40 g Sodium bicarbonate 3 g Potassium sulfite
7g sodium bromide
0.5 g hydroxylamine sulfate 3
．． 2g 4-Amino-3-methyl-N 73 Ethyl-N-(β-hydroxyethyl) Aniline sulfate 6.0g Diethylenetriaminepentaacetic acid 3.0g Potassium hydroxide
Add 2 g water to make 1 liter and adjust the pH to 10.12 using potassium hydroxide or 20% sulfuric acid.

The composition of the bleaching solution used is as follows.

1,3 diaminopropane tetraacetic acid 0.35 mol ferric ammonium ethylene diamontetraacetic acid 2 2 g sodium ammonium bromide 150 g glacial acetic acid
40mj! Add ammonium nitrate 40g water and make 17! Close and adjust the pH to 5.4 using ammonium water or glacial acetic acid.

The composition of the bleach replenishment solution used is as follows.

1,3 diaminopropanetetraacetic acid 0.40 mol7
4 Ferric ammonium ethylene diamontetraacetic acid 2 2 g Sodium ammonium bromide 170 g Ammonium nitrate 50 g Glacial acetic acid
61 mjl! Add water to make 1β, adjust to pH 3.5 using aqueous ammonia or glacial acetic acid,
Adjust as appropriate to maintain the PL+ of the bleach tank solution.

The compositions of the fixer and fixer replenisher used are as follows.

Ammonium thiosulfate 100g Ammonium thiocyanate 150g Anhydrous sodium bisulfite 20g Sodium metabisulfite
4.0g ethylenediaminetetraacetic acid 2
Add 1.0 g of sodium water to make 700 mn, and adjust the pH to 6.5 using glacial acetic acid and aqueous ammonia.

The composition of the stabilizing solution and stabilizing replenisher used is as follows: It is as follows.

1,2-benzisothiazoline 0.1 g 3-one (50% aqueous solution) Hexamethylenetetramine 0.2 g Hexahydride L3.5-}lith 0.3 g (2-hydroxyethyl) Add 5-triamine water to make 1 liter, The pH was adjusted to 7.0 using potassium hydroxide and 50% sulfuric acid.

When the gradation properties of each sample obtained by development were evaluated in the same manner as in Example-1, the same effects as in Example-1 were obtained.

Claims (1)

[Claims] In a silver halide color light-sensitive material containing colloidal silver, a colored coupler and a water-soluble dye on a support,
The photosensitive material contains at least one type of monodisperse silver halide, and the spectral reflection density of the photosensitive layer side surface is 1.0 to 1.4 at 450 nm, or 0 at 550 nm. A silver halide color photosensitive material having a reflection density of 0.8 to 1.2, or 0.6 to 1.0 at 650 nm.