JPH03296049A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material having superior bleaching performance in color development, satisfactory shelf stability and high sensitivity by incorporating at least one kind of silver salt of a compd. having bleaching accelerating action into at least one of photographic constituent layers. CONSTITUTION:When at least one silver halide emulsion layer contg. a silver iodobromide emulsion having >=8mol% average silver iodide content and at least one nonphotosensitive colloidal layer are formed on a base as photographic constituent layers to obtain a silver halide color photographic sensitive material, at least one kind of silver salt of a compd. having bleaching accelerating action is incorporated into at least one of the photographic constituent layers. A silver halide color photographic sensitive material having superior bleaching performance in color development, high sensitivity and superior desilverability can be obtd. The shelf stability of this sensitive material is not deteriorated.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, in particular a silver halide color photographic material that has high sensitivity, excellent storage stability, good desilvering properties, and can be processed quickly. This invention relates to silver color photographic materials.

[Background of the invention]

In recent years, demands for higher sensitivity and higher image quality for silver halide color photographic materials have been increasing. In order to meet these demands, research to improve silver halide emulsions has been actively carried out, and for example, Japanese Patent Application Laid-Open No. 131933/1987 describes a silver halide color photograph with improved photographic performance by increasing the silver iodide content. A photosensitive material is disclosed.

However, it is known that silver halide color photographic materials with increased silver iodide content have the disadvantage of deteriorating rapid processing properties, particularly bleaching properties in the desilvering process.

On the other hand, as a technique for improving such desilvering properties, for example, JP-A-62-168130 discloses the use of a compound having a bleaching accelerating effect or a precursor thereof in a light-sensitive material.

Thiols, thiones, dithiones, etc. are known as typical compounds that have bleach-accelerating properties, but these compounds have good compatibility with silver ions and easily form silver salts, so they cannot be directly used in photosensitive materials. When used for applications, it has the disadvantage of significantly lowering photographic sensitivity and deteriorating the storage stability of latent images after photography or the storage stability of photosensitive materials over time. In order to eliminate such drawbacks, for example, in Japanese Patent Application Laid-open No. 1@61-201247,
So-called bleach accelerator releasing couplers are disclosed which release bleach accelerators by coupling reaction with oxidized forms of developing agents.

However, since this compound reacts with the oxidized form of the developing agent, if it is used in a large enough amount to promote bleaching, it may inhibit the coloring reaction due to a competitive reaction with the coupler, which should originally contribute to coloring. There is a problem that it forms an undesirable color-forming pigment by itself when reacting with an oxidized product of oxidant, and it has the disadvantage that it is difficult to obtain a sufficient bleaching accelerating effect.

[Purpose of the invention]

Accordingly, a first object of the present invention is to provide a silver halide color photographic material which has excellent desilvering performance and good bleaching properties in color development.

A second object of the present invention is to provide a silver halide color photographic material which is highly sensitive and has excellent desilvering properties without deterioration in storage stability over time.

Other objectives will become apparent from the description below.

[Structure of the invention]

The above object of the present invention has been achieved by discovering that the above object can be achieved by the following method.

That is, on a support, at least one silver halide emulsion layer containing a silver iodobromide emulsion having an average silver iodide content of 8 mol % or more and at least one non-photosensitive colloid layer are photographically constructed. This is achieved by a silver halide color photographic light-sensitive material having a layer containing at least one silver salt of a compound having a bleaching accelerating effect in at least one of the photographic constituent layers.

The present invention will be explained in detail below.

The silver halide color photographic light-sensitive material of the present invention contains a silver iodobromide emulsion in which at least one silver halide emulsion layer has an average silver iodide content of 8 mol % or more,
The average silver iodide content is preferably 9 mol% or more,
Particularly preferably 10 to 15 mol%.

The silver iodobromide emulsion layer having an average silver iodide content of 8 mol % or more is preferably a high-sensitivity layer, particularly preferably a color-sensitive high-sensitivity layer closest to the support, and a highly sensitive layer next to the support. It is a highly sensitive layer with color sensitivity close to that of the body.

In the silver halide color photographic light-sensitive material of the present invention, the silver halide grains in the silver halide emulsion-containing layer having an average silver iodide content of 8 mol % or more have an average grain diameter equivalent to a projected area of 0.5 mol %. It is preferably 8 μm or more, more preferably 1.0 μm or more and 5.0 μm or less, and particularly preferably 1
．． It is 5 μm or more and 4.0 pm or less.

The silver halide color photographic light-sensitive material of the present invention has a multilayer structure in which a red-sensitive silver halide emulsion, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer are coated on a support. Preferably, it is a color photographic light-sensitive material, and each photosensitive layer is preferably composed of two or three silver halide emulsion layers having different sensitivities.

Further, the silver halide color photographic light-sensitive material of the present invention has a non-photosensitive colloid layer in addition to the silver halide emulsion layer. Non-photosensitive colloid layers include gelatin layers or gelatin layers containing photographically useful additives. Specifically, in addition to the outermost protective layer, yellow filter layer, and antihalation layer, it also contains a color stain inhibitor, fine-grain silver halide, etc. between layers with different color sensitivities, or layers with the same color sensitivities but different sensitivities. Examples include an intermediate layer located between layers.

The layer structure that can particularly exhibit the effects of the present invention includes, in order from the support, a colloidal silver halide B prevention layer (intermediate layer), a red-sensitive layer (intermediate layer), a green-sensitive layer (intermediate layer), a colloidal silver color filter layer, A blue-sensitive layer (intermediate layer), a protective layer coated, and a colloidal silver antihalation layer (intermediate layer), a red-sensitive layer (intermediate layer), a green-sensitive layer (intermediate layer), and a blue-sensitive layer in order from the support. (intermediate layer), red-sensitive layer (intermediate layer), green-sensitive layer (colloidal silver color filter layer), blue-sensitive layer (intermediate layer), and protective layer.

Note that the layers in parentheses may be omitted. The red-sensitive layer, green-sensitive layer and blue-sensitive layer may each be divided into low-sensitivity and high-sensitivity layers. Furthermore, a layer structure in which at least one of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive columnar layer is divided into three partial layers as seen in Japanese Patent Publication No. 49-15495 (1987-49027)
The layer structure that separates the high-speed emulsion layer unit and the low-speed emulsion layer unit as seen in No.
No. 2,622,923, No. 2622.924, No. 2,704.826, and No. 2.704797.

Further, the present invention is disclosed in Japanese Patent Application Laid-open No. 59-177551 and Japanese Patent Application Laid-open No. 59-177551.
It is also possible to apply the layer configurations described in Publications No. 177552 and No. 59-180555.

In the silver halide color photographic light-sensitive material of the present invention, the total amount of silver halide emulsion coated on the support is 6.0 g.
/m” or more, more preferably 7.
0-15.0 g/m", particularly preferably 8.0-12-
0g/m".

The silver salt of the compound having a bleaching accelerating effect according to the present invention includes:
Examples include compounds represented by the following general formulas [I] to (XI[[).

In the formula, Q represents an atomic group necessary to form a nitrogen-containing heterocycle, and %R1 represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or an amino group.

In the formula, Q represents an atomic group necessary to form a sulfur-containing heterocycle, and X is 0. represents S or NR (R is a hydrogen atom or an alkyl group).

General Formula [II[) In the formula, R2 and R1 each represent a hydrogen atom, an alkyl group, a hydroxyl group, a carboxyl group, an amine group, an acyl group, an aryl group, or an alkenyl group. A represents on, and R4 and Rs are synonymous with R1 and R3, respectively. However, R4 and R may each represent -B-SZ, or R3 and R1, R and R' R6 and Rs
may be combined with each other to form a ring.

General formula (IV) or represents an n1-valent heterocyclic residue, X represents -51-0 or -NR", where R and R' are respectively synonymous with R2 and R5 2 is an ammonium group,
an amino group, a nitrogen-containing heterocyclic residue, where R8 and R9 each represent a divalent metal atom group, and R' is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic residue, or represents an amide 7 group, n1 to n, m, to m each represent an integer of 1 to 6, and m represents an integer of 0 to 6. B represents an alkylene group, Rla is an alkyl group or -(
CH*) represents nasO3e. (However, R10 is -(C
H2)n1sO3'', a represents O, and when it is an alkyl group, it represents l.)Ge represents an anion.

n represents an integer from 1 to 6.

General formula [v] -505M', -CONHz, -5OJJ, -NH
x, -CN, -COJ+s.

SOJ+a, -OR+s, -NR+mR+t, -5
RI@, -5OaR+s.

-NHCORr s , -NH3OJ+ M , -0C
ORI I or -5OJ+s, in which Y2 represents an atomic group necessary to form a nitrogen-containing heterocycle.

General formula (Vl) where D ,, p ! +D s and D4 each represent a simple bond or a hydrocarbon chain, and Q ++Q zeQ
s and q represent 0.1 or 2, respectively.

General formula [■] In the formula, X is a hydrogen atom, Rr *, -COOM'
-0)I.

m and n each represent an integer of 1 to 10. Rll+Rl! IR131R141RliR17 and RIM each represent a hydrogen atom, an alkyl group, an acyl group, or an alkyl group of R1, and R11 is -NR. R1
1° -0Rzz or -8Ro, R,0 and Rff
il each represents a hydrogen atom or an alkyl group, Ro
represents an atomic group necessary to combine with R1 to form a ring.

R7° or R21 may be combined with R18 to form a ring. M' represents a hydrogen atom or a cation.

General formula [■] Represents an elementary atom or a carboxyl group.

General formula [x] In the formula, Ar represents an arylene group or a divalent organic group containing an arylene group, B and B each represent an alkylene group, and R2s, R14, R2s and R2° each represent a hydroxyl group. It represents a substituted alkyl group, and X and y each represent 0 or 1. G' represents anion, 2 is 0
, 1 or 2.

General formula [11] In the formula, Z l+Z ! , Z3 and z4 each represent a carbon atom or a nitrogen atom, and at least one of these
One is a nitrogen atom.

General Formula (U) In the formula, R31 and R3z each represent a hydrogen atom or a substituent.

General formula [11] In the formula, R1 and R1 each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R2# represents a hydrogen atom or an alkyl group, R3° is a water formula, and R33r
Rs4r RSs and R3M each represent a hydrogen atom or a substituent.

General formula [XI[l] RR37-5A In the formula, R8 represents an alkyl group, an aryl group, a heterocyclic group, an acyl group, a thioacyl group, a carbamoyl group, or a thiocarbamoyl group, and each group has a substituent. You can leave it there.

In general formula CI), the heterocycle formed by Q and the heterocycle represented by R8 are each a fused heterocycle (
For example, R
The alkyl group represented by 1 preferably has 1 to 5 carbon atoms. Further, the heterocycle formed by Q and the polygroup represented by R include those having a substituent (for example, an alkyl group, a carboxyl group, a sulfo group, an acyl group, etc.).

In general formula [11), the heterocycle formed by Q includes a fused heterocycle (for example, one in which 5- to 6-membered unsaturated rings are fused), and a substituent (for example, an alkyl group,
aryl group, carboxyalkyl group, alkoxycarbonylalkyl group, halogen atom, vinyl group, anilino group, acylamino group, sulfonamide group, etc.).

In the general formula CI[[], the alkyl group represented by R1+ R3+ R# and the alkylene group represented by B each preferably have 1 to 6 carbon atoms, and the acyl group represented by R8゜R3 has carbon atoms Preferably, the number is 2 to 4.

In addition, the heterocyclic group represented by A, R~ is a fused heterocyclic group (
For example, R
, , R, , A and R" include those having substituents (eg, hydroxyl group, alkyl group, etc.).

In general formula [IV), the groups represented by Ra and Re include those having substituents.

In general formula (V), the heterocycle formed by Ql contains a fused heterocycle (e.g., a fused 5- to 6-membered unsaturated ring or saturated ring) and a substituent (e.g., carboxyl group, sulfo group). etc.).

In general formula [Vl], the hydrocarbon chains represented by DI to D4 may be saturated or unsaturated, such as alkylene,
Examples include alkenylene, and those having 1 to 8 carbon atoms are preferred. In addition, the sulfur-containing heterocycle is a fused heterocycle (for example, 5-
6-membered saturated ring, fused unsaturated ring), and substituents (e.g., hydroxyalkyl group, hydroxyl group,
carboxyalkyl group, etc.).

In the general formula [■], Ro, ~R,,,R1°.

The alkyl group represented by R11 preferably has 1 to 1 carbon atoms.
6.

In the general formula [■], the arylene group represented by Ar includes a phenylene group, a biphenylylene group, etc.
Examples of the divalent organic group containing an arylene group include combinations of an arylene group and an alkylene group and/or a hetero atom (eg, an oxygen atom).

Alkylene group represented by Bz, Bs and R13 to R2-
The hydroxy-substituted alkyl group represented by is preferably one having 1 to 6 carbon atoms.

In general formula (X), when Zl, Zt, Z, or 2° is a carbon atom, a substituent (for example, an alkylthio group, an aryl group, a carboxyalkyl group, an amide group, a carboxyalkylthio group, an arylthio group, a heterocyclic group) , aryloxy group, acyloxy group).

In the general formula [■], examples of the substituent represented by R31 or R1 include an alkyl group, an alkoxy group, an aryl group, a carboxyl group, a haloken atom, an amino group, a hydroxyl group, and a sulfo group.

In the general formula (ff), examples of the substituents represented by R33 to R0 include an alkyl group, an alkoxy group, an amino group, a hydroxyl group, a mercapto group, an acylamino group, and a carbamoyl group.

In general formula (xm), when R3 has a substituent, examples of the nuclear substituent include an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, a carboxyl group, an ammonium group, an ammonium group, an alkoxy group, and a sulfonyl group. , a sulfo group, an acyl group, a thioacyl group, a carbamoyl group, a thiocarbamoyl group, and a 5Rss group (CRsa represents a hydrogen atom or a silver atom).

( ■ ) The above general formula %formula%[[) The present invention represented by The compound is (BA)・Ag and can be expressed as Ru.

The following is the compound (BA) and the general formula %formula%[[) ( ) Typical specific examples of the compounds shown are listed below. ( ■ ) ( ■ -7) (I -9) (D -10) (I[-7) Shit13 (II-9) (■ -11) (Il- ) (If-2) (n -11) Shinn3 (n-3) (I[-4) (It　　　-13) (■ 5) (I[-6) (n -15) ( ■ = 2) ( ■ -4) ( -6) ( ■ -8) (It-8) (n -10) (n -12) (n-14) (II-16) (n -17) (n -19) 21) (n -23) (I[[-1 (I[[-10) (Ill-11) (nl　-12) (III-13) (m-14) (n -18) (n-20) (I[-22) (I[l-4) (I[[-5) CH, -NH 5 1(lI C-NH-NH-C-NH CH2 (II[-6) H2N-C5NHNHC5 NH2 (I[l-7) C5NH(CHz)tNHcs N.H.

(I[[-8) (I[[-9) (III-17) (II-18) υ (I[I-19) (I[I-20) (I[[-21) (I[[-22) (m-23) (m-24) (III-25) N.H. (I[[-26) (TV-1) H3 (VI-7) (Vl-8) (■ 9) (Vl　-10) (VI-11) (Vl-12) H (Vl　-13) (Vl-14) (Vl-15) (Vl　-16) ('111-17) (V- ) (V 2) (■ 3) (Vl- 1) (Vl-2) (VI-3) (VI-4) (VI-5) (VI-6) (■ ) (■-2) (■ 3) (■-4) (■-5) (■-7) (■ 8) (■-9) (■ 10) (■-11) (■ 7) (■ ) (ff-3) (ff-5) (■-12) (I!-2) (ff-4) (■− ) (■-3) (■-5) (X-1) (X-3) (X-5') (It-1 ) (n 3) (■-2) (■-4) (■-6) (X-2) (X-4) (X-6) (n-2) (I[-4) (II-5) (n-6) (IN- ) (n-2) (n-3) (n-4) (IN-5) (■ 6) CH.

(ff-7) (n-8) XII[-11 XII[-12 m 3 XI[[-14 C, H, CC00 HX-15 XII[-16 XII[-17 xl[[-18 XI[[-19 XII[-20 x■ NHx CH2CH2SAg XI[l　　　-2 Illll- 3X -4 HOOCCH2CH2-5Ag Xnl-5 XI[[-6 XII[-9 XI[l　　-10 XI[[-21 m-22 XII[-23 x■ 4 XI[[-25 m-26 Xn[-32 Xl11-33 XI[[-34 Xllr-44 m-45 m-47 ugly CH) CHxCH, C5Ag xm-s.

X111 -51 XI[[-52 XI[l-36 XI[[-37 XI[[-39 (BA) is, for example, British Patent 1°138
．． No. 842, JP-A-52-20832, JP-A No. 53-28
No. 426, No. 53-95630, No. 53-10423
No. 2, No. 53-141632, No. 55-17123, No. 60-95540, No. 61-75352, No. 6
1-83537, U.S. Patent No. 3,232.936, U.S. Patent No. 3,772.020, U.S. Patent No. 3,779.757, U.S. Patent No. 3
, 893.85& etc., it can be easily synthesized by the known technique described in .

The silver salt of the present invention can be easily synthesized by mixing an aqueous solution of the above compound and an aqueous solution of silver nitrate.

The silver salt of the present invention only needs to be present in the color photographic light-sensitive material, and may be present in either the photosensitive layer or the non-photosensitive layer, but is preferably present in the non-photosensitive layer, particularly in the photosensitive layer closest to the support. Preference is given to a non-photosensitive layer present between the layer and the support.

The amount added is l x 10-' per 1I118 of the photosensitive material.
~100 g is preferred, and lXl0-''~1 g is particularly preferred.

Next, a typical synthesis example of the silver salt of the present invention will be described. Incidentally, since it is preferable to add the compound to the photosensitive material in the form of a dispersion, the method for preparing the dispersion is also described.

Synthesis of silver salt of compound I-2 19.1 g of rhodanine-3-acetic acid (I-2) was
Dissolved in 0 mQ of water, 169 g of 10% silver nitrate aqueous solution was added to
Added in 5 minutes. After further stirring for 2 hours, the white crystals formed were collected by filtration, washed with 2000 mff of water, and dried in vacuum to obtain 24.1 g of the target compound.

Preparation of dispersion 14.9 g of the compound synthesized above (silver salt of ■-2)
and 5% alkanol XC (manufactured by DuPont) lOIof
f and 300 mQ of water were added and dispersed in a ball mill for 12 hours to obtain a dispersion.

Synthesis of silver salt of compound r1-2 31 g of 4-sulfobenzotriazole (n-2) was
338g of 10% silver nitrate aqueous solution dissolved in 0100O water
was added over 30 minutes. After further stirring for 2 hours, the white crystals formed were collected by filtration, washed with 2000 mQ of water, and dried under vacuum to obtain 46.3 g of the target product (silver 4-sulfobenzotriazole).

Preparation of dispersion 20 g of 4-sulfobenzotriazole silver, 10 mQ of 5% alkanol XC (manufactured by DuPont) and 400 i of water
was added and dispersed in a ball mill for 12 hours to obtain a milky white dispersion.

The silver halide color photographic light-sensitive material of the present invention has a silver halide emulsion layer other than the layer according to the present invention containing conventional halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any material used in silver oxide emulsions can be used.

Silver halide grains used in silver halide emulsions may have a uniform silver halide composition distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the grain interior and the surface layer. It's okay.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination. It can be chemically sensitized using sensitizing dyes, and it 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.

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

Furthermore, by coupling with a colored coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent,
Compounds that release photographically useful fragments, such as toning agents, hardeners, capri agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers, can be used for 4° sensitization. The material can be provided with auxiliary layers such as filter layers, antihalation layers, antiirradiation layers, etc. 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.

For photosensitive materials, formalin scavenger-fluorescent brightener,
A matting agent, a lubricant, an image stabilizer, a surfactant, a color antifoggant, a development accelerator, a development retardant, and a bleach accelerator can be added.

As a support, use paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

Typical specific examples of processing steps used to process the photographic material of the present invention are shown below.

(1) Color development - Bleach fixing - Washing (2) Color development → Bleach fixing - Small amount of water washing → Water washing (3) Color development → Bleach fixing → Water washing - Stable (4) Color development → Bleach fixing → Stable (5) Color development - Bleach-fixing - 1st stability - 2nd stability (6)
Color development - washing with water → bleach-fixing → washing with water (7) color development - bleaching acceleration - bleach-fixing → stable (8) color development - bleaching acceleration → bleach-fixing → washing with water (9) color development → pre-fixing → bleach-fixing → stable (
10) Color development - pre-fixing - bleaching -> stable (11) color development - bleaching - constant washing - constant fixing - washing - stable (12) color development - bleaching - fixing - washing - stable (13) color development - bleaching - constant fixing -
1st stability - 2nd stability (14) Color development → bleaching → washing with a small amount of water constant setting → washing with a small amount of water →
Washing → Stability (15) Color development - Bleach - Bleach fixing - 1st stability → 2nd stability (16) Color development → Bleaching acceleration - Bleach fixation → 1st stability →
2nd stability (17) Color development - Small amount of water washing - Bleach - Small amount of water washing -> Fixing -
Washing with a small amount of water - Washing with water - Stable (18) Color development - Acceleration of bleaching - Bleaching → Washing with a small amount of water → Fixation →
Small amount of water washing → water washing - stable (19) Black and white development - water washing (or stable) - reversal, one color development, one bleaching, constant washing, one water washing (or omitted) (20) black and white development - water washing (or stable) - reversal, color development → bleaching Accelerate → Bleach → Fix → Wash (or omit) - + Stable (21) Black and white development → Wash (or stabilize) - Reverse → Color development - Bleach-fix - Wash (or omit) - Stable (22) Black and white development - Wash (or - Stability) - Reversal - Color development -> Bleach acceleration -> Bleach fixing -> Stabilization -> Water washing (or omitted) - Stable In the above process, bleach acceleration is a pre-bath containing a bleach accelerator.

In the bleach solution or bleach-fix solution for processing the photographic light-sensitive material of the present invention, bleaching agents such as red blood salt, iron chloride (British Patent No. 736,881) may also be used.
No. 56-44424), persulfuric acid (described in German Patent No. 2,141.199, etc.), hydrogen peroxide (described in German Patent No. 2,141.199, etc.)
(described in Japanese Patent Publication No. 58-11617, No. 58-11618, etc.), aminopolycarbon jljiE2 iron complex salts such as ethylenediaminetetraacetic acid ferric rust salts can be mentioned, but particularly preferred specific examples are as follows. It is a ferric complex salt of aminopolycarboxylic acid represented by:

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid [4]] 1.3-diaminopropanetetraacetic acid 5 pieces Ethylenetetraminehexaacetic acid [6] Cyclohexanediaminetetraacetic acid [711,2-diami/glopanetetraacetic acid [8]] 1.3
-Diaminogloban-2-ol 2-tetraacetic acid [9] Ethyl ether diamine tetraacetic acid [lO] Glycol ether diamine tetraacetic acid Acetic acid 1] Ethylene diamine tetrapropionic acid [12] Phenyl diamine tetra acetic acid [13] Disodium ethylene diamine tetra acetate salt [14
] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16]
] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid sodium salt [18]
Propylenediaminetetraacetic acid sodium salt [19] Ethylenediaminetetramethyleneposponic acid [20] Cyclohexanediaminetetraacetic acid sodium salt [21] Diethylenetriaminepentamethylenephosphonic acid [22] Cyclohexanediaminetetramethylenephosphonic acid "23" Nitrilotriacetic acid 24] Iminodiacetic acid 25]Hydroxyethyliminodimethyleneacetic acid 26]Nitrilotripropionic acid 27]Nitrilotrimethylenephosponic acid 281Iminodimethylenephosponic acid [29]Hydroxyethyliminodimethyleneposponic acid [30]Nitrilotriacetic acid monosodium salt Among the ferric complex salts of organic acids, the effects of the present invention are effectively exhibited for compounds with large molecular weights, and preferably the molecular weight of the organic acids is 300 or more.

Among these organic acids, compounds that more preferably exhibit the effects of the present invention include diethylenetriaminepentaacetic acid,
1.3-diaminopropanetetraacetic acid, l.

Examples include 2-diaminopropanoacetic acid a, 1,4-diaminobutanetetraacetic acid, glycol ether diaminetetraacetic acid and cyclohexanediaminetetraacetic acid, and particularly preferred are diethylenetriaminepentaacetic acid and 1,3-diaminopropanetetraacetic acid.

Ferric complex salts of aminopolycarboxylic acids can be used as free acids (hydrogen salts), alkali metal salts such as sodium salts, potassium salts, lithium salts, ammonium salts, or water-soluble amine salts, such as triethanolamine salts. Preferably potassium, sodium and ammonium salts are used. At least one type of these ferric complex salts may be used, but two or more types can also be used in combination.

The amount used can be arbitrarily selected and must be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but it is generally used at a lower concentration than other aminopolycarboxylate salts because of its high oxidizing power. can. For example, the working liquid Iff
It can be used in an amount of 0.01 mol or more, preferably 0.0
It is used in an amount of 5 to 0.8 mol.

In addition, the solubility of the replenisher is -
It is preferable to use it concentrated in a cup.

〔Example〕

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

Example 1 In the examples, the amount added in the photosensitive material is expressed in grams per rn2 unless otherwise specified. Furthermore, silver halide and colloidal silver are shown in terms of silver. Furthermore, sensitizing dyes are expressed in moles per mole of silver.

A comparative multilayer color photographic material 1 was prepared on a cellulose triacetate film support, comprising each layer having the composition shown below.

1st layer: Halic acid prevention layer Black colloidal silver 0.2 Gelatin 1.7 UV-1 (ultraviolet absorber) 0. S CM-1 (colored coupler) 0.2 0il-1 (solvent for dispersing ultraviolet absorber) 0.150i+
-2 (for ultraviolet absorber dispersion) 0.150il-3
(For colored coupler dispersion) 0.2 2nd layer: Intermediate layer gelatin l.2 3rd layer:
First red-sensitive emulsion layer Silver iodobromide emulsion 1.5 Gelatin 1.3S-1 (sensitizing dye) 0.5X 10-'5-2 (sensitizing dye) 2X 10-ken 5-3 (sensitizing dye) ”
) 2X 10-'C-1 (Coupler)
0.07C-2 (Coupler) 0
．． 3 O-4 (Coupler) 0.3 CC-1 (Colored coupler) 0.07D-1 (DIR
coupler) 0.0050i 1-1
(For C-1, C-2, CC-1°D-1 dispersion) 0.2 4th layer: Intermediate layer gelatin 0.8 5th layer:
First green-sensitive emulsion layer Silver iodobromide emulsion 1.5 Gelatin 1.45-4 (sensitizing dye) 1.8X 10-'5-5 (sensitizing dye) 1.3X 10-'5-6 (sensitizing dye) Sensitizing dye) 9.2X 10- 5-7 (Sensitizing dye) 6.8X 10-5
-8 (sensitizing dye) ' 6.2X 10-
'M-1 (Coupler) 0.15
CM-1 (Colored coupler') 0.08
Of 1-3 (for M-1, CM-1 dispersion) 0.23
6th layer: Intermediate layer gelatin 0.83 C-
10,05 0i 1-3 (for SC-1 dispersion) 0.05
7th layer: @1 Blue-sensitive emulsion layer Silver iodobromide emulsion 0.8 Gelatin 0.65-9 (sensitizing dye) 3X 10-'S -10 (sensitizing dye) lXl0-'Y-1 (coupler)
0.3 0il-3 (for Y 1 dispersion) 0.3 8th layer: Intermediate layer gelatin 0.8S C-
10,05 041-3 (for SC-1 dispersion) 0.05 No. 9
Layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion 3.0 fine grain A
gX emulsion CAg1 = 2 rnoΩ% silver iodobromide, average grain size 0.08 μm) 0.5 gelatin
2.43-1 (sensitizing dye)
0.2X 10-'5-2 (sensitizing dye)
1. OX 10-'C-1 (coupler) 0
．． 2 0-3 (Coupler) 0.0
50-4 (Coupler) 0.1
0C-1 1l-1 (C ■ C-3.

C 0.05 1 for dispersion) 0.4 10th layer: Intermediate layer gelatin 0.85 C-
10,07 CM-1 (colored coupler) 0.040
i l-3 (for SC-1, CM-1 dispersion) 0.25 11th layer 12 green-sensitive emulsion layer Silver iodobromide emulsion 2.4 Gelatin 16S-4 (sensitizing dye)
6.8X 10-'5-5 (sensitizing dye)
6.7X 1O-65-6 (sensitizing dye)
2. IX 10-'M-1 (Coupler) 0.2 CM-1 (Colored Coupler) 0.020
i 1-4 (for M-1, CM-1 dispersion) 0.2 12th
Layer: Intermediate layer fine grain AgX emulsion (Agl-21110β% silver iodobromide, average grain size 0.08 μ), 0.3
Gelatin 0.85 C-
10,05 0i 1-3 (for SC-1 dispersion) 0.05
13th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion 2.1 Fine grain A
gX emulsion (Agl = 2 mo 12% silver iodobromide, average grain size 0.08 p m) 0.1 fine grain Ag
X emulsion (A g (-2 moff% silver iodobromide, average grain size 0.3 μm) 0.1 gelatin
2.1S-1,0 (sensitizing dye) 0.4X 10-line S-11 (sensitizing dye> 1.2X 10-'Y-1 (coupler) 0.8 0i1-3 (for Y-1 dispersion) )0.8 14th layer: 1st protective layer gelatin 1.5UV-1
(Ultraviolet absorber) 0.1 UV-2 (Ultraviolet absorber) 0. I HS-1 (Formalin Scavenger) 0.5H3-
2 (Formalin Scavenger') 0.20il
1 (For ultraviolet absorber dispersion) 0.1 O4l 2 (For ultraviolet absorber dispersion) 0.1 15th layer: #2 protective layer gelatin 0.6 Alkali-soluble matting agent (average particle size 2 μm) 0.12 Polymethyl Methacrylate (average particle size 3μm) 0.02 WAX-1 (slip agent> 0.04W
-1 (charge control agent) 0.004 In addition to the above composition, each layer also contains coating aid 5U-1, dispersion aid 5U-2, 5U-3, hardening agents H-1 and H-2, Stabilizer 5T-1 and antifoggants AF-1 and AF-2 were added.

1 − − − -9 10 -11 − -8 C-1 -1 M-1 H Q 1 -2 CH V-1 C,H.

CH -3 c, Hs(t) CH V AX C2H4 - CH ■ To○ To CH T-1 F- S S -1 -1 CH NaOsS CHCOOCH2 (CF2CF2)3H
CH2COOCR2(CF2CF2)sHU - ■ Na0sS-CHCOOCaH+t CH2C00Ca H+ t U-3 -1 ((CH2 CHSO2CHri3CCH!5Ch(CHriri2N(C
Hri! SOJSC-1 0H The sample coated in multiple layers in this way is comparative sample No.

1, and as shown in Table 1 below, samples with different emulsion grain sizes and silver iodide contents were prepared in the same manner as comparative samples No. 2.3.
And so.

Furthermore, samples Nos. 4 to 21 in which the bleaching accelerator according to the present invention was added using these emulsions were prepared as shown in Table 1. Expose to light and perform the following development process.

Processing process (38°C) Color development 3 minutes 15 seconds bleaching
White Fixed as listed in Table 2
6 minutes 30
Second wash
3 minutes 15 seconds stabilization 1 minute 3
0 second drying The composition of the treatment liquid used in each treatment step is shown below.

Color developer 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine l/2 sulfate 2, 0 g anhydrous potassium carbonate
37.5g potassium iodide
1.9mg potassium bromide
1.3g nitrilotriacetic acid trisodium salt (l hydrate) 2-5g potassium hydroxide 1
．． Add 0g of water to make 1ff. (pH-10,02)
Bleach solution (formulation A) Iron ethylenediaminetetraacetic acid (I[[) Ammonium salt 100.0g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
Add 10.0g water and make 1
g, and adjust the pH to 6.0 using aqueous ammonia.

Bleach solution (Formula B) 1.3-diaminopropanetetraacetic acid iron (I[[) ammonium salt 180.0g1.3-diaminopropanetetraacetic acid diammonium salt 4.0g ammonium bromide 228.0g ammonium nitrate 118.0g glacial acetic acid
69.0g ammonium water (25
%) Add 30 mQ water to make 1Q, and adjust to pH 4.5 using aqueous ammonia.

Fixer Ammonium thiosulfate 175.0g Anhydrous ammonium sulfite 8.6g Sodium metasulfite 2.3g Add water and 1
g and adjust the pH to 6-o using acetic acid.

Stabilizing liquid formalin (37% aqueous solution) 1.5m
+2 Konidax (manufactured by Konica Corporation) 7.5
Add rnQ water to make lQ.

Next, the same samples 1 to 21 were subjected to wedge exposure according to a conventional method, and the following development treatment was performed.

Processing steps (38°C) Color development 3 minutes 15 seconds Bleach fixing Table 2 Water Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the processing solution used in each processing step is shown below.

Color developer: Same bleach-fix solution as above. Iron (In) ethylenediaminetetraacetate. Ammonium 60.0g. Ammonium salt of ethylenediaminetetraacetate 3.0g. Ammonium thiosulfate (70% solution). 130. omQ ammonium sulfite (40% solution) 27.5 mQ color developer 100.0 mQ Add water to bring the total volume to 1Q, and adjust to pH 7.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution: Measure the amount of remaining silver in the maximum concentration area of the same sample as above using fluorescent X-rays, take this as 100% of the remaining silver amount, and calculate the relative silver remaining in the maximum concentration area of each sample. The rate was calculated.

The smaller the value, the better the bleaching performance.

In addition, for samples 1 to 21, each sample was divided into two,
One part was stored at 50°C with a relative humidity of 80% for 7 days, and the other part was stored in a refrigerator (5°C) for 7 days, then wedge exposed according to the usual method, and the following processing steps were carried out. The storage stability of the photosensitive material was evaluated based on the change in sensitivity of the red-sensitive layer. Sensitivity in the table is expressed as relative sensitivity.

Processing steps (38°C) Color development bleaching water washing fixing washing stabilizing drying In each processing step, the processing solution used was the same as above (however, the bleaching solution used was formulation A).

3 minutes 15 seconds 6 minutes 30 seconds 3 minutes 15 seconds 6 minutes 30 seconds 3 minutes 15 seconds 1 minute 30 seconds As is clear from Table 2, the samples according to the present invention have excellent bleaching performance and are desilvered in a short time. I understand that.

Furthermore, it is shown that the photosensitive material has good storage stability over time and maintains high sensitivity.

Example 2 According to the method of Example 1, samples shown in Table 3 below were prepared regarding changes in silver iodide mol% of silver halide emulsions and bleaching accelerators.

The obtained sample was treated in the same manner as in Example 1, and the results shown in Table 4 were obtained.

As is clear from Table 4, the present invention has a remarkable effect when silver iodide is contained in a range from 8 mol% to 15 mol%. [Effect of the Invention] The present invention has excellent bleaching performance in color development, and A highly sensitive silver halide color photographic material with good storage stability over time can be obtained.

Claims (1)

[Claims] At least one silver halide emulsion layer containing a silver iodobromide emulsion having an average silver iodide content of 8 mol % or more and at least one non-photosensitive colloid layer are formed on a support as photographic constituent layers. 1. A silver halide color photographic material comprising at least one silver salt of a compound having a bleaching accelerating effect in at least one of said photographic constituent layers.