JPH0367247A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having satisfactory fog resistance and aging stability by forming a photographic constituent layer contg. a specified compd. on a support. CONSTITUTION:At least one photographic constituent layer contg. a compd. represented by formula I is formed on a support. In the formula I, A is a group represented by formula II, each of L<1>-L<4> is methine, L<2> and L<4> may bond to each otther to form a ring together with L<2>-L<3>, O is a group of nonmetallic atoms required to form a ring such as isoxazolone or oxazolidinedione and each of l and m is 0 or 1. In the formula II, R1 is aliphat. hydrocarbon or aryl, each of R2 and R3 is H, aliphat. hydrocarbon or aryl, R2 and R3 may bond to each other to form a 5-membered condensed ring and R4 is H, aliphat. hydrocarbon, etc. Fog resistance and aging stability are improved.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material containing a new dye, and more specifically, to a silver halide photographic material containing a novel dye, which is dyed with a novel dye and which has poor fogging and aging stability. This invention relates to an improved silver halide photographic material.

[Background of the Invention] In recent years, photographic materials are required to have high image quality characteristics such as sharpness and color reproducibility.

In addition, particularly recently, in order to compete with the immediacy of competing electrophotographic materials, there has been a demand for further reduction in processing time, that is, ultra-rapid processing capability. In order to achieve the high image quality characteristics and ultra-rapid processing suitability required of such photographic materials, efforts have been made to make the film thinner and to optimize silver halide and additive compound materials.

Incidentally, it is well known that dyes are incorporated into silver halide photographic materials for the purpose of improving image quality or adjusting emulsion sensitivity. used in the form.

Recently, dyes (hereinafter referred to as YC dyes) have been developed to replace yellow colloidal silver in color photographic materials, dyes for cross-over cut layers in X-ray photographic materials, and non-light-sensitive emulsion layers in printed photographic materials. It has a wide range of uses, including dyes.

The dyes used for these purposes must: 1. have a good absorption spectrum, 2. not diffuse from the colored layer to other layers, 3. 4. Stable in silver halide photographic materials 5. Easy to add 6. Stable in emulsion coating solution and not affecting solution viscosity 7. IA theory The properties required include that no color remains behind.

A large number of dyes have been proposed in the past for the purpose of satisfying these desired properties, such as U.S. Patent No. 1.878.
,961, 2,150,695, 2,274,78
2, 3.094.418, 3,933,798, 4.187.225, 4,234,677, 4.2
88.534, 4,266.014, 4,379,
No. 838, British Patent No. 506,385, 1,52
Pyrazolooxonol dyes represented by US Patent No. 1.083 and US Pat. No. 2,117,346, US Pat.
247,127, 3,468.883, 3,469
,985, 3,480.436, 3,540,88
8, 3,398.145, 3,417,084, 3,440.051, 4,042,397,
British Patent No. 506,385, No. 1,077.049, No. 1
, 265,485, US Pat. No. 1.424.515, Research Disclosure No. 14,416, etc., barbylic acid and thiobarbylic acid oxonol dyes, US Pat. No. 3,637, 678, US Pat. No. 3,681,
081, 3,540.888, 4,232,115
Oxonol dyes having other skeletons as typified by US Pat. Nos. 2,538,008 and 3,497
, 502, 3,540,888, 3.544.32
5, 4,042,397, 4,420.555, Belgian Patent No. 780,011, Japanese Patent Publication No. 31-10578, 51-3623, 56-499
53, 57-46778, 59-26940, 5
Benzylidene and cinnamylidene type dyes represented by Publication No. 9-37303, etc., U.S. Patent No. 1,845,504
, No. 2,461,484, No. 4,232,115, British Patent No. 369,721, No. 506.385, Japanese Patent Publication No. 31-5920. 48-27927, 5
Styryl dyes typified by US Pat. Nos. 7-46056 and 59-28898, U.S. Pat.
25.448, 3,148,187, 3,469,
985, 3,540,888, 4.232.115
merocyanine dyes represented by Belgian Patent No. 739,874, British Patent No. 2,083,241, U.S. Patent No. 1.884,035, U.S. Pat.
71,234, 2.322,006, 2,390,
707, 2,464,785, 2,503,717
, 2,527,583, 2,956,879, 4
．． Examples include azo dyes as typified by Patent No. 276.373.

The general method is to dissolve these dyes in water or an organic solvent that is miscible with water and add them to the photographic constituent layers. However, if the dye is water-soluble, it will not remain in the layer to be dyed but will dye the entire emulsion. It will spread into layers. Therefore, in order to achieve the original purpose, it is necessary to add a large amount of dye to the amount that will diffuse into other layers, which may cause undesirable effects on both the white layer and other layers, such as decreased sensitivity, gradation fluctuations, Capri abnormality, etc. In particular, when photosensitive materials are stored over time, fogging and desensitization appear. If the amount used is reduced to avoid this, the original light absorption effect will not be sufficiently obtained.

Dyes with suppressed diffusion properties that dye specific layers are also known, and examples of diffusion-resistant dyes include US Pat. No. 2,538.
,008, 2,539.009, 4,420,55
5, each specification, JP-A-61-204630. 61-2
05934, 62-32460, 62-56958
, 62-92949, 62-222248, 63
-40143, 63-184749, 63-316
YC dyes are described in various publications such as No. 852. These dyes are commonly used in color photographic elements.
Yellow colloidal silver called ey Lea 5ilver absorbs not only the blue light region but also some long wavelengths, which reduces green sensitivity and increases fog in adjacent layers.It is a valuable silver resource. Many proposals have been made to save money. However, the disclosed compounds have not yet optimized their absorption region, their effects on photographic properties have not been completely eliminated, or their bleaching properties are insufficient and color stains remain after processing, resulting in color degradation. It had the disadvantage of causing turbidity.

[Object of the Invention] An object of the present invention is to provide a silver halide photographic material containing a novel dye and having improved capri and stability over time.

[Structure of the Invention] The above object of the present invention is to form a photographic constituent layer containing a compound represented by -e formula [1] on a support at least 1111
This was achieved by a silver halide photographic material characterized by having the following characteristics.

General formula [11 [wherein, A is an aliphatic hydrocarbon group or an aryl group, R7
and R5 is a hydrogen atom, an aliphatic hydrocarbon group or an aryl group, or an atomic group necessary to form a 5-membered condensed ring by bonding between R2 and R8, and R4 is a hydrogen atom, an aliphatic hydrocarbon group or aryl group, respectively.

t, lt, 2t, 3 and L4 represent a methine group, L2 and L4 may be combined to form a ring with L3, Q is an isoxacilone ring, an oxazolidinedione ring, a hydantoin ring, a thiazolidinedione ring,
Represents a group of nonmetallic atoms necessary to form a pyridinedione ring, thiobarbital acid ring, 1,3-indanedione ring, oxythianaphthene ring, oxindole ring, and pyrazolopyridinedione ring, and A and m are O or 1 is an integer. ] Hereinafter, the present invention will be specifically explained.

In the compound represented by the general formula [I] used in the present invention, the aliphatic hydrocarbon groups represented by R1, R2, R3 and R4 preferably have 1 to 20 carbon atoms and are saturated or unsaturated. , specific examples include methyl, ethyl, 2-propenyl, butyl, pentyl, 1so-pentyl, 2-ethylhexyl, octyl, decyl, fso-hexadecyl and the like. R1, R2, Rs and R4
The aryl group represented by is preferably an aryl group having 6 to 20 carbon atoms, such as phenyl, naphthyl, and the like. Each of these groups represented by R, R2, R3 and R4 includes those having a substituent, such as a silver halide atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydroxy group, etc. , alkoxy groups (e.g., methoxy group, ethoxy group, t-butoxy group, t-amyloxy group, etc.), aryloxy group (e.g., phenoxy group, p-f-lyloxy group, p-butanesulfonyloxy group, etc.) , amino group (e.g. N,
N-dibutylamino group, N-ethyl-N-propylamino group, etc.), cyano group, carbamoyl group (e.g. carbamoyl group, N-methylcarbazoyl group, N,N-tetramethylenecarbamoyl group, etc.), carbamoyloxy group ( For example, N-butylcarbamoyloxy group, N-methylcarbamoyloxy group, etc.), ureido group (for example, hexylureido group, dodecyloxyphenylureido group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-3
-oxapentamethyleneaminosulfonyl group, N-benzene N-ethylsulfamoyl group, etc.), sulfamoylamino group (e.g. N-benzene N-ethylsulfamoylamino group, N-hexylsulfamoylamino group, etc.) , sulfonyl group (e.g. methanesulfonyl group, butanesulfonyl group, octanesulfonyl group, l)-toluenesulfonyl group, etc.), sulfinyl group (propanesulfinyl group, p-methoxybenzenesulfinyl group, etc.)
, alkoxycarbonyl group (e.g., butoxycarbonyl group, 2-ethylhexyloxycarbonyl group, etc.), aryloxycarbonyl group, (e.g., 4-butoxyphenyloxycarbonyl group, p-amylphenyloxycarbonyl group, etc.), alkoxycarbonylamino group (e.g. butoxycarbonylamino group, ethoxycarbonylamino group, etc.), aryloxycarbonylamino group (e.g. p-methoxyphenyloxycarbonylamino group, p-
t-butylphenyloxycarbonylamino group, etc.), alkyl groups (e.g. methyl group, ethyl group, 3-propenyl group, t-butyl group, t-amyl group, benzyl group, phenethyl group, etc.), aryl groups (e.g. phenyl group) , Ri-
2-ethylhexylcarbonylaminophenyl group, etc.),
Heterocyclic groups (e.g., pyridyl group, furyl group, etc.), imide groups (e.g., succinimide group, etc.), amide groups (e.g., acetamido group, butanoylamino group, benzoylamino group, etc.), sulfonamide groups (e.g., butanesulfonylamino group, etc.), group, octanesulfonylamino group, benzenesulfonylamino group, 5-(t-octyl)-2-butoxybenzenesulfonylamino group, etc.), acyl group (e.g., acetyl group, propyl group, benzoyl group, etc.), phosphoryl group (e.g. ditolylphosphoryl group, dibutoxyphosphoryl group, ethoxytolylphosphoryl group, etc.), carboxy group, etc.

R2 and R5 can each be combined to form a saturated or unsaturated 5-membered condensed ring, and these condensed rings may have a substituent, and the substituent is exemplified as the substituent for Ro above. The following can be mentioned.

Specific examples of these condensed rings include a cyclopenta[d-cooxazole nucleus, a cheno[2,3-d]oxazole nucleus, and the like.

The methine groups represented by t, lt, 2t, 3 and L4 include those having substituents, such as alkyl groups (e.g. methyl group, ethyl group, benzyl group, etc.), aryl groups ( Examples include phenyl group, p-tolyl group, p-carboxyphenyl group, etc.), alkoxy groups (eg, methoxy group, ethoxy group, etc.), and aryloxy groups (eg, phenoxy group, etc.). Also L
The ring formed by combining 2 and L4 with L3 includes, for example, a 6-membered carbon ring (eg, 5,5-dimethyl-2-cyclohexene ring, etc.).

In the compound represented by the general formula [1F, an isoxacilone ring formed by Q, an oxazolidinedione ring, a hydantoin ring, a thiazolidinedione ring, a pyridinedione ring, a thiobarbylic acid ring, a 1,3-indanedione ring,
The oxythionaphthene ring, oxindole ring and birazolopyridinedione ring have the following formula [''1 a
] to [Hj] are preferred.

Below are the blank spaces General formula (lIa) General formula [■C] General formula (nb) General formula (I[d] General formula (Ile) General formula (]IIi General formula (ffg) General formula (IIi) General formula CTI h) General formula (nj) [wherein R1(+ and R1+ represent a hydrogen atom, an aliphatic hydrocarbon, an alicyclic group, an aryl group or a heterocyclic group,
(2) and W represent a hydrogen atom or a monovalent group, and Y represents an oxygen atom or a sulfur atom. ] General formula It a ]
In ~[II j ], examples of the aliphatic hydrocarbon group represented by RIG and Ro and the aryl group include those described for R+, R2, Rs and R4.

Examples of the alicyclic group represented by RIG and R include a cyclopentyl group and a cyclohexyl group, and examples of the heterocyclic group include a pyridyl group, a pyrimidyl group, a thiazolyl group, an imidazolyl group, a sulfolanyl group, a furyl group,
Examples include multiple groups such as a thienyl group, and these groups include those having the substituents described above for Ro.

The monovalent group represented by (2) and W is not particularly limited, and examples thereof include those shown as the substituent for R described above.

In the dye represented by the general formula [I], RIRIG, R2
It is preferable that the total number of carbon atoms in the alkyl or aryl groups represented by 1, () and W is at least 8, and at least one sulfamoyl group, sulfonamide group, carboxy group, hydroxy group, or phosphoryl group in the molecule. , those having an amide group or a carbamoyl group are particularly preferred. Furthermore, as the group formed by Q, those represented by the general formula % are preferred.

Specific examples of the dye represented by the general formula [I] are shown below,
The dyes used in the present invention are not limited to these compounds.

The dyes according to the present invention are described, for example, in The Cyanine Dice and Related Compounds (Francis Balmer Interfishers, 1964) [Th
e Cyantne Dyes and Re
latedCompounds (Frances
Hamer, Interscishers.

1964)] and the like.

Synthesis examples will be described below, but other dyes can be synthesized in the same manner.

Synthesis example (synthesis of dye (I-1!b-4)) 2-(2-anilinovinyl)-1-(4-carboxyphenyl)methyl-5,5-dimethyl-2-oxazolinium iodo salt 24 g, 3 -(3-benzenesulfonylamino)phenyl-2-thioxazolidine-2,4-dione 17.4g
was suspended in 100 mJ2 of acetonitrile, 15 g of triethylamine was added, and the mixture was heated on a water bath.

10.2 g of acetic anhydride was added dropwise while stirring, and the mixture was refluxed for 3 hours.

Thereafter, the reaction solution was allowed to cool, and the orange precipitate was collected by filtration and washed with acetonitrile.

The filtered material was recrystallized using a methanol-ethanol mixed solvent containing triethyleneamine to obtain orange crystals with a concentration of 11.5%.
I got g. Maximum absorption in methanol solution is 439 nm
(Molar extinction coefficient was 85,000).

Synthesis example (synthesis of dye [I-II a-9]) 2-(
2-anilinovinyl)-1-benzyl-5,5-dimethyl-2-oxazolinium iodo salt 8.8 g, 3-
8.8 g of (3-(2,4-di-t-arybenzene)sulfonylamino)phenyl]-2-isoxazolin-5-one was suspended in 25+af of acetonitrile, and 4. 5 g was added and heated on a water bath.

While stirring, 4 g of acetic anhydride was added dropwise and the mixture was refluxed for 3 hours.

Thereafter, the reaction solution was allowed to cool, and the orange precipitate was collected by filtration and washed with acetonitrile.

The filtered material was recrystallized using methanol to obtain orange crystals.
I got 9g.

The absorption maximum in the methanol solution was 403 nm (molar extinction coefficient was 78,000).

In addition to the photosensitive silver halide emulsion layer, the photographic constituent layers to which the dye represented by formula [I] is added according to the present invention include
Examples include non-photosensitive layers (protective layer, intermediate layer, filter layer, antihalation layer, etc.).

Examples of methods for adding the dye used in the present invention include:
Water-soluble organic solvents (methanol, propyl alcohol, methylcellosolve, phenylcellosolve, DMF, etc.)
A solid dispersion method in which the dye is added as a solid in the form of fine particles, a method in which a latex polymer is impregnated with the dye and added in a dispersed manner, or a high boiling point organic material such as tricresyl phosphate or dibutyl phthalate is added. Various methods can be selected and used, including a method in which a low-boiling point solvent is used in combination with a solvent if necessary to dissolve the material, and then the material is added in an emulsified dispersion state using a surfactant in a wood-philic binder.

In order to take advantage of the characteristics of the dye according to the present invention and obtain a larger desired effect of the present invention, it is possible to dissolve the dye in a high boiling point organic solvent and disperse it in a wood-philic binder, or furthermore, to add it in solid form in the form of fine particles. The method is preferred.

The dye according to the present invention has an optical density of 0.05 to 0.05 depending on the purpose.
3.0 range.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any of the conventional silver halide emulsions can be used.

The emulsion 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.

Couplers are used in the emulsion layer of color photographic materials.

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, a toning agent, a hardening agent, Compounds that release photographically useful fragments such as fogging agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an anti-irradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process.

A formalin scavenger-1 fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fog preventive agent, a development accelerator, a development retarder, and a bleach accelerator can be added to the photosensitive material.

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

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

[Examples] Specific examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 In all the following examples, the amount added in the silver halide photographic light-sensitive material indicates the weight (g) per 112 unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver.

Sample 1-1 of a multilayer color photographic element was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Sample 1-1 (comparison) 1st layer: Antihalation 719 (HC-1) black colloidal silver 0.20 ultraviolet absorber (U
V-1) 0.20 colored coupler (CC-1) 0.05 colored coupler (CM
-2) o, os high boiling point solvent (011-1)
0.20 gelatin
1.5 Second layer: Intermediate layer (IL-1) Ultraviolet absorber (UV-1) 0.01
High boiling point solvent (Oil-1) 0.0
1 Gelatin 1.5 Third layer: Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.8 Silver iodobromide emulsion (El-2) 0.8 Sensitizing dye (S- 1) 2.5X10-' (mol/1 mole of silver) sensitizing dye (S-2) 2.5X10-'
'(mol/silver 1 mol) Sensitizing dye (S-3) 0
．． 5XlO-' (mol/silver 1 mol) cyan coupler (C
-1) 0.5 cyan coupler (C-2)
0.05 cyan coupler (C-4)
0.5 colored cyan coupler (CC-1) 0
．． 05DIR compound (D-1) 0.
002 High boiling point solvent (Oll-1)
o, s Gelatin 1.5 4th layer: High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (E++-3) 2.0
Sensitizing dye (S-1) 2. OX 10-' (mol/
1 mol of silver) Sensitizing dye (S-2) 2. OX 10-
'(mol/silver 1 mol) Sensitizing dye (S-3) 0
．． IX 10'''4 (mol/silver 1 mol) Cyan coupler (C-2) 0.015 Cyan coupler (C-3) 0.10 Cyan coupler (C-
4) 0.25 colored cyan coupler (C
C-1) 0.015DIR compound (D-2)
0.05 high boiling point solvent (Oll-1
) 0.2 gelatin
1.5 5th layer: Intermediate layer (IL-2) Gelatin 0.5 6th layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 1.0 Sensitizing dye (S -4) 5.0X 10-' (mol/silver 1 mol) Sensitizing dye (S-5) 1.0XlO-' (
mole/silver 1 mole) magenta coupler (M-1)
0.5 color magenta coupler (CM-1)
0.01 DIR compound (D-3) DIR compound (D-4) High boiling point solvent (Oll-2) Gelatin 0.02 0.02 0.3 1.0 7th layer: Intermediate layer (IL-3) Gelatin 0.8 8th layer: High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Ea+-3), 1.
3 Sensitizing dye (S-6) 1.5X10-' (mol/
1 mol of silver) Sensitizing dye (S-7) 2.5 X
10-' (mol/silver 1 mol) sensitizing dye (S-8)
0.5 x 10-' (mol/mol of silver) Magenta coupler (M-2) 0.05 Magenta coupler (M-3) 0.15 Colored magenta coupler (CM-2) 0.05DIR
Compound (D-3) 0.01 High boiling point solvent (Oil-3) 0.5 Gelatin l.0 9th layer: Yellow filter layer (yc) Yellow colloidal silver
0.1 color stain prevention agent (SC-1)
0.1 high boiling point solvent (Oil-3)
0.1 gelatin 0.8
10th layer: Low-speed blue-sensitive emulsion layer (BL) silver iodobromide emulsion (
Em-1) 0.25 silver iodobromide emulsion (
Em-2) 0.25 sensitizing dye (S-
10) 7 X 10-' (mol/silver 1
Mol) Yellow coupler (Y-1) 0.5
Yellow coupler (Y-2) 0.1DI
R compound CD-2) 0.01 High boiling point solvent (Oil-3) 0.3 Gelatin 1.0 11th layer: High sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-4)
0.50 silver iodobromide emulsion (Em-1)
0.20 Sensitizing dye (S-9) I
X 10-' (mol/silver 1 mol) sensitizing dye (S-1
0) 3X10-' (mol/mol of silver) Yellow coupler (Y-1) 0.30 Yellow coupler (Y-2) 0.05 High boiling point solvent (
Oll-3) 0.15 gelatin
1.1 12th layer: 1st protection 1
11 (PRO-1) Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) High boiling point solvent (Oil-1) High boiling point solvent (Oil-4) Formalin scavenger (Hs-i) Formalin scavenger ( l (S-2) Gelatin 13th layer 2's2 protective layer (PRO-2) Surfactant (S
u-1) Alkali 2 soluble matting agent (average particle size 2μm) Polymethyl methacrylate (average particle size 3μm) 0.10 0.05 0.1 0.1 0.5 0.2 1.0 (5u -2), dispersion aid (Su-3>, hardening agent ()l
-1.40mg/g, gelatin), stabilizer (Stab-
1) and an antifoggant (^F-1) were added.

Lm-1 average grain size 0.46μα, average silver iodide content 7.
0% monodisperse surface low silver iodide content emulsion Em-2 Average grain size 0.30μ, average silver iodide content 2.
Emulsion Em-3 with 0% monodispersity and uniform composition, average grain size 0.81 μm, average silver iodide content 7.
Q% monodisperse surface low silver iodide content emulsion Em-4 average grain size 0.95μ glaze, average silver iodide content 8.
0% monodisperse surface low silver iodide content emulsion 0.005 0.05 Below margin 0.05 0.005 0.01 0.04 0.6 In addition to the above compounds, cyan dye (AIc) is used as a coating aid. -1) Magenta dye (^IM-1) Slip agent (WAX-1) Gelatin In addition, -t -5 -2 -6- -7- -8 S-9 S-t O -1 -2 or less Margin -1 υ1tllllL+LluIJt+3 Nal13) )υ3■a CM-1 CJso S-1 S-2 u-1 2 u-2 11J2 ■ -1 ■ -1 5tab-1 AF-1 Comparison-2 11-1 11-2 Below Margin 11-3 11-4 Comparison-1 (Preparation of Samples 1-2.1-6 to 1-7) Next, instead of the yellow colloidal silver in the 9th layer, dyes shown in Table 1 were added to a high boiling point solvent ( Sample 1-1 except that the color stain preventive agent (Sc-1), surfactant Alkanol Multilayer color photographic elements (Samples 1-2.1-6 to 1-7) were prepared in the same manner as described above.

(Preparation of samples 1-3 to 1-5.1-8 to 1-13) Samples 1-3 to 1-5.1-8 to 1-13 shown in Table-1
For each dye, solid fine particle dispersion was performed using a ball mill according to the following procedure.

Water and a surfactant Alkanol XC (alkylnaphthalene sulfonate, manufactured by DuPont) were placed in a ball mill container, and each dye was added.

Next, zirconium oxide beads were added, the container was sealed, and the mixture was dispersed in a ball mill for 4 days.

Then, add the gelatin aqueous solution and mix for 10 minutes.
The beads were removed to obtain a coating solution.

A multilayer color photographic element (
Samples 1-3 to 1-5, 1-8 to 1-13) were prepared.

In samples 1-2 to 1-13, the amount of dye used was 0.3 g/+2, respectively.

(Preparation of Sample 1-A) Sample 1-A was prepared except that yellow colloidal silver was not added to the 9th layer.
A sample similar to Sample 1 was prepared and designated as Sample 1-A.

After each of the samples 1-1 to 1-13 prepared in this way was wedge exposed using white light, the following development treatment A was performed.
I did it.

Treatment step A (38℃) Color development phenomenon Bleach for 3 minutes 15 seconds
Wash with water for 6 minutes and 30 seconds
Fixation for 3 minutes and 15 seconds, washing with water, stabilization and drying for 6 minutes and 30 seconds, 3 minutes and 15 seconds, and 1 minute and 30 seconds.The composition of the processing solution used in each processing step is as follows.

[Color developer] anhydrous sodium sulfite Hydroxyl ayone 1/2 sulfate Anhydrous potassium carbonate sodium bromide potassium hydroxide Add water to make one flood.

[Bleach solution] 4.25g 2.0g 37.5g 1.38 1.0g Ethylenediaminetetraacetic acid iron ammonium salt xoo, o8 ammonium bromide 150.0g glacial acetic acid
10. Add Omj2 water and add 1
℃ and adjusted to p)I-6.0 using aqueous ammonia.

[Fixer ammonium cothiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to bring the temperature to 1°C, and adjust the pH to -6.0 using acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5+n
, g Konidax (manufactured by Konica) 7.5+
Add +fl water to make iiL.

Further, a processing solution is prepared by removing 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate from the color developing solution in the above processing step, and color development is performed using this, Then, bleaching, fixing, and stabilization treatments were performed in the same manner as in Processing Step A.

(This is referred to as processing step B.) The influence of the dye on fogging was evaluated as follows.

Effect on fog qI: ΔDB2” Processing step A of each sample when measured with blue light
8 at 55°C to evaluate the difference in minimum density between processing step B and processing step B.
After storage for 3 days at 0% relative humidity, the above treatment step A
The sensitivity of the blue-sensitive emulsion layer was compared.

Table 1 *The sensitivity of the blue-sensitive emulsion layer is expressed as the reciprocal of the exposure amount at (minimum density factor 0, 3).

The results obtained are shown in Table-1.

As shown in Table 1, yellow colloidal silver increases fog in the blue-sensitive emulsion layer.

In addition, the comparative dyes (Samples 1-2 to 1-3) have a slight effect on fog and a decrease in the sensitivity of the blue-sensitive layer during storage, whereas the dye used in the present invention has a slight effect on fog. It can be seen that there is little influence on the food and the storage stability is good.

Example 2 On a subbed triacetyl cellulose film support, each layer having the following composition was formed and coated sequentially from the support side.
Sample 2-1 was prepared as a comparative sample of a multilayer color photographic element. The coating amount of each component is indicated by gem2.

Sample 2-1 (comparison) 1st layer: antihalation layer ultraviolet absorber (IJV-1) 0.3
Ultraviolet absorber (UV-2) 0.4 High boiling point solvent (Oil-1) 1.0 Black colloid M O, 24 Gelatin 2.0 Second layer: Intermediate layer 2.5-di-t-octylhydroquinone 0. 1 High boiling point solvent (Oil-1) '0.2
Gelatin 1.0 3rd layer: low sensitivity red-sensitive silver halide emulsion layer (AgI 4.0 mol%
, average particle size 0.25μ) coupler (C-5)
0.1 mol high boiling point solvent (Oil-3)
0.6 gelatin
1.3 4th layer: High sensitivity red-sensitive silver halide emulsion layer (Agl 2.0 mol%, average grain size 0.8 μ) Coupler (C-5) High boiling point solvent (Oll-3) Gelatin 0.2 mol 5th layer: Intermediate layer 2.5-di-t-octylhydroquinone 0.1 High boiling point solvent (Oil-4) 0.2
Gelatin 0.9 6th layer: low-sensitivity green-sensitive silver halide emulsion layer (AgI 4.o mol%,
average particle size 0.25μ) coupler (M-4) coupler (M-5) high boiling point solvent (Oil-1) gelatin 7th layer: high-sensitivity green-sensitive silver halide emulsion layer (AgI2.
o mol%, average particle size 0.6 μ) Coupler (M-4) Coupler (M-5) High boiling point solvent (Oil-1) Gelatin 0.04 mol 0.01 mol 0.5 1.4 0.10 mol 0.02 mol 1.0 1.5's 8th layer: Same as interlayer intermediate layer 9th layer: Yellow filter layer Yellow colloidal silver 0.1 Gelatin
0,92.5-di-t-octylhydroquinone 0.1 High boiling point solvent (011-4) 0.2
3410 layer: Low-speed blue-sensitive silver halide emulsion layer (All
4.0 mol%, average particle size 0.35μ) coupler (Y-
2) 0.3M high boiling point solvent (Ol
l-1) 0.8 gelatin
1,3 Eleventh layer: Highly sensitive blue-sensitive silver halide emulsion layer (AgI 2.0 mol%, average grain size 0.
9μ) Kabuo (Y-2) High boiling point solvent (ott-t) 0.5 mol 1.4 Gelatin 2.1 1st zN1
: First protective layer ultraviolet absorber (UV-1) 0.3 ultraviolet absorber (UV-2) 0.4 high boiling point solvent (Oil-1) 0.8 gelatin 1.22.5-di-t
-Octylhydroquinone 0.1 Sensitizing dye S- 13th layer: N2-protected FiN Average particle size (F) 0. f) Non-photosensitive fine-grain silver halide emulsion consisting of silver iodobromide containing 1 mol% of 8μ silver iodide
Silver amount 0.3 Polymethyl methacrylate particles (diameter 1.5 μm) 0.05 Surfactant (Su-1) 0.0
05 Gelatin 0.7 In addition to the above compounds, gelatin hardener (l(
-1) and a surfactant were added.

Sensitizing Dye S- Sensitizing Dye S- Sensitizing Dye 5-i (Preparation of Sample 2-2.2-7) Next, in place of the yellow colloidal silver in the 9th layer, dyes shown in Table 2 were added with high boiling point. The multilayer color photographic element (Sample 2-2 .2-7) was produced.

(Preparation of samples 2-3 to 2-6.2-8 to 2-10) Samples 2-3 to 2-6.2-8 to 2-10 shown in Table-2
For each dye, solid fine particle dispersion was performed using a ball mill according to the following procedure.

Water and a surfactant Alkanol XC (alkylnaphthalene sulfonate, manufactured by DuPont) were placed in a bowl and an ice container, and each dye was added.

Next, zirconium oxide beads were added, the container was sealed, and the mixture was dispersed in a ball mill for 4 days.

Then, add the gelatin aqueous solution and mix for 10 minutes.
The beads were removed to obtain a coating solution.

A multilayer color photographic element (
Samples 2-3 to 2-6, 2-8 to 2-10) were prepared.

In samples z-t to 2-10, the amount of dye used was 0.3 g/m''.

After each of the samples 2-1 to 2-10 prepared in this manner was wedge exposed using white light, the following development treatment was performed.

[Reversal process] Process Time Temperature First development 6 minutes 38℃ Water washing 2 minutes 38℃ Incubation
Transfer 2 minutes 38℃ Color development 6 minutes 38℃ Adjustment 2 minutes 38℃ bleaching
White 6 minutes 38℃
Fixation 4 minutes 38℃ water
Wash 4 minutes at 38℃
Constant drying for 1 minute at room temperature The composition of the treatment liquid used in the above treatment step is as follows:.

[First developer] Sodium tetrapolyphosphate Sodium sulfite Hydroquinone monosulfonate Sodium carbonate (monohydrate) 1-phenyl-4-methyl-4-hyxymethyl-3-pyrazolidone Potassium bromide Potassium thiocyanate Potassium iodide (0 , 1% solution) Add water [Reverse solution Chodronitrilotrimethylenephosphonic acid 6 sodium salt Stannous chloride (dihydrate) p-aminophenol g 2.5 g 1.28 2 [111 1000 mjl g g 0. Add 1 g of sodium hydroxide and glacial acetic acid water [color developer] Sodium tetrapolyphosphate Sodium sulfite Sodium tertiary phosphate (decahydrate) Potassium bromide Potassium iodide (0.1% solution) Sodium hydroxide citradinic acid -4-Aminoaniline sulfate 2. Add water to 2-ethylenedithiogetanol [adjustment solution] Sodium sulfite ethylenediaminetetraacetate (dihydrate) g 5 2 000 R 8 g 6 g g 90 ml g 1. 5 g 1 000 rnll 2 g Add glacial acetic acid water [bleaching solution] 3 rnll 1000 mi) Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Ethylenediaminetetraacetate iron (■I) ammonium (dihydrate) 12o, og
Ammonium bromide too, add water 1000 ml [Fixer] Ammonium thiosulfate 80.0 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Add water
1000 mjl [stabilizing liquid] Formalin (37% by weight) 5.0 m
j Konidax (manufactured by Konica Corporation) 5.0+
+il water added 1000
mj For each sample treated above, a maximum concentration CD, , ) and a minimum concentration of thioglycerin 0.4 ml (D old.) measured in blue light were determined.

The samples were stored at 55° C. and 80% relative humidity for 4 days, then exposed and processed as described above, and the sensitivities of the blue-sensitive emulsion layers were compared.

The sensitivity of the blue-sensitive emulsion layer is expressed as the reciprocal of the exposure amount at a density of 2.0.

The results are shown in Table-2.

As shown in Table 2 below, yellow colloidal silver has a low maximum concentration. Furthermore, in the comparative sample, a decrease in the sensitivity of the blue-sensitive layer is observed during storage, whereas the dye used in the present invention has a sufficient maximum concentration and has good storage stability.

Other dyes according to the present invention also exhibited the effects of the present invention.

[Effects of the Invention] In the present invention, by using a compound represented by the formula [IJ in a photographic constituent layer, a silver halide photographic light-sensitive material having good fogging and stability over time can be obtained.

Claims (1)

[Scope of Claims] A silver halide photographic material comprising, on a support, at least one photographic constituent layer containing a compound represented by the general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_1 is an aliphatic hydrocarbon group or aryl group, R
_2 and R_3 are hydrogen atoms, aliphatic hydrocarbon groups or aryl groups, or R_2 and R_3 are bonded to form 5
Furthermore, R_4 represents a hydrogen atom, an aliphatic hydrocarbon group, or an aryl group, respectively. L^1, L^2, L^3, and L^4 represent methine groups, L^2 and L^4 may be combined to form a ring with L^3, and Q is an isoxazolone ring. , oxazolidinedione ring, hydantoin ring, thiazolidinedione ring, pyridinedione ring, thiobarbituric acid ring, 1,3-indanedione ring, oxythianaphthene ring, oxindole ring, pyrazolopyridinedione ring. It represents a nonmetallic atomic group, and l and m are integers of 0 or 1. ]