JPH03144438A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material less in fog and improved in stability against time lapse by forming at least one of photographic constituent layers containing a specified water-insoluble compound disposed in it. CONSTITUTION:At least one of the photographic constituent layers formed on a support contains the dispersion of the water-insoluble compounds represented by formula I in which R<1> is alkyl, alkenyl, aryl, or a heterocyclic group; each of R<2>, R<4>, and R<5> is H, alkyl, alkenyl, or cyano; R<3> is alkyl, alkenyl, aryl, a heterocyclic group, or amino: each of L1 - L3 is methine; and (n) is integer of 0, 1, or 2, thus permitting the obtained silver halide photographic sensitive material to be little in fog, improved in storage stability, and freed of deterioration of photographic characteristics.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material containing a novel dye, and more specifically to a fogging material in which a specific layer is dyed with a novel dye. The present invention also relates to a silver halide photographic material that exhibits little desensitization over time.

[Prior Art] Silver halide photographic materials are required to have high image quality characteristics such as excellent sharpness and color reproducibility.

Furthermore, in recent years, in order to compete with the immediacy of competing electrophotographic materials, there has been a demand for further reduction in processing time, that is, suitability for ultra-rapid processing. In order to achieve the high image quality characteristics and ultra-rapid processing suitability required of such photographic materials, the industry is making efforts to further reduce the film thickness of photographic materials and to optimize silver halide and additive compound materials. It has been done.

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

Recently, dyes aimed at replacing yellow colloidal silver in color photographic materials (hereinafter referred to as "YC dyes"), dyes for cross-over cut layers in X-ray photographic materials, and dyes intended to replace yellow colloidal silver in printed photographic materials, and Its uses are expanding, including dyes for dyeing photosensitive emulsion layers.

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 does not affect solution viscosity 7. After processing The properties required include that no color remains.

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. 3.540.
．． No. 887, No. 3.544.325, No. 3.56
0.214, Japanese Patent Publication No. 31-10578, and Japanese Patent Publication No. 51-3623, etc., benzylidene dyes, British Patent No. 506.385 and Japanese Patent Publication No. 39-22069, oxonol dyes, and U.S. Patent No. 2.493. No. 747 proposes a merocyanine dye, and US Pat. No. 1,845,404 proposes a styryl dye. Also, JP-A-1-
No. 196040 and No. 1-196041 disclose heterocyclic arylidene dyes.

[Problems to be Solved by the Invention] 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 layer. It does not stay in the desired layer but spreads to all layers. Therefore, in order to achieve the original purpose, it is necessary to add a large amount of dye to the extent that it will diffuse into other layers, and undesirable phenomena such as decreased sensitivity, gradation fluctuations, and abnormal fogging may occur in both the white layer and other layers. It will appear.

In particular, when photosensitive materials are stored over time, fogging and desensitization occur significantly, and if the amount used is reduced to avoid these problems, the original light absorption effect cannot be obtained sufficiently. To solve this problem, dyes with suppressed diffusion properties that dye specific layers are known. Examples of diffusion-resistant dyes include U.S. Pat.
No. 9, specifications of No. 4,420,555, JP-A No. 1983
-204630, 61-205934, 62-
No. 32460, No. 62-56958, No. 62-929
No. 49, No. 62-222248, No. 63-4014
No. 3, No. 63-184749, No. 63-31685
YC dyes are described in each publication of No. 2. These dyes are also commonly used in color photographic elements.
Yellow colloidal silver called ``arey Lea 5ilver'' absorbs not only the blue light region but also part of the long wavelength side, which reduces green sensitivity and increases fogging of adjacent layers.It is a valuable silver resource and it improves the drawbacks. Many proposals have been made to save money.

Although these diffusion-resistant dyes improve the above drawbacks to some extent, they also have problems such as poor storage stability, desensitization over time, and insufficient bleaching properties, which can cause color staining. A new occurrence has occurred. In order to solve these problems, new diffusion-resistant dyes are required.

Therefore, an object of the present invention is to provide a silver halide photographic material that meets the above-mentioned requirements for a diffusion-resistant filter dye and has less fog and improved stability over time.

[Means for Solving the Problems] The present inventors have conducted intensive studies in view of the above problems, and as a result, the above object of the present invention has been found to be as follows:
It has been found that this can be achieved by a silver halide photographic light-sensitive material characterized by having at least one photographic constituent layer containing a dispersion of a water-insoluble compound represented by the formula.

General formula [I] (wherein, R1 is an alkyl group, alkenyl group, aryl group, or heterocyclic group, and R2, R4, R5, and R6 are each a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group) , carboxyl group, amino group, alkyloxy group, aryloxy group, carbamoyl group, amido group, ureido group, oxycarbonyl group, acyl group, sulfonamido group, sulfamoyl group, sulfonyl group, sulfinyl group, alkylthio group, arylthio group, or a cyano group, R3 is an alkyl group, an alkenyl group, an aryl group,
A heterocyclic group or an amino group, L1L2 and L3 each represent a methine group, and n represents an integer of 0 to 2. ) The present invention will be explained in more detail below.

In general formula [I], examples of the alkyl group represented by each of R+ to R6 include methyl group, ethyl group, n-propyl group, 1so-propyl group, [-butyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-dodecyl group, n-pentadecyl group,
Examples include eicosyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. These groups include those having substituents, such as halogen atoms (e.g. chlorine, bromine, iodine,
each atom such as fluorine), aryl group (e.g. phenyl group,
naphthyl group, etc.), heterocyclic group (e.g. pyrrolidyl group, pyridyl group, etc.), sulfo group, sulfinic acid group, carboxylic acid group, nitro group, hydroxyl group, mercapto group, amino group (e.g. amine group, diethylamino group, etc.), alkyl Oxy groups (e.g. methyloxy, ethyloxy, n-butyloxy, n-octyloxy, isopropyloxy, etc.), aryloxy groups (phenyloxy, naphthyloxy, etc.), carbamoyl groups (e.g. aminocarbonyl, methylcarbamoyl group, n-pentylcarbamoyl group, phenylcarbamoyl group, etc.), amide group (e.g. methylamide group, benzamide group, n-octylamide group, etc.), sulfamoyl group (e.g. methylsulfamoyl group, phenylsulfamoyl group, n-butylsulfamoyl group, etc.), sulfonamide group (e.g. methanesulfonamide group, n-hebutanesulfonamide group, benzenesulfonamide group, etc.), sulfinyl group (e.g. methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group) , alkylsulfinyl groups such as octylsulfinyl group, 7-arylsulfinyl group such as phenylsulfinyl group), alkyloxycarbonyl group (e.g. methyloxycarbonyl group, ethyloxycarbonyl group, 2-hydroxyethyloxycarbonyl group, n-octyl group) oxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), alkylthio group (e.g., methylthio group, ethylthio group, n-hexylthio group, etc.), arylthio group (e.g., phenylthio group, naphthylthio group) etc.), alkylcarbonyl groups (e.g. acetyl group, ethylcarbonyl group, n-butylcarbonyl group, n-octylcarbonyl group, etc.), arylcarbonyl group (e.g. benzoyl group, p-methanesulfonamidobenzoylbenzoyl group, naphthoyl group, etc.) , cyano group, ureido group (e.g. methylureido group, phenylureido group, etc.)
, thioureido groups (eg, methylthioureido group, phenylthioureido group, etc.).

In the general formula [I], examples of the aryl group represented by each of R1 to R6 include a phenyl group and a naphthyl group. These groups include those having substituents, such as the alkyl groups represented by each of R1 to R6, or the above-mentioned substituents for the alkyl groups represented by each of R1 to R6. The following groups are mentioned.

Examples of the alkenyl group represented by each of R+ to R6 in the general formula [I] include a vinyl group, an allyl group, a 1-propenyl group, a 1,3-butadienyl group, a 2-pentenyl group, etc. It includes those having a substituent, and examples of the substituent include those listed as substituents for the alkyl group represented by each of R1 to R6 above.

In the general formula [I], examples of the heterocyclic group represented by each of R1 to R6 include a pyridyl group (2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 5-sulfo-2-
Pyridyl group, 5-carboxy-2-pyridyl group, 3.5
-dichloro-2-pyridyl group, 4,6-cymethyl-2-
Pyridyl group, 6-hydroxy-2-pyridyl group, 2,3
．． 5゜6-tetrafluoro-4-pyridyl group, 3-nitro-2-pyridyl group, etc.>, oxasilyl group (5-sulfo-2-benzoxasilyl group, 2-benzoxasilyl group, 2-oxasilyl group, etc.) , thiazolyl group (5-sulfo-2-benzthiazolyl group, 2-benzthiazolyl group, 2-thiazolyl group, etc.), imidazolyl group (1-methyl-2-imidazolyl group, 1-methyl-5-sulfo-2-
benzimidazolyl group, etc.), furyl group (3-furyl group, etc.), pyrrolyl group (3-pyrrolyl group, etc.), thienyl group (2
-thienyl group, etc.), pyrazinyl group (2-pyrimidinyl group, etc.), pyrimidinyl group (2-pyrimidinyl group, 4-chloro-2-pyrimidinyl group, etc.), pyridazinyl group (2-pyridazinyl group, etc.), purinyl group (8-pyrimidinyl group, etc.), purinyl group, etc.>, isoxasilyl group (3-isoxasilyl group, etc.), selenazolyl group (5-sulfo-2-selenazolyl group, etc.), sulfolanyl group (3-sulfolanyl group, etc.), piperidinyl group (1-methyl- 3-piperidinyl group, etc.), pyrazolyl group (3-pyrazolyl group, etc.), tetrazolyl group (1-methyl-5-tetrazolyl group, etc.), and these groups include those having a substituent, and the substituent is an alkyl group represented by each of the above R1-R6 and R1-
Examples of substituents for the alkyl group represented by R6 include those exemplified.

Examples of the amine group represented by each of R2 to R6 in the general formula ['I] include an alkylamino group, a dialkylamino group, and an arylamino group. Examples of the alkyl and aryl groups include those exemplified as the alkyl groups and aryl groups represented by each of R1 to R6 above, including those each having a substituent. Examples of substituents for the aryl group represented by each are listed below.

In the general formula [I], examples of the oxycarbonyl group represented by each of R2 and R4-R6 include an alkyloxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, and examples of the acyl group include an alkylcarbonyl group. The carbamoyl group includes, for example, an alkylcarbamoyl group, an arylcarbamoylheterocyclic carbamoyl group, a 1-biperidinocarbonyl group,
Nitrogen-containing heterocyclic carbonyl groups such as 4-morpholinocarbonyl group, etc., amide groups include, for example, alkylcarbonylamino groups, arylcarbamoryl groups, heterocyclic carbonylamino groups, etc., and sulfonamide groups include, For example, an alkylsulfonylamino group, an arylsulfonylamino group, a heterocyclic sulfonylamine group, etc.; as a sulfamoyl group, for example, an alkylsulfamoyl group, an arylsulfamoyl group, a heterocyclic sulfamoyl group, etc.; as a sulfonyl group, for example, Examples of the sulfinyl group include an alkylsulfonyl group, an arylsulfonyl group, a heterocycle sulfonyl group, and the like, and in these groups and general formula [I], R2- The alkyl or aryl of the alkyloxy group, aryloxy group, alkylthio group or arylthio group represented by each of R6 is, for example, the above-mentioned R1 to R
Examples of the alkyl group or aryl group represented by each of R1 to R6 above include those exemplified as the alkyl group or aryl group, including those each having a substituent. The following are examples.

In general formula [I], each of R1 to R6 is an alkyl group, an aryl group, an alkenyl group, or a heterocyclic group.
More preferably an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 1 to 12 carbon atoms, and 0 to 12 carbon atoms.
phenyl group having 1 substituents, or 0 to 1 carbon atoms
Represents a pyridyl group having a 2Im substituent.

In the general formula [I], the substituents represented by each of R1 to R6 are preferably a carboxyl group, a hydroxyl group, a sulfamoyl group, a sulfonamide group, an acyl group, a phosphono group,
It has a phosphoryl group, a sulfate ester group, etc., and more preferably a carboxyl group, a hydroxyl group, a sulfamoyl group, or a sulfonamide group.

R1 is a phenyl group, a pyridyl group, or a carbon atom number of 1 to
An alkyl group having 12 fiN or an aralkyl group having 1 to 12 carbon atoms is preferred.

R2 is preferably an alkyl group, carboxyl group, carbamoyl group, sulfamoyl group, alkyloxycarbonyl group, acyl group, sulfonyl group, sulfinyl group or acyl group.

In the general formula [I], R2 preferably represents a cyan group, an alkylcarbonyl group, an arylcarbonyl group, an alkyloxy group, an aryloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylamino group, or a sulfamoyl group.

R3 is preferably an alkyl group, an aryl group or an amino group.

Each of R4 to R6 is preferably a hydrogen atom, an alkyl group, or an aryl group, and particularly preferably a hydrogen atom or an alkyl group.

In addition, compounds represented by the general formula [E] include those having at least one carboxyl group, hydroxyl group, sulfamoyl group, sulfonamide group, or acyl group, especially carboxyl group, sulfamoyl group, or sulfonamide group in the molecule. preferable.

In the present invention, the water-insoluble compound represented by the general formula [I] (hereinafter referred to as the compound of the present invention) refers to a compound whose solubility in pure water (25°C) is 1 g/2 or less, and the solubility is 0.10#. ! The following compounds are preferably used.

Specific examples of the compounds of the present invention are listed below, but the present invention is not limited thereto.

(1) (2) (3) (4) (5) (6) (9) C) (11) (12) (14) (16) (18) (19) (20) (21) (22) (23) OOH (24) (25) (26) CO(Jti (27) (28) (30) (31) (32) (33) (34) (35) (37) (38) (40) (41) (42) (43) (44) (45) (46) to H3 (47) (48) (49) (50) (51) (52) (53) (55) (56) Eight (58) (59) 1" 1 piece Hs (60) (61) (62) 0OH (63) (64) (65) (66) (67) (68) OOH (69) (70) (71) (72) (74) (75) 0OH (76) (77) (78) (79) Shimonko N(CH2COOH)x (80) Specific synthesis examples of the compounds of the present invention are shown below.

Other compounds in the present invention can also be easily synthesized by methods similar to those described below.

<Synthesis example> Synthesis of exemplified compound (1) 7.3 g of n-butylamine and 13 g of acetonyl acetone,
71) and heated at 70 to 80°C for 8 hours.

After cooling to room temperature, the resulting solid was dried.

Keep dimethylformamide 25 yen below 20°C and add phosphorus oxychloride 19.5 while stirring! After dropping If over 30 minutes, the solid obtained above 12.1! A solution of It dissolved in dimethylformamide 501 was added dropwise over 30 minutes. After the addition, the mixture was stirred at 35 to 40°C for 1 hour. Then, the above reaction solution was poured into lfl ice water, and an aqueous sodium hydroxide solution was added. Make it alkaline and precipitate the solid,
It was filtered and dried. A light brown solid 9,89 was obtained. To 1.8 g of the obtained solid (3-formyl-1-n-butyl-2,5-dimethylvirol) and 2.2 g of 3-cyano-1-(4-carboxyphenyl>-5-pyrazolone sodium) was added 1012 g of ethanol. After heating under reflux for 2 hours, the reaction mixture was cooled to room temperature, and the resulting product was separated by filtration.Then, the product was purified by suspension under heating in ethanol 501!2. By repeating the steps above, the target product (compound 1) was obtained.

Yield 2. og: Yield 51% The compound was confirmed by IR, 'HNMR, and FAB/MS measurements.

The compound of the present invention is used in silver halide photographic materials so that the optical density is in the range of 0.05 to 3.0 depending on the purpose.

As a method of adding a dispersion of the compound of the present invention to a photosensitive material, for example, a method of dissolving and dispersing it in a high boiling point organic solvent such as tricresyl phosphate, dioctyl phthalate, etc. is described in European Patent No. 323.728. Specific examples include the method of adding in the form of solid fine particles shown below, and among these methods, the method of adding in the form of solid fine particles is particularly preferred.

In the present invention, photographic constituent layers include photosensitive layers such as blue-sensitive emulsion layers, green-sensitive emulsion layers, red-sensitive emulsion layers, intermediate layers, protective layers, filter layers, antihalation layers, and anti-irradiation layers, or non-photosensitive layers. Indicates gender.

The compound of the present invention is preferably contained in the non-photosensitive layer, particularly preferably in the filter layer.

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.

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

Furthermore, by coupling a colored coupler having a color correction effect with 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, fogging agents, antifogging agents, chemical sensitizers, spectral sensitizers, and sensitizers are used.

A photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, an antiirradiation layer, etc., but these layers and/or emulsion layers contain substances that may flow out of the photosensitive material during development. Alternatively, a bleaching dye may be included.

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 the support for the photosensitive material, paper containing polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

To obtain an image using the photosensitive material of the present invention, commonly known photographic processing can be performed after exposure.

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

Example-1 In all the following examples, the amount added in the silver halide photographic light-sensitive material is ffi per 112 unless otherwise specified.
fi(g> is shown. Silver halide and colloidal silver are shown in terms of silver.

A multilayer color photographic element sample 1-1 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 layer (HC-1) black colloidal silver 0.20Uv absorber (UV-
1) 0.20 colored coupler (CC
-1) 0.05 colored coupler (CM-2
>0.05 high boiling point solvent (Oif -1)
0.20 gelatin
15 2nd layer; Intermediate layer (1, L, -1) UV absorber (UV-1) 0.01 High boiling point solvent (Oif -1) 0.01 Gelatin 1.5 3rd layer; Low sensitivity red-sensitive emulsion Layer (RL) Silver iodobromide emulsion (Effl-1) 0.8 Silver iodobromide emulsion (Em-2) o, g Sensitizing dye (S-1) 2.5X10-4 (mol/
1 mol of silver) 2.5XiO-4 (mol/1 mol of silver) 0.5x 10-now (mol/1 mol of silver) 0.5 0.05 0.5 Sensitizing dye (S-2) Sensitizing dye ( S-3> Cyan coupler (C-1) Cyan coupler (C-2”) Cyan coupler (C-4) Colored cyan coupler (CC-1> 0.05DI
R compound (D-1>0.002 High boiling point solvent (Oil-1) 0.5 Gelatin 1.5 4th layer; High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Effl-3) 2. 0 sensitizing dye (S-1) 2.ox 1O-
4 (mol/silver 1 mol) Sensitizing dye (S-2) 2. Ox10
-Dou (mol/silver 1 mol) Sensitizing dye (S-3> 0.1X1O-4
(Mole/1 mole of silver) Cyan coupler (C-2> 0.015 cyan coupler (C-3) 0.10 cyan coupler (C-4) 0.25 colored cyan coupler (CC-1) 0.015 DIR compound ( D-2) 0.05 high boiling point solvent (Of
f-1) 0.2 gelatin
1.5 5th layer; middle layer (1, L, -
2) Gelatin 6th layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Elf-1) 1.0 sensitizing dye (S-4) 5X10-→ (mol/silver 1 mol) Sensitizing dye (S-5) lX1O-4(
Mol/1 mole of silver> Magenta coupler (M-1) 0.5 Colored magenta coupler (CM-1) 0.5 DIR compound (D-3) DIR compound (D-4) High boiling point solvent (Oil-2) Gelatin 7th layer; Intermediate layer (1, L, -3) Gelatin 8th layer; High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Ell+-3) Sensitizing dye (S-6) 1.5X 10 -Dou〈mol/silver 1mol) 0.01 0.02 0.020 0.3 1.0 0.8 1.3 Sensitizing dye (S-7) Sensitizing dye (S-8> Magenta coupler (M -2) Magenta coupler (M-3) 2.5X10-4 (mol/1 mole of silver) 0.5X10-4 (mol/1 mole of silver) 0.05 0.15 Colored magenta coupler (CM-2) O, 0S DIR compound (D-3) 0.01 High boiling point solvent (Oil-3) 0.5 Gelatin 1.0 9th layer: Yellow filter layer (YC) Yellow colloidal silver
0.1 color stain prevention agent (SC-1)
O11 high boiling point solvent (Oil-3) 0.
1 gelatin 0.8 10th
Layer; low-speed blue-sensitive emulsion layer (B) silver iodobromide emulsion (El
-1) 0.25 silver iodobromide emulsion (EI!+
-2) 0.25 sensitizing dye (S -10)
7X 10-4 yellow coupler (
Y-1) Yellow coupler (Y-2) DIR compound (D-2) High boiling point solvent (Oil-3) Gelatin 11th layer: High sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (Ea-4) Iodobromide Silver emulsion (En+-1) Sensitizing dye (S-, 9) Sensitizing dye (S-10) (mol/silver 1 mol) 0.5 0.1 01 3 0 <8H) 0.50 0.20 1 ×10-now (mol/1 mole of silver) Oil-3) Gelatin 112FJ: Ill [[(PRO-1) Fine grain silver iodobromide emulsion 0.4 (average grain size 0.08μ, A
g12 mol%) UV absorber (UV-1>
0.10 UV absorber (UV-2) 0
．． 05 High boiling point solvent (Oif -1) 0
．． 1 High boiling point solvent (○1f-4) 0.1
Formalin scavenger (S-1) 0.5 Formalin scavenger (S5-2) 0.2 Gelatin
1.0 13th layer: 2nd protective layer (PRO-2) Surfactant (Su -1) 0.005
Alkali-soluble matting agent 0.05 (average particle size 2 μm) Polymethyl methacrylate 0.05 (average particle size 3 μm) Cyan dye (A I C-1) 0.00
5 Magenta dye (AIM-1) 0.01 Slip agent (WAX-1) 0.04 Gelatin 0 and 6 Both pot layers contain coating aid Su-2 and dispersion aid 5u in addition to the above coarse material.
-3, hardener Rho 1 (401m (+/++ gelatin)), stabilizer 3tab-1, and antifoggant AF-1 were added.

m -1 Average grain size 0.46 μm, average silver iodide content monodisperse surface, low silver iodide content emulsion m -2 Average grain size 0.30 μm, average silver iodide content monodisperse, uniform Composition emulsion i-3 Average grain size 0.81 μm, average silver iodide content Monodisperse surface low silver iodide content emulsion m-4 Average grain size 0.95 μm, average silver iodide content 7.0 %.

2.0%.

0%.

8.0%.

-6 S-7 -9 s-i.

-1 M-2 CC-1 M-1 M-2 -1 -2 I -3 -4 UV-1 C4HI(L) UV-2 -1 CH2=CHSO2CH20CHISOzCH=CHt
u-1 N t Os S C-COOCH2(CF-CF
* ) s HC-C00C)l, (CF, CF,)
3HH7 u 2 Na03S-C-COOC, H4 CHz-COOC*H+t u 3 (J?1 TC-1 8LM-1 CH.

CH.

11-3 4 C2H.

(Preparation of Samples 1-2 and 1-5 to 1-8) Instead of the yellow colloidal silver in the 9th layer, dyes shown in Table 1 were added to a high boiling point solvent (Oil-3), a color stain inhibitor (SC Multilayer color photographic elements 1-2 and 1-1 were prepared in the same manner as Sample 1-1 except that the surfactant Alkanol 1-5 to 1-8 were produced.

(Preparation of samples 1-3.1-4 and 1-9 to 1-11) Samples 1-3.1-4 and 1-9 to 1-11 shown in Table 1
The dyes used in each were subjected to ball mill solid fine particle dispersion according to the following procedure.

Water and a surfactant Alkanol XC (alkylnaphthalene sulfonate, manufactured by DuPont) were placed in a ball mill container, zirconium oxide beads containing each dye were added, the container was sealed, and ball mill dispersion was performed for 4 days.

Thereafter, an aqueous gelatin solution was added and mixed for 10 minutes, and the beads were removed to obtain a coating solution. Multilayer color photographic elements 1-3.1-4 and 1-9 to 1 were prepared in the same manner as Sample 1-1 except that this coating liquid was used as the ninth layer in Sample 1-1.
1-11 was produced.

In addition, in samples 1-1 to 1-11, the amount of dye used was 0.3 (1/f) Comparative dye 1 Comparative dye 2 Comparative dye 3 ○ Each sample 1- After each of Samples Nos. 1 to 1-11 was wedge exposed using white light, the following development treatment was performed.

Processing step A (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Wash 3 minutes 15 seconds Fix
Wash with water for 6 minutes and 30 seconds
Stabilized for 3 minutes and 15 seconds 1
Drying for minutes and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline Ta-acid 4.759 Anhydrous sodium sulfite 4.2 sg Hydroxylamine 1/2@acid 2 ．． og anhydrous potassium carbonate 37.5 g sodium bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5.

Potassium hydroxide 1.0g Add water to make 11.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100. OIll
Ethylenediaminetetraacetic acid diammonium salt 10. OQ ammonium bromide 750.0 (J wood vinegar M
10. Add 01fi water to make it 11, and adjust to p=6.0 using ammonia water.

[Fixer 1 Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 t
and adjust to I)H=6.0 using acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5te Konidax (Konica ■It) 7.5t12
Add water to make 1 fl.

In addition, 4-amino-3-
Methyl-N-ethyl-N-(β-hydroxyethyl)-
A processing solution excluding aniline and sulfate is prepared, and color development is performed using this, followed by bleaching and bleaching in the same manner as processing step A.
Fixation and stabilization treatments were applied. (Referred to as processing step B) The influence of dyes on fogging was evaluated as follows.

(Influence on fog) ΔDB2 = Difference between the minimum yellow density in processing step A and the minimum yellow density in processing step B for each sample (1-1 to 1-12) Also, to evaluate the storage stability of the photosensitive material over time After forced storage at 55° C. and 80% relative humidity for 3 days, the above processing step A was applied, and the decrease in sensitivity of the blue-sensitive emulsion layer was expressed as ΔS8 and compared.

Δ5B 55℃80%R'', after storage for 3 days = sensitivity of blue-sensitive emulsion layer, 100 (%) Sensitivity of blue-sensitive emulsion layer before forced storage However, the sensitivity of the blue-sensitive emulsion layer is (minimum density , 3) is expressed as the reciprocal of the exposure amount.

The results obtained are shown in Table 1.

Table 1 As shown in Table 1, the fog in the blue-sensitive layer of the sample of the present invention is improved compared to the case where yellow colloidal silver is used.

On the other hand, in Comparative Dyes 1, 2, or 3 (Samples 1-2 to 1-4), a decrease in sensitivity of the blue-sensitive layer was observed due to storage. In contrast, it can be seen that the samples using the dye of the present invention have less influence on fog and have good storage stability.

Example 2 Sample 2-1 was prepared as a comparative sample of a multilayer color light-sensitive material by sequentially coating each layer having the following composition on a subbed triacetylcellulose film support from the support side.

The coating amount of each component is expressed as (J/f).

(Sample 2-1) 1st layer (antihalation layer) Ultraviolet absorber (UV-1) 0.3 Ultraviolet absorber (UV-2) 0.4 High boiling point solvent (O
it -1 > 1.0 black colloidal silver
0.24 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 Third layer; low sensitivity red-sensitive silver halide emulsion layer red sensitizing dye (S-2
, 8-11) spectrally sensitized by ΔqBrl (Atll 1 4.0 mol%, average particle size 0.25μ)
0.5 Coupler (C-5) 0.1 mol High boiling point solvent (0+I -3> 0.6 Gelatin 1.3 4th layer; High sensitivity red-sensitive silver halide emulsion layer Red sensitizing dye (S-2, S-
11) AgBr1 (Aa 1 2 mol %, average particle size 0.6 μ) 0.8 coupler (C-5) 0.2 mol high boiling solvent co 1+-3) 1.2 gelatin
1.8 5th layer (intermediate layer) 2.5-di-t-octylhydroquinone 0.1 High boiling point solution* (Oil-4> 0.2 Gelatin 0.9 6th layer (low sensitivity green sensitive silver halide Emulsion layer) Aasri (A(It I 4 mol%, average grain size 0.25μ) 6 Cobra (M-4>0.04) spectrally sensitized by green sensitizing dyes (S-12 and S-13) Molar coupler (M-5 > 0.01 mol High boiling point solvent (Oil-1 > 0.5 gelatin
1.4 7th layer (high sensitivity green-sensitive silver halide emulsion layer) green sensitizing dye (S-12, S-13)
A(l[3r1 (Ag1 2 mol%, average particle size 0.6μ) High boiling point solvent (Oit -1)' 1.0 Gelatin 1,5 8th layer (intermediate layer) 9th layer (yellow filter layer) same as 5th layer Yellow colloidal silver 0.1 Gelatin 0.92.5-di -t-
Octylhydroquinone 1 High boiling point solvent (Oil-4) 0.2 1st
0 layer (low sensitivity blue-sensitive silver halide emulsion layer) AgBr1 spectrally sensitized with blue sensitizing dye (S-14) (AOr 4 mol%, average grain size 0.35μ) 6 Cobra (Y-2) 0.3 mol High boiling point solvent (Oil-1) 0.6 Gelatin 1,3 11th layer (high sensitivity blue-sensitive silver halide emulsion layer) Blue sensitizing dye (S-14
) spectrally sensitized by AQ 3r 1 (Ag I 2 mol %, average particle size 0.9 μ) 0.9 coupler (Y-2) 0.5 mol high boiling point solvent (Oil -1 > 1.4 gelatin 2 .1 12th layer; 1st protective layer Ultraviolet absorber (LIV-1) 0.3 Ultraviolet absorber (UV-2) 0.4 High boiling point solvent (Oil -1) 0.6 Gelatin
1.22.5-zyl-t-octylhydroquinone 0.1 13th layer: second protective layer average grain size (r) 0.08 μ layer, non-photosensitive layer made of silver iodobromide containing 1 mol% of silver iodide Fine grain silver halide emulsion Silver amount 0.8 Polymethyl methacrylate particles (diameter 1.5 μm) Surfactant (SLI-1
) Gelatin 07 In addition to the above composition, a gelatin hardening agent (day 1) and a surfactant were added to each layer.

Sensitizing dye 5-11 Sensitizing dye-12 Sensitizing dye 5-13 Sensitizing dye 5-14 Coupler M-4 I Coupler-5 (Preparation of samples 2-2 and 2-5 to 2-7) Sample 1 except that instead of the nine layers of yellow colloidal silver, the dye shown in Table 2 was dissolved in ethyl acetate together with a high boiling point solvent (Oil-4, 2°5-dioctylhydroquinone) and dispersed and coated with gelatin. Multilayer color photographic elements 2-2 and 2-5 to 2-7 were prepared in the same manner as in Example 1.

(Preparation of samples 2-3.2-4 and 2-8 to 2-10) Samples 2-3.2-4 and 2-8 to 2-10 shown in Table 2
For each dye, perform solid fine particle dispersion 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, zirconium oxide beads containing each dye were added, the container was sealed, and ball mill dispersion was performed for 4 days.

Thereafter, an aqueous gelatin solution was added and mixed for 10 minutes, and the beads were removed to obtain a coating solution. Multilayer color photographic elements 2-3, 2-4 and 2-8 to 2-8 were prepared in the same manner as Sample 2-1 except that this coating liquid was used as the ninth layer in Sample 1-1.
2-10 was produced.

Further, in samples 2-1 to 2-10, the amounts of the dyes used were set to o and sg/f, respectively.

Samples 2-1 to 2-10 thus obtained were wedge-exposed to white light and then subjected to the following development treatment.

Processing process Processing time Processing temperature First development 6 minutes 38℃ Water washing 2 minutes 38℃ Inversion 2 minutes 38℃ Color development 6 minutes 38℃ Adjustment 2 minutes 38℃
Bleach 6 minutes 38℃
Fixation 4 minutes Wash with water at 38℃ 4 minutes Stable at 38℃ 1 minute Dry at room temperature
The composition of the treatment liquid used in the drying step is as follows.

Sodium tetrapolyphosphate 2 g Sodium sulfite 20 (1 hydroquinone monosulfonate 309 Sodium carbonate (monohydrate) 30 g 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone 2g potassium bromide
2.5g potassium thiocyanate
1.2g potassium iodide (0.1% solution)2
1 (Add water to 1000 tN inversion liquid Nitrilotrimethylenephosphonic acid 6-sodium salt 3g 1st chloride
Tin (dihydrate) IC1p-aminephenol 0.1g Sodium hydroxide
8g ice vinegar M
15 Add Tsuru water
1000t12 color developer Sodium tetrapolyphosphate 3g Sodium sulfite 7g Sodium tertiary phosphate (dihydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90i12 Sodium hydroxide 8g Citrazine acid
1,5g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline/Fa
Butyrate ii g2. Add 2-ethylenedithiogetanol 1g water
1000 iR adjustment solution Sodium tatrite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 d Glacial acetic acid
312 Add water
10001p Bleach Solution Sodium Ethylenediaminetetraacetate (Dihydrate) 2゜Iron (II) Ammonium Ethylenediaminetetraacetate (Dihydrate)
1201; Add 100g of ammonium monobromide water
1000 iR fixer Ammonium thiosulfate 80 Q Sodium sulfite 5g Sodium bisulfite 5g Add water
Conidax (Konica Corporation'SJ> hI2
The maximum density (DWaX) and minimum density (Dmin) of each sample developed with water for 1000 d under blue light were measured.

Further, each sample was stored at 55° C. and 80% relative humidity for 4 days and then subjected to the above exposure and processing, and the decrease in sensitivity of the blue-sensitive emulsion layer was expressed as ΔSs and compared.

Δ58 Sensitivity of the blue-sensitive emulsion layer after storage for 4 days at 55°C, 80% R, H = 100 (%) Sensitivity of the blue-sensitive emulsion layer before forced storage The sensitivity of the blue-sensitive emulsion layer is at a density of 2.0. It is expressed as the reciprocal of the exposure amount.

Table 2 As shown in Table 2, the sample of the present invention has a higher maximum concentration than when using yellow colloidal silver. In addition, the sample using the comparative dye has a large minimum density (and a decrease in the sensitivity of the blue-sensitive layer during storage is observed, whereas the sample using the compound of the present invention has a small minimum density and a sufficient maximum density). It had high concentration and good storage stability.

Example 3 A silver chlorobromide emulsion was prepared at 40° C. with a silver bromide content of 4 mol % and an added amount of rhodium chloride 1×10′ (1 mol AaX).
XjI was prepared using the simultaneous mixing method for 0 minutes.

The emulsion thus prepared y4 was desalted and redispersed to obtain a monodispersed emulsion with an average grain size of 0.21 μm. Rhodium chloride was dissolved in a sodium chloride solution and added to the halide solution.

These emulsions were chemically sensitized by adding a small amount of sodium thiolIiIate at 55°C for 30 minutes, and using 6 as a stabilizer.
-Methyl-4-hydroxy-1,3,38.

7-Chitrazaindene was added. Next, the compounds shown in Table 3 were added to these emulsions as a solid dispersion in the same manner as in Example 1 in an amount of 0.8 (]1 mol AgX, and 1-phenyl- C 3 (amount -20, l+n-15) was added as a 5-mercaptotetrazolone oxide compound, saponin was added as a spreading agent, and mucochloric acid was added as a hardening agent, so that the silver amount was 3.5 g/l. 'Apply on the film base and dry.

Samples 3-1 to 3-9 obtained in this way were heated under a fading light (
Toshiba FL40SW-NU) 60 under approximately 300 Lux
A safelight property test was conducted for the separation example, and the following developer was used to develop the sample and fog was measured. Immediately after coating and after forced deterioration by leaving it in an atmosphere with a temperature of 50°C and humidity of 70% RH for 2 days, it was exposed through a light wedge using a bright room printer (HMW-215 manufactured by Oak Seisakusho) and developed as described below. It was developed using a solution.

Developer formulation> Hydroquinone 15g Formaldehyde, sodium bisulfite and adduct 50g Potassium sulfite 4g Potassium carbonate
so ghou F11
2 (JKBr
2a Triethylene glycol 49EDTA-2Na
2 diethanolamine
75-Nitroindazole 3 Ethylene urea 0.5 Polyethylene glycol (average molecular weight 1500) 0.4 Sodium hydroxide 1 Add water to 1
Set it to 2.

The developing conditions were 27° C. and 1 minute and 40 seconds.

Comparative dye 4 Comparative dye 5 Comparative dye 6 As is clear from Table 3, samples 3-4 to 3-9 of the present invention
It can be seen that it has an ultra-low sensitivity that can be handled as a light-sensitive material for bright rooms, has an improved relationship between safelight properties and sensitivity, has a high contrast, and has extremely low sensitivity changes and N-tone changes during storage. .

Example 4 3.5 g of gelatin was added and dissolved in 3.5 g of distilled water, and 2.5 g of each of the exemplified compounds shown in Table 4 was added thereto. OX10
-4 mol Added as a solid dispersion in the same manner as in Example 1, and further added 1 mol.
Add 1.25 tffi of 0% saponin solution and 0.75 tffi of 1% formalin solution, and add water to bring the total volume to 50 tf.
It was set as 2. This dye solution was applied onto an acetyl cellulose film support and dried to give samples 4-5 to 4-14. Moreover, instead of the compound of the present invention, comparative dye (2)
, (3), (4), and the comparative dye (7) shown below, Comparative Dye 7 Each of these samples was immersed in a developer having the following composition for 1 minute at 25°C, and then washed with water for 20 seconds. After that, it was dried.

(Composition of developer) Metol 3.0 (1 Sodium sulfite (anhydrous) 45.0 (1 Hydroquinone 12.OQ Sodium carbonate (monohydrate) go, o g Potassium bromide
2.0 (Add J water to make 11.

The decolorization state of each sample was visually evaluated before and after immersion in the developer. The results are shown in Table 4. 〈○ mark indicates that no color stain was observed, Δ mark indicates that color stain was slightly observed, and X mark indicates that color stain was significant. > Table 4 As is clear from Table 4, the compounds of the present invention were found to exhibit superior decolorizing properties compared to the comparative dyes. Also,
In the comparative sample, the treatment solution was colored and contaminated by the eluted dye, but in the sample of the present invention, no such colored stain was observed.

[Effects of Enrichment] As explained in detail above, by containing the water-insoluble compound of the present invention as a dispersion, fogging is reduced, stability over time during storage is improved, and halogen without deterioration of photographic properties is achieved. A silver oxide photographic material is provided.

Claims (1)

[Scope of Claims] A silver halide photographic material comprising, on a support, at least one photographic constituent layer containing a dispersion of a water-insoluble compound represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 is an alkyl group, alkenyl group, aryl group or heterocyclic group, R^2, R^4, R^5 and
^6 is a hydrogen atom, an alkyl group, an alkenyl group, respectively.
Aryl group, heterocyclic group, carboxyl group, amino group,
Alkyloxy group, aryloxy group, carbamoyl group, amido group, ureido group, oxycarbonyl group, acyl group, sulfonamide group, sulfamoyl group, sulfonyl group, sulfinyl group, alkylthio group, arylthio group or cyano group, R^3 is an alkyl group, an alkenyl group,
Aryl group, heterocyclic group or amino group, L_1, L_
2 and L_3 each represent a methine group, and n represents an integer of 0 to 2. )