JP2852440B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material containing a novel dye, and more particularly, to a fog in which a specific layer is dyed with a novel dye. And a silver halide photographic material having 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.

Further, in recent years, in order to counter the immediateness of competing electrophotographic materials, further reduction in processing time, that is, ultra-rapid processing aptitude is required. In order to achieve the high image quality characteristics and ultra-rapid processing suitability required for such photographic materials, the industry is working to further reduce the thickness of photographic materials and optimize silver halide and additive compound materials. It has been done.

It is well known that a dye is included in a silver halide photographic material for the purpose of improving image quality or adjusting the sensitivity of a silver halide emulsion. For example, it is used for preventing halation, preventing irradiation, and using a light absorption filter. Have been.

Recently, dyes (hereinafter referred to as “YC dyes”) for replacing yellow colloidal silver in color photographic light-sensitive materials, the first dyes in crossover cut layers in X-ray photographic light-sensitive materials, and non-photosensitive Applications such as dyes for dyeing the emulsion layer are widespread.

The dye used for these purposes depends on the purpose of use. 1. It must have a good absorption spectrum. 2. It must not diffuse from the colored layer to other layers. No effect 4. Stable in silver halide photographic light-sensitive material 5. Easily added 6. Stable in emulsion coating solution and do not affect solution viscosity 7. After processing It is required that the color does not remain.

Numerous dyes have been proposed for the purpose of satisfying these desired properties, for example, US Pat. No. 3,540,88
No. 7, No. 3,544,325, No. 3,560,214, Tokiko 31-1
No. 0578 and JP-A-51-3623, benzylidene dyes, British Patent No. 506,385 and JP-B-39-2269, oxonol dyes, U.S. Pat.No. 2,493,747, merocyanine dyes, Styryl dyes and the like have been proposed. Also, JP-A-1-196040, JP-A-1-196040
In 196041, a heterocyclic arylidene dye is disclosed.

[Problem to be Solved by the Invention] It is a general method to dissolve these dyes in water or an organic solvent miscible with water and add them to a photographic component layer.
When the dye is water-soluble, it is diffused not only in the layer to be dyed but also in all layers. Therefore, in order to achieve the original purpose, it is necessary to add a large amount of dye to the other layer in order to diffuse into the other layer, and undesired phenomena such as a decrease in sensitivity, gradation fluctuation and fog abnormality in both the own layer and the other layer are required. It will appear.
In particular, when the photosensitive material is stored over time, fogging and desensitization are remarkable, and if the amount used is reduced to avoid these, the original light absorbing effect cannot be sufficiently obtained. Dyes with suppressed diffusivity such as dyeing a specific layer for such a problem are known, and as diffusion-resistant dyes, for example, U.S. Patent Nos. 2,538,008, 2,539,009, and 4,420,555
Nos., JP-A-61-204630, JP-A-61-205934,
62-32460, 62-56958, 62-92949, 62
-222248, 63-40143, 63-184749, 63-3
Each publication of 16852 describes a YC dye. Also, these dyes are commonly used in color photographic elements
Improvement of the drawback that yellow colloidal silver called Carey Lea Silver absorbs not only the blue light region but also a part of the longer wavelength side, thereby lowering the green sensitivity, increasing the fogging of the adjacent layer, and precious silver resources Many have been proposed to save money.

Although these deficiencies are improved to some extent by these diffusion-resistant dyes, on the other hand, storage stability is deteriorated, desensitization occurs with time, and bleaching is insufficient, which causes color contamination. Newly occurred. In order to solve these problems, a new diffusion-resistant dye is required.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material which satisfies the above-mentioned requirements for a diffusion-resistant filter dye and has little 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 object of the present invention was to provide a water-insoluble compound represented by the following general formula [I] on a support. And at least one photographic constituent layer containing the dispersion of (1).

General formula [I] (Wherein, R ¹ represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; R ² represents a hydrogen atom, an alkenyl group, a heterocyclic group, an amino group, an alkyloxy group, an aryloxy group, an albamoyl group, An amide group, a ureido group, an oxycarbonyl group, an acyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfanyl group, an alkylthio group, an arylthio group or a cyano group, and R ³ represents an alkyl group, an alkenyl group, an aryl group, or a hetero group. Represents a ring group or an amino group, R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group,
Amino group, alkyloxy group, aryloxy group, carbamoyl group, amide group, ureido group, oxycarbonyl group, acyl group, sulfonamide group, sulfamoyl group,
Represents a sulfonyl group, a sulfanyl group, an alkylthio group, an arylthio group or a cyano group, L ₁ , L ₂ and L ₃ each represent a methine group, and n represents an integer of 0 to 2. Hereinafter, the present invention will be described in more detail.

In the general formula [I], examples of the alkyl group represented by each of R ¹ , R ^{3 to} R ₆ include a methyl group, an ethyl group and an n-
Propyl group, iso-propyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-dodecyl group, n-pentadecyl group,
Examples include an eicosyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. These groups include those having a substituent, and examples of the substituent include a halogen atom (eg, chlorine, bromine, iodine,
Each atom such as fluorine), an aryl group (for example, a phenyl group,
Naphthyl group, etc.), heterocyclic group (eg, pyrrolidyl group, pyridyl group, etc.), sulfo group, sulfinic acid group, carboxylic acid group, nitro group, hydroxyl group, mercapto group, amino group (eg, amino group, diethylamino group, etc.), alkyl Oxy group (for example, methyloxy group, ethyloxy group, n-butyloxy group, n-octyloxy group, isopropyloxy group, etc.), aryloxy group (phenyloxy group, naphthyloxy group, etc.), carbamoyl group (for example, aminocarbonyl group, A methylcarbamoyl group, an n-pentylcarbamoyl group, a phenylcarbamoyl group, an amide group (eg, a methylamide group, a benzamide group, an n-octylamide group, etc.), a sulfamoyl group (eg, a methylsulfamoyl group, a phenylsulfamoyl group, n-butylsulfamoyl group), A sulfonamide group (eg, a methanesulfonamide group, an n-heptanesulfonamide group, a benzenesulfonamide group, etc.), a sulfinyl group (eg, an alkylsulfinyl group such as a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, an octylsulfinyl group, etc.), and a phenylsulfinyl group Aryloxycarbonyl group (e.g., methyloxycarbonyl group, ethyloxycarbonyl group, 2-hydroxyethyloxycarbonyl group, n-octyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group). Carbonyl group, naphthyloxycarbonyl group, etc.), alkylthio group (eg, methylthio group, ethylthio group, n-hexylthio group, etc.), arylthio group (eg, phenylthio group) , Naphthylthio group, etc.), an alkylcarbonyl group (e.g. acetyl group, ethylcarbonyl group, n- butyl group, n- octyl group, etc.), an arylcarbonyl group (e.g. benzoyl group, p- methanesulfonamide benzoyl group,
p-carboxybenzoyl group, naphthoyl group, etc.), cyano group, ureido group (eg, methylureide group, phenylureide group, etc.), thioureide group (eg, methylthioureide group, phenylthioureide group, etc.).

In the general formula [I], examples of the aryl group represented by each of R ¹ and R ^{3 to} R ⁶ include a phenyl group and a naphthyl group. These groups include those having a substituent,
Examples of the substituent, for example, the aforementioned R ^1, an alkyl group represented by each of R ³ to R ^6, or the aforementioned groups mentioned as substituents for the alkyl group represented by each of R ^1, R ³ to R ⁶ Is mentioned.

In the general formula [I], examples of the alkenyl group represented by each of R ^{1 to} R ⁶ include a vinyl group, an allyl group, a 1-propenyl group, a 1,3-butadienyl group, and a 2-pentenyl group. Include those having a substituent, and examples of the substituent include those described above as the substituent of the alkyl group represented by each of R ^{1 to} R ⁶ .

In the general formula [I], examples of the heterocyclic group represented by each of R ^{1 to} R ⁶ 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-dimethyl-2-pyridyl group, 6-hydroxy-2-pyridyl group, 2,3,5,6-tetrafluoro-4-pyridyl group, 3-nitro-2-pyridyl group, etc., oxazolyl group (5-sulfo-2-benzoxazolyl group) , 2-benzoxazolyl group, 2-oxazolyl group, etc.), thiazolyl group (5-sulfo-2-benzthiazolyl group, 2-benzothiazolyl group, 2-thiozolyl group, etc.), imidazolyl group (1-methyl-2-imidazolyl group) 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- Pyridinyl group), pyrimidinyl group (2-pyrimidinyl group, 4-chloro-2-pyrimidinyl group, etc.), pyridazinyl group (2-pyridazinyl group, etc.), purinyl group (8-purinyl group, etc.), isoxazolyl group (3-isoxazolyl) 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.) ), A tetrazolyl group (e.g., a 1-methyl-5-tetrazolyl group), and the like, including those having a substituent, and examples of the substituent include R ¹ , R ³ ,.
Those exemplified as substituents for the alkyl group represented by each of R alkyl group and R ¹ is represented by each of ^6, R ³ to R ⁶ may be mentioned.

In the general formula [I], examples of the amino group represented by each of R ^{2 to} R ⁶ include an alkylamino group, a dialkylamino group, and an arylamino group. Examples of the alkyl and aryl include those exemplified as the alkyl group and the aryl group represented by each of R ¹ and R ^{3 to} R ⁶ , including those having a substituent, and the substituent includes, for example, Examples of the substituent of the aryl group represented by each of R ¹ and R ^{3 to} R ⁶ are given.

In the general formula [I], the oxycarbonyl group represented by each of R ² and R ^{4 to} R ⁶ includes, for example, an alkyloxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, and the like. For example, an alkylcarbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group and the like, as the carbamoyl group, for example, an alkylcarbamoyl group, an arylcarbamoyl group, a heterocyclic carbamoyl group, a 1-piperidinocarbonyl group,
Nitrogen-containing heterocyclic carbonyl groups such as 4-morpholinocarbonyl group and the like, amide groups such as alkylcarbonylamino group, arylcarbonylamino group and heterocyclic carbonylamino group, and sulfonamide groups such as alkylsulfonylamino Group, an arylsulfonylamino group, a heterocyclic sulfonylamino group, etc., as the sulfamoyl group, for example, an alkylsulfamoyl group, an arylsulfamoyl group, a heterocyclic sulfamoyl group, etc., and as the sulfonyl group, for example, an alkylsulfonyl group, Examples of the arylsulfonyl group, heterocyclic sulfonyl group, and the like, and examples of the sulfinyl group include an alkylsulfinyl group, an arylsulfinyl group, and a heterocyclic sulfinyl group. These groups and the general formula [I]
An alkyloxy group represented by each of R ^{2 to} R ⁶ ,
Examples of the aryloxy group, the alkyl and the aryl of the alkylthio group and the arylthio group include those exemplified as the alkyl group or the aryl group represented by each of R ^{1 to} R ⁶ , including those having a substituent. Examples of the substituent include those exemplified as the substituent of the aryl group represented by each of R ¹ , R ^{3 to} R ⁶ .

In the general formula [I], each of R ¹ , R ^{3 to} R ⁶ is an alkyl group, an aryl group, an alkenyl group and a heterocyclic group, more preferably an alkyl group having 1 to 12 carbon atoms,
Represents an aralkyl having 1 to 12 carbon atoms, a phenyl group having a substituent having 0 to 12 carbon atoms, or a pyridyl group having a substituent having 0 to 12 carbon atoms.

In the general formula [I], the substituent represented by each of R ¹ , R ^{3 to} R ⁶ is preferably a carboxyl group, a hydroxyl group, a sulfamoyl group, a sulfonamide group, an acyl group, a phosphono group, a phosphoryl group, a sulfate group, or the like. And more preferably a carboxyl group, a hydroxyl group, a sulfamoyl group or a sulfonamide group.

R ¹ is a phenyl group, a pyridyl group, having 1 to 1 carbon atoms.
Preferred are 12 alkyl groups or aralkyl groups having 1 to 12 carbon atoms.

R ² is preferably a carbamoyl group, a sulfamoyl group, an alkyloxycarbonyl group, an acyl group, a sulfonyl group or a sulfinyl group.

In the general formula [I], R ² preferably represents a cyano 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. .

R ³ is preferably an alkyl group, an aryl group or an amino group.

Each of R ^{4 to} R ⁶ is preferably a hydrogen atom, an alkyl group or an aryl group, and particularly preferably a hydrogen atom or an alkyl group.

Further, as the compound represented by the general formula [I], a compound having at least one carboxyl group, hydroxyl group, sulfamoyl group, sulfonamide group or acyl group in the molecule, particularly having carboxyl group, sulfamoyl group or sulfonamide group, is preferred. 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 having a solubility in pure water (25 ° C.) of 1 g / or less.
Compounds of 0.1 g / or less are preferably used.

Hereinafter, specific examples of the compound of the present invention will be given, but the present invention is not limited thereto.

(1) (2) (3) (4) (5) (6) (7) (8) (9) (Ten) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) (twenty three) (twenty four) (twenty five) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (36) (37) (38) (39) (40) (41) (42) (43) (44) (45) (46) (47) (48) (49) (50) (51) (52) (53) (54) (55) (56) (57) (58) (59) (60) (61) (62) (63) Hereinafter, specific synthesis examples of the compound of the present invention will be described. Other compounds in the present invention can be easily synthesized in the same manner as described below.

<Synthesis Example> Synthesis of Exemplified Compound (1) 7.3 g of n-butylamine and 13.7 g of acetonylacetone were mixed and heated at 70 to 80 ° C for 8 hours. After cooling to room temperature, the resulting solid was dried.

After maintaining 25 ml of dimethylformamide at 20 ° C. or lower and adding dropwise 19.5 g of phosphorus oxychloride over 30 minutes with stirring,
A solution of 12.1 g of the solid obtained above in 50 ml of dimethylformamide was added dropwise over 30 minutes. 35-40 ° C after dropping
For 1 hour. Thereafter, the above reaction solution was poured into ice water 1, an aqueous solution of sodium hydroxide was added to make the solution alkaline, and a solid was precipitated. 9.8 g of a light brown solid was obtained. The resulting solid (3-formyl-1-n-butyl-
1.8 g of 2,5-dimethylpyrrole and 3-cyano-1- (4
-Carboxyphenyl) -5-pyrazolone sodium 2.
10 ml of ethanol was added to 2 g, and after heating under reflux for 2 hours, the reaction product was cooled to room temperature, and the obtained product was separated by filtration. Next, the product was subjected to heat suspension purification in 50 ml of ethanol, and this treatment was repeated to obtain the desired product (compound 1).

The compound was confirmed by IR, ¹ HNMR, and FAB / MS measurements.

The compound of the present invention is used in a silver halide photographic material 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 light-sensitive material, for example, a method of dissolving and dispersing in a high-boiling organic solvent represented by tricresyl phosphate, dioctyl phthalate, or the like, a solid shown in European Patent No. 323,728 Specific examples thereof include a method of adding in the form of fine particles, and among them, a method of adding in the form of solid fine particles is particularly preferable.

In the present invention, the photographic constituent layer is, for example, a blue-sensitive emulsion layer,
And photosensitive or non-photosensitive layers such as a green-sensitive emulsion layer, a red-sensitive emulsion layer, an intermediate layer, a protective layer, a filter layer, an antihalation layer, and an anti-irradiation layer.

The compound of the present invention is preferably contained in a non-photosensitive layer,
In particular, it is preferable to include it in the filter layer.

As the silver halide emulsion used in the light-sensitive material of the present invention, any conventional silver halide emulsion can be used.

The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as a van binder of 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 hardly soluble synthetic polymer.

A coupler is used in the emulsion layer of the color photographic material.

Further, the development accelerator, the bleaching accelerator, the developer, the silver halide solvent, the toning agent, the hardener, by the coupling with the colored coupler having the effect of color correction, the competitive coupler and the oxidized form of the developing agent, Compounds that release photographically useful fragments, such as fog agents, antifoggants, chemical sensitizers, spectral sensitizers, and sensitizers are used.

Photosensitive materials include filter layers, antihalation layers,
Auxiliary layers such as an anti-irradiation layer can be provided. In these layers and / or the emulsion layer, a dye which flows out of the light-sensitive material or is bleached during the development processing may be contained.

To the light-sensitive material, a formalin scavenger, a fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fogging inhibitor, a development accelerator, a development retarder and a bleaching accelerator can be added.

As a support of the photosensitive material, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate, or the like can be used.

In order to obtain an image using the light-sensitive material of the present invention, generally known photographic processing can be performed after exposure.

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

Example-1 In all of the following examples, the amount added in a silver halide photographic light-sensitive material indicates a weight (g) per 1 m ² unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of silver.

On a triacetylcellulose film support, layers having the following compositions were sequentially formed from the support side to prepare a multilayer color photographic element sample 1-1.

Sample 1-1 (comparative) First layer; anti-halation layer (HC-1) Black colloidal silver 0.20 UV absorber (UV-1) 0.20 Colored coupler (CC-1) 0.05 Colored coupler (CM-2) 0.05 High boiling point Solvent (Oil-1) 0.20 Gelatin 1.5 Second layer; Intermediate layer (IL-1) UV absorber (UV-1) 0.01 High boiling solvent (Oil-1) 0.01 Gelatin 1.5 Third layer; Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.8 Silver iodobromide emulsion (Em-2) 0.8 Sensitizing dye (S-1) 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S -2) 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.5 × 10 ^-4 (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) 0.05 DIR compound (D-1) 0.002 High boiling solvent (Oil-1) 0.5 Gelatin 1.5 4th layer; Sensitivity Red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3) 2.0 Sensitizing dye (S-1) 2.0 × 10 -4 ( mol / mole of silver) Sensitizing dye (S-2) 2.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 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 (CC-1) 0.015 DIR compound (D-2) 0.05 high boiling point solvent (Oil-1) 0.2 gelatin 1.5 fifth layer; intermediate layer (IL-2) gelatin 0.5 sixth layer; low sensitivity Green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 1.0 Sensitizing dye (S-4) 5 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-5) 1 × 10 ^{− 4} (mol / mole of silver) magenta coupler (M-1) 0.5 colored magenta coupler (CM-1) 0.01 DIR compound (D-3) 0.02 DIR compound (D-4) 0.020 high boiling solvent (Oil 2) 0.3 gelatin 1.0 seventh layer; intermediate layer (IL-3) gelatin 0.8 eighth layer; high-sensitivity green-sensitive emulsion layer (GH) silver iodobromide emulsion (Em-3) 1.3 sensitizing dye (S-6) 1.5 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-7) 2.5 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-8) 0.5 × 10 ⁻⁴ (mol / silver 1 mol) Mol) Magenta coupler (M-2) 0.05 Magenta coupler (M-3) 0.15 Colored magenta coupler (CM-2) 0.05 DIR compound (D-3) 0.01 High boiling solvent (Oil-3) 0.5 Gelatin 1.0 9th layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 Color stain inhibitor (SC-1) 0.1 High boiling solvent (Oil-3) 0.1 Gelatin 0.8 10th layer; Low sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion ( em-1) 0.25 silver iodobromide emulsion (em-2) 0.25 sensitizing dye (S-10) 7 × 10 -4 ( mol / mole of silver) yellow coupler (Y-1) 0.5 Yellow coupler (Y-2) 0.1 DIR compound (D-2) 0.01 High boiling solvent (Oil-3) 0.3 Gelatin 1.0 11th layer; Highly sensitive blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-4) 0.50 silver iodobromide emulsion (Em-1) 0.20 sensitizing dye (S-9) 1 × 10 ^-4 (mol / silver 1 mol) sensitizing dye (S-10) 3 × 10 ^-4 (mol / silver 1 Mol) Yellow coupler (Y-1) 0.30 Yellow coupler (Y-2) 0.05 High boiling solvent (Oil-3) 0.15 Gelatin 1.1 12th layer; 1st protective layer (PRO-1) Fine grain silver iodobromide emulsion (average Particle size 0.08μ, AgI2mol%)
0.4 UV absorber (UV-1) 0.10 UV absorber (UV-2) 0.05 High boiling solvent (Oil-1) 0.1 High boiling solvent (Oil-4) 0.1 Formalin scavenger (HS-1) 0.5 Formalin scavenger (HS -2) 0.2 gelatin 1.0 13th layer; 2nd protective layer (PRO-2) Surfactant (Su-1) 0.005 Alkali-soluble matting agent (average particle size 2 μm) 0.05 Polymethyl methacrylate (average particle size 3 μm) ) 0.05
Cyan dye (AIC-1) 0.005 Magenta dye (AIM-1) 0.01 Sliding agent (WAX-1) 0.04 Gelatin 0.6 In each layer, other coating aid Su-2, dispersing aid Su-3, Hardener H-1 (40mg / g gelatin), Stabilizer St
Ab-1 and antifoggant AF-1 were added.

Em-1 Average grain size 0.46 μm, average silver iodide content 7.0%, monodisperse surface low silver iodide content emulsion Em-2 Average grain size 0.30 μm, average silver iodide content 2.0%, monodisperse Emulsions with uniform composition Em-3 Average grain size 0.81 μm, average silver iodide content 7.0%, monodisperse surface low silver iodide-containing emulsion Em-4 Average grain size 0.95 μm, average silver iodide content 8.0% monodisperse surface low silver iodide-containing emulsion (Preparation of Samples 1-2 and 1-5 to 1-8) Instead of the yellow colloidal silver of the ninth layer, the dyes shown in Table 1 were mixed with a high boiling solvent (Oil-3) and a color stain inhibitor (SC). −
1-) and a surfactant alkanol XC (alkylnaphthalene-sulfonate, manufactured by DuPont) were dissolved in ethyl acetate, dispersed with gelatin, and then coated.
1 and multi-layer color photographic elements 1-2 and 1-5
1-8 were fabricated.

(Preparation of Samples 1-3, 1-4 and 1-9 to 1-11) Regarding the samples 1-3, 1-4 and 1-9 to 1-11 shown in Table 1, the dyes used for each are as follows. The ball mill solid fine particles were dispersed in accordance with the above procedure.

Water and a surfactant alkanol XC (alkylnaphthalene-sulfonate, manufactured by DuPont) were placed in a ball mill container, zirconium oxide beads to which the respective dyes were added were placed, and the container was sealed and dispersed in a ball mill 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 in the same manner as in Sample 1-1 except that this coating solution was used as the ninth layer in Sample 1-1.
-11 was produced.

In Samples 1-1 to 1-11, the amounts of the dyes used were each set to 0.3 g / m ² .

Each of the samples 1-1 to 1-11 thus prepared was subjected to wedge exposure using white light, and then subjected to the following development processing.

Processing step A (38 ° C) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fixed 6 minutes 30 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry Use in each processing step The composition of the treated solution is as follows.

[Color developing solution] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1

[Bleaching solution] Iron ammonium salt of ethylenediaminetetraacetic acid 100.0 g Diammonium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Water was added to adjust the pH to 1, and the pH was adjusted to 6.0 using aqueous ammonia.
Adjust to

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to adjust the pH to 1, and the pH was adjusted to 6.0 using acetic acid.

[Stabilizing solution] Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Water is added to make 1.

In addition, 4-amino-3
-Methyl-N-ethyl-N- (β-hydroxyethyl)
-A processing solution from which aniline / sulfate was removed was prepared, color development was performed using this, and then bleaching, fixing, and stabilization were performed in the same manner as in the processing step A. (Process B) Evaluation of the effect of the dye on fog was performed as follows.

(Effect on fog) ΔD _B2 = difference between minimum yellow density in processing step A and minimum yellow density in processing step B of each sample (1-1 to 1-12). At 55 ° C
After forced stored for 3 days at 80% relative humidity treated as described above step A, it was compared showed a decrease in the sensitivity of blue-sensitive emulsion layer in [Delta] S _B.

However, the sensitivity of the blue-sensitive emulsion layer is represented by the reciprocal of the exposure at a density of (minimum density + 0.3).

 Table 1 shows the obtained results.

As shown in Table 1, the fog of the blue-sensitive layer was improved in the sample of the present invention as compared with the case where yellow colloidal silver was used. On the other hand, comparative dyes 1, 2 or 3 (samples 1-2 to 1-4)
Shows a decrease in the sensitivity of the blue-sensitive layer due to storage. On the other hand, it is understood that the sample using the dye of the present invention has little effect on fog and has good storage stability.

Example 2 Each layer having the following composition was sequentially applied to a subbed triacetyl cellulose film support from the support side to prepare Sample 2-1 as a comparative sample of a multilayer color photosensitive material. The coating amount of each component is shown in g / m ² .

(Sample 2-1) First layer (antihalation layer) Ultraviolet absorber (UV-1) 0.3 Ultraviolet absorber (UV-2) 0.4 High boiling solvent (Oil-1) 1.0 Black colloidal silver 0.24 Gelatin 2.0 Second layer (Intermediate layer) 2,5-Di-t-octylhydroquinone 0.1 High boiling solvent (Oil-1) 0.2 Gelatin 1.0 Third layer; Low sensitivity red-sensitive silver halide emulsion layer Red sensitizing dye (S-2, S- AgBrI spectrally sensitized by 11) (AgI 4.0 mol%, average particle size 0.25μ) 0.5 Coupler (C-5) 0.1 mol High boiling solvent (Oil-3) 0.6 Gelatin 1.3 4th layer; High sensitivity red sensitivity Silver halide emulsion layer AgBrI (AgI 2 mol%, average particle size 0.6 μm) spectrally sensitized by red sensitizing dye (S-2, S-11) 0.8 Coupler (C-5) 0.2 mol High boiling solvent (Oil) -3) 1.2 Gelatin 1.8 Fifth layer (intermediate layer) 2,5-Di-t-octylhydroquinone 0.1 High boiling solvent (Oil-4) 0.2 Gelatin 0.9 6th layer (low-sensitivity green-sensitive silver halide emulsion layer) AgBrI (AgI 4 mol%, average particle size 0.25μ) spectrally sensitized by green sensitizing dyes (S-12 and S-13) 0.6 Coupler (M-4) 0.04 mol Coupler (M-5) 0.01 mol High boiling point solvent (Oil-1) 0.5 Gelatin 1.4 7th layer (highly sensitive green-sensitive silver halide emulsion layer) Green sensitizing dye (S-12, AgBrI spectrally sensitized by S-13) (AgI 2 mol%, average particle size 0.6 μ) 0.9 Coupler (M-4) 0.10 mol Coupler (M-5) 0.02 mol High boiling solvent (Oil-1) 1.0 Gelatin 1.5 8th layer (intermediate layer) Same as 5th layer 9th layer (yellow filter layer) Yellow colloidal silver 0.1 Gelatin 0.9 2,5-Di-t-octylhydroquinone 0.1 High boiling solvent (Oil-4) 0.2 10th layer (Low-sensitivity blue-sensitive silver halide emulsion layer) Spectral sensitized by blue sensitizing dye (S-14) Was AgBrI
(AgI 4 mol%, average particle size 0.35μ) 0.6 Coupler (Y-2) 0.3 mol High boiling point solvent (Oil-1) 0.6 Gelatin 1.3 11th layer (highly sensitive blue-sensitive silver halide emulsion layer) Blue sensitizing dye AgBrI spectrally sensitized by (S-14)
(AgI 2 mol%, average particle size 0.9 μ) 0.9 Coupler (Y-2) 0.5 mol High boiling solvent (Oil-1) 1.4 Gelatin 2.1 12th layer; 1st protective layer UV absorber (UV-1) 0.3 UV Absorbent (UV-2) 0.4 High boiling solvent (Oil-1) 0.6 Gelatin 1.2 2,5-Di-t-octylhydroquinone 0.1 13th layer; 2nd protective layer Average particle size () 0.08 μm, silver iodide 1 Non-photosensitive fine-grain silver halide emulsion composed of silver iodobromide containing 0.8% by mole Silver content 0.8 Polymethyl methacrylate particles (1.5 μm in diameter) Surfactant (Su-1) Gelatin 0.7 Gelatin hardener (H
-1) and a surfactant were added.

(Preparation of Samples 2-2, 2-5 and 2-6) Next, instead of the yellow colloidal silver of the ninth layer, the dyes shown in Table 2 were mixed with a high boiling solvent (Oil-4), 2,5- Multilayer color photographic elements 2-2, 2-5 and 2-6 were prepared in the same manner as in Sample 1-1, except that the solution was dissolved in ethyl acetate together with dioctyl hydroquinone, dispersed and coated with gelatin.

(Preparation of Samples 2-3, 2-4 and 2-8 to 2-10) The dyes used for each of Samples 2-3, 2-4 and 2-7 to 2-9 shown in Table 2 are as follows. The ball mill solid fine particles were dispersed in accordance with the above procedure.

Water and a surfactant alkanol XC (alkylnaphthalene-sulfonate, manufactured by DuPont) were placed in a ball mill container, zirconium oxide beads to which the respective dyes were added were placed, and the container was sealed and dispersed in a ball mill 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 2-7 to 2 in the same manner as in Sample 2-1 except that this coating solution was used as the ninth layer in Sample 1-1.
-9 was produced.

Further, in Samples 2-1 to 2-9, the amount of the dye to be used was set to 0.3 g / m ² .

The samples 2-1 to 2-9 thus obtained were subjected to wedge exposure with white light, and then subjected to the following development processing.

Processing time Processing time Processing temperature First development 6 minutes 38 ° C Washing water 2 minutes 38 ° C Inversion 2 minutes 38 ° C Color development 6 minutes 38 ° C Adjustment 2 minutes 38 ° C Bleaching 6 minutes 38 ° C Fixed 4 minutes 38 ° C Water Washing 4 minutes 38 ° C Stability 1 minute Room temperature Drying The composition of the processing solution used in the above processing step is as follows.

First developer Sodium tetrapolyphosphate 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-
3-Pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Add water 1000 ml Reversal solution Nitrilotrimethylene phosphonic acid 6 sodium salt 3 g Stannous chloride (dihydrate) 1 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Add water 1000 ml Color developing solution Sodium tetrapolyphosphate 3 g Sodium sulfite 7 g Sodium tertiary phosphate (dihydrate) 36 g Potassium bromide 1 g Iodine Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 8 g Citrazinic acid 1.5 g N-ethyl-N-β-methanesulfonamidoethyl-
3-methyl-4-aminoaniline / sulfate 11 g 2,2-ethylenedithiodiethanol 1 g Add water to 1000 ml Adjustment solution Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 ml Glacial acetic acid 3 ml Add water 1000 ml Bleaching solution Sodium ethylenediaminetetraacetate (dihydrate) 2 g Iron (III) ammonium ethylenediaminetetraacetate (2
Water salt) 120 g Ammonium bromide 100 g Add water 1000 ml Fixer Ammonium thiosulfate 80 g Sodium sulfite 5 g Sodium bisulfite 5 g Add water 1000 ml Stabilizer Formalin (37% by weight) 5 ml KONIDAX (manufactured by Konica Corporation) The maximum density (Dmax) and the minimum density (Dmin) were measured with blue light of each sample which had been developed by adding 5 ml of water and 1000 ml.

Moreover, it subjected to the exposure and processing Each sample after storage for 4 days at 55 ° C. 80% relative humidity, showed a decrease in the sensitivity of blue-sensitive emulsion layer in [Delta] S _B, were compared.

The sensitivity of the blue-sensitive emulsion layer is represented by the reciprocal of the exposure at a density of 2.0.

 Table 2 shows the obtained results.

As shown in Table 2, the sample of the present invention has a higher maximum concentration than the case where yellow colloidal silver was used. In addition, the sample using the comparative dye has a large minimum density, and the sensitivity of the blue-sensitive layer is reduced during storage, whereas the sample using the compound of the present invention has a small minimum density and a sufficient maximum density. Have
Also, the storage stability was good.

Example 3 A silver chlorobromide emulsion was prepared by a simultaneous mixing method at 40 ° C. for 50 minutes at a silver bromide content of 4 mol% and an addition amount of rhodium chloride of 1 × 10 ⁻⁴ (mol / mol AgX). The emulsion thus prepared was desalted and redispersed to obtain a monodispersed emulsion having an average particle size of 0.21 μm. Rhodium chloride dissolved in a sodium chloride solution was added to the halide solution.

A small amount of sodium thiosulfate was further added to these emulsions, chemically sensitized at 55 ° C. for 30 minutes, and 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer. Next, the compounds shown in Table 3 were added to these emulsions in the form of solid dispersion in the same manner as in Example 1 with the addition amount of 0.8 g / mol AgX, and 1-phenyl-
5-mercaptotetrazole as a polyethylene oxide compound, (M = 20, l + n = 15), saponin as a spreading agent and mucochloric acid as a hardening agent, respectively, to give a silver amount of 3.5 g / m
^The composition was applied on a film base so as to be ² and dried.

The samples 3-1 to 3-8 thus obtained were subjected to a safelight test of irradiation for 60 minutes under a fading lamp (FL40SW-NU manufactured by Toshiba) at about 300 lux, and developed using the following developer. The fog was measured. Immediately after application and at a temperature of 50
The specimen that had been forcibly degraded by leaving it in an atmosphere of 70 ° C. and a humidity of 70% RH for 2 days was exposed through a light wedge with a light room printer (HMW-215, manufactured by Oak Manufacturing Co., Ltd.) and developed using the following developer. .

<Developer formulation> Hydroquinone 15 g Formaldehyde and sodium bisulfite adduct 50 g Potassium sulfite 4 g Potassium carbonate 50 g Boric acid 2 g KBr 2 g Triethylene glycol 49 g EDTA-2Na 2 g Diethanolamine 7 g 5-Nitroindazole 3 g Ethylene urea 0.5 g Polyethylene glycol (average molecular weight 1500) 0.4 g Sodium hydroxide 1 g Add water to make 1.

 The development condition is 27 ° C. for 1 minute and 40 seconds.

 Table 3 shows the results.

As is clear from Table 3, the samples 3-4 to 3-
No. 8 has an ultra-low sensitivity that can be handled as a photosensitive material for a light room, improves the relationship between safelight property and sensitivity, is further high contrast, and has extremely little change in sensitivity and gradation during storage. Recognize.

Example 4 3.5 g of gelatin was added to and dissolved in 35 ml of distilled water.
2.0 × 10 ^-4 mol of each of the exemplified compounds shown in Table-4 were dispersed in solid form in the same manner as in Example 1, and 1.25 ml of a 10% aqueous saponin solution and 0.75 ml of a 1% formalin solution were further added. Water was added. The total volume was 50 ml. This sample solution was applied on an acetylcellulose film support, dried, and
-5 to 4-10. Further, instead of the compound of the present invention,
Using Comparative Dyes (2), (3) and (4) and Comparative Dye (7) shown below, Comparative Samples 4-1 to 4-
4 was created.

Each of these samples was immersed in a developer having the following composition at 25 ° C. for 1 minute, washed with water for 20 seconds, and then dried.

(Developer composition) Methol 3.0 Sodium sulfite (anhydrous) 45.0 g Hydroquinone 12.0 g Sodium carbonate (monohydrate) 80.0 g Potassium bromide 2.0 g Add water to make 1

Before and after immersion in the developer, the decolorized state of each sample was visually evaluated. Table 4 shows the results. (The mark ○ indicates that no coloring contamination was observed, the mark △ indicates that coloring staining was slightly observed, and the mark × indicates that coloring staining was remarkable.) As is evident from Table 4, the compounds of the present invention exhibited excellent decoloring properties as compared with the comparative dyes. Further, in the comparative sample, the treatment liquid was colored and contaminated by the eluted dye, but such a colored contamination was not observed at all in the sample of the present invention.

[Effects of the Invention] As described in detail above, by containing the water-insoluble compound of the present invention as a dispersion, fog is reduced,
A silver halide photographic light-sensitive material having improved storage stability over time and without deterioration of photographic characteristics is provided.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-196040 (JP, A) JP-B-48-42175 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 1/83 G03C 1/40

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising at least one photographic constituent layer containing a dispersion of a water-insoluble compound represented by the following general formula [I] on a support. General formula [I] (Wherein, R ¹ represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; R ² represents a hydrogen atom, an alkenyl group, a heterocyclic group, an amino group, an alkyloxy group, an aryloxy group, a carbamoyl group, An amide group, a ureido group, an oxycarbonyl group, an acyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfanyl group, an alkylthio group, an arylthio group or a cyano group, and R ³ represents an alkyl group, an alkenyl group, an aryl group, or a hetero group. R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, an amino group, an alkyloxy group, an aryloxy group, a carbamoyl group , Amide group, ureido group, oxycarbonyl group, acyl group, sulfonamide group, sulfamoyl group,
Represents a sulfonyl group, a sulfanyl group, an alkylthio group, an arylthio group or a cyano group, L ₁ , L ₂ and L ₃ each represent a methine group, and n represents an integer of 0 to 2. )