JP3252232B2 - Silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material containing a dye, and more particularly, to a halogenated dye having a specific layer dyed with a novel dye and having little desensitization due to fogging and aging. It relates to a silver photographic light-sensitive material.

[0002]

2. Description of the Related Art Silver halide photographic materials are required to have high image quality such as excellent sharpness and color reproducibility.

In recent years, in order to counteract the immediacy of competing electrophotographic materials, the processing time has been further reduced,
That is, ultra-rapid processing suitability 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 contained in a silver halide photographic light-sensitive material for the purpose of improving image quality or adjusting the sensitivity of a silver halide emulsion. For example, it is known to prevent halation, irradiation, and light. Used in absorption filters.

Recently, a dye (hereinafter referred to as "YC dye") for replacing yellow colloidal silver in a color photographic light-sensitive material, a dye for forming a crossover cut layer in an X-ray photographic light-sensitive material, a printing photographic light-sensitive material, The use of dyes for dyeing non-light-sensitive emulsion layers in materials has been widespread.

The dye used for these purposes depends on the purpose of use. 1. have a good absorption spectrum; 2. Do not diffuse from the colored layer to other layers. 3. Do not affect the photosensitive silver halide emulsion photographically. 4. Stable in silver halide photographic materials. 5. Easy to add 6. It is stable in the emulsion coating solution and does not affect the solution viscosity. It is required that the color does not remain after processing.

Numerous dyes have been proposed for the purpose of satisfying these required properties. For example, azo dyes, oxonol dyes are described in British Patent No. 506,385 and Japanese Patent Publication No. 39-22069, and US Patent No. 2,493,747. Discloses a merocyanine dye, and U.S. Pat. No. 1,845,404 proposes a styryl dye and the like.

[0008]

It is a general method to dissolve these dyes in water or an organic solvent miscible with water and to add them to a photographic component layer. It diffuses to all layers without remaining in the layer to be made. 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 which suppress the diffusibility such as dyeing a specific layer against such a problem are known, and as a diffusion-resistant dye, for example, US Pat. No. 2,538,008
Nos. 2,539,009, 4,420,555
61-204630, 61-205934, 62-32460, 62-569
No. 58, No. 62-92949, No. 62-222248, No. 63-40143,
JP-A-63-184749 and JP-A-63-316852 describe YC dyes. In addition, these dyes reduce the green sensitivity because the yellow colloidal silver called Carey Lea Silver, which is commonly used in color photographic elements, absorbs not only the blue light region but also part of the long wavelength side, Numerous proposals have been made to improve the drawback of increasing the fogging of adjacent layers and to save valuable silver resources.

Although the above-mentioned disadvantages are improved to some extent by these diffusion-resistant dyes, on the other hand, the storage stability is deteriorated, the sensation of aging occurs over time, and the bleaching property is insufficient, which causes color contamination. Such a problem newly occurred. In order to solve these problems, a new diffusion-resistant dye is required.

[0010]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a silver halide photographic light-sensitive material which satisfies the above-mentioned requirements for a dye which has been made resistant to diffusion and which has little fog and improved stability over time.

[0011]

Means for Solving the Problems The present inventors have made intensive studies in view of the above problems, and as a result, the object of the present invention is to provide a support containing a compound represented by the following general formula [I]. This is achieved by a silver halide photographic light-sensitive material having at least one photographic constituent layer.

[0012]

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(R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ represent a hydrogen atom or a substituent. R ₇ and R ₈ are bonded to each other to form a heterocyclic ring; L ₁ , L ₂
And L ₃ represents a methine group, and m represents 0, 1 and 2. Hereinafter, the present invention will be described in more detail.

As the substituents represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ (hereinafter referred to as R _{1 to} R ₈ ), alkyl groups, cycloalkyl groups An aryl group, a heterocyclic group, an alkylcarbonyl group, an alkylsulfonyl group, an arylcarbonyl group, an alkoxycarbonyl group,
Aryloxycarbonyl group, arylsulfonyl group,
Alkylsulfinyl group, arylsulfinyl group, carbamoyl group, sulfamoyl group, cyano group, amino group, alkylamino group, arylamino group, sulfonamide group, amide group, ureido group, thioureido group, alkoxy group, aryloxy group, alkylthio group , An arylthio group, a carboxyl group, a sulfo group, a hydroxyl group, and a halogen atom.

The alkyl group represented by R _{1 to} R ₈ includes, for example, methyl group, ethyl group, propyl group, i-propyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, dodecyl Group, pentadecyl group, eicosyl group and the like. The alkyl group includes those having a substituent, and examples of the substituent include, for example,
A halogen atom (eg, each atom of chlorine, bromine, iodine, fluorine, etc.), an aryl group (eg, phenyl group, naphthyl group, etc.), a cycloalkyl group (eg, cyclobentyl group,
Cyclohexyl group), heterocyclic group (eg, pyrrolidyl group, pyridyl group, etc.), sulfinic acid group, carboxyl group, sulfo group, nitro group, hydroxyl group, mercapto group, amino group (eg, amino group, diethylamino group, etc.), alkyloxy Groups (eg, methyloxy, ethyloxy,
n-butyloxy group, n-octyloxy group, isopropyloxy group, etc.), aryloxy group (phenyloxy group,
Carbamoyl group (eg, aminocarbonyl group, methylcarbamoyl group, n-pentylcarbamoyl group, phenylcarbamoyl group, etc.), amide group (eg, methylamide group, benzamide group, n-octylamide group, etc.), aminosulfonyl Amino group (eg, aminosulfonylamino group, methylaminosulfonylamino group, anilinosulfonylamino group, etc.), sulfamoyl group (eg, sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, n-butylsulfamoyl group, etc.) ), A sulfonamide group (eg, a methanesulfonamide group, an n-heptanesulfonamide group, a benzenesulfonamide group, etc.), a sulfinyl group (eg, an alkylsulfonyl group such as a methylsulfinyl group, an ethylsphinyl group, an octylsulfinyl group, etc.) An arylsulfinyl group such as a phenyl group and a phenylsulfinyl group), an alkyloxycarbonyl group (eg, a methyloxycarbonyl group, an ethyloxycarbonyl group, a 2-hydroxyethyloxycarbonyl group, an n-octyloxycarbonyl group, etc.), an aryloxycarbonyl group Groups (eg, phenyloxycarbonyl, naphthyloxycarbonyl, etc.), alkylthio groups (eg, methylthio, ethylthio, n-hexylthio, etc.), arylthio groups (eg, phenylthio, naphthylthio, etc.), alkylcarbonyl groups (eg, acetyl Group, ethylcarbonyl group, n-butylcarbonyl group,
n-octylcarbonyl group, etc.), arylcarbonyl group (eg, benzoyl group, p-methanesulfonamidobenzoyl group, p-carboxybenzoyl group, naphthoyl group, etc.), cyano group, ureido group (eg, methylureido group, phenylureido group, etc.) ), A thioureido group (eg, a methylthioureido group, a phenylthioureido group, etc.).

The aryl group represented by R _{1 to} R ₈ includes, for example, a phenyl group and a naphthyl group. The aryl group includes those having a substituent, and examples of the substituent include an alkyl group represented by R _{1 to} R ₈ or R ₁
The foregoing groups mentioned as substituents for the alkyl group represented by to R ₈ can be mentioned.

The heterocyclic groups represented by R _{1 to} R ₈ include:
For example, a pyridyl group (2-pyridyl group, 3-pyridyl group, 4-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
-Carboxy-2-benzoxazolyl group, 2-benzooxazolyl group, 2-oxazolyl group, etc.), thiazolyl group (5-sulfamoyl-2-benzothiazole group, 2-benzothiazolyl group, 2-thiazolyl group, etc.), Imidazolyl group (l-methyl
2-imidazolyl group, 1-methyl-5-carboxy-2-benzimidazolyl group, etc.), furyl group (3-furyl group, etc.), pyrrolyl group (3-pyrrolyl group, etc.), thienyl group (2-thienyl group, etc.) , A pyrazinyl group (such as a 2-pyrazinyl group), a pyrimidinyl group (such as a 2-pyrimidinyl group, a 4-chloro-2-pyrimidinyl group), a pyridazinyl group (such as a 2-pyridazinyl group), a brinyl group (such as an 8-brynyl group), Isoxazolyl group (3-isoxazolyl group etc.), selenazolyl group (5-carboxy-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 (l-methyl-5-tetrazolyl) group) and the like, the heterocyclic groups include those having a substituent, the alkyl group as the該置ring group represented by alkyl group or R ₁ to R ₈ are represented, for example, R ₁ to R ₈ The above-mentioned groups exemplified as the substituents are exemplified.

Examples of the cycloalkyl group represented by R _{1 to} R ₈ include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. Examples of the alkylcarbonyl group represented by R _{1 to} R ₈ include Examples of the arylcarbonyl group represented by R _{1 to} R ₈ such as a methylcarbonyl group, an ethylcarbonyl group, an i-propylcarbonyl group, a t-butylcarbonyl group, an octylcarbonyl group, a dodecylcarbonyl group include a phenylcarbonyl group and a naphthyl Examples of the alkoxycarbonyl group represented by R _{1 to} R ₈ such as a carbonyl group include an ethoxycarbonyl group,
i-propoxycarbonyl group, t-butoxycarbonyl group,
Examples of the aryloxycarbonyl group represented by R _{1 to} R ₈ , such as a benzyloxycarbonyl group and a dodecyloxycarbonyl group, include, for example, a phenyloxycarbonyl group and a naphthyloxycarbonyl group, and examples of the alkylsulfonyl group include a methylsulfonyl group, Ethylsulfonyl group, i-propylsulfonyl group, t-butylsulfonyl group,
Octylsulfonyl group, octadecylsulfonyl group, etc.
As the arylsulfonyl group, for example, a phenylsulfonyl group, a naphthylsulfonyl group, and the like, and as the alkylsulfinyl group, for example, a methylsulfinyl group, an ethylsulfinyl group, an i-propylsulfinyl group, a t-butylsulfinyl group, an octylsulfinyl group, dodecylsulfinyl Groups such as an arylsulfinyl group such as phenylsulfinyl group and naphthylsulfinyl group; and carbamoyl groups such as aminocarbonyl group, methylcarbamoyl group, ethylcarbamoyl group, i-
As a sulfamoyl group such as a propylcarbamoyl group, a t-butylcarbamoyl group, a dodecylcarbamoyl group, a phenylcarbamoyl group, a 2-pyridylcarbamoyl group, a 4-pyridylcarbamoyl group, a benzylcarbamoyl group, a morpholinocarbamoyl group, and a piverazinocarbamoyl group, For example, aminosulfonyl, methylsulfamoyl, i-propylsulfamoyl, t-butylsulfamoyl, dodecylsulfamoyl, phenylsulfamoyl, 2-pyridylsulfamoyl, 4-pyridyl Examples of the amino group such as a sulfamoyl group, a morpholinosulfamoyl group, and a piperazinosulfamoyl group include, for example, an amino group, a methylamino group, an ethylamino group, an i-propylamino group, a t-butylamino group, and octylamino. Group, dodecylamino group, dimethyla Amino group, an anilino group, naphthylamino group, morpholino group, piperazino group, etc. Examples of the sulfonamide group, for example methyl sulphonamide group, an ethyl sulfonamide group, i- propyl sulfonamide group,
Amide groups such as t-butylsulfonamide group, dodecylsulfonamide group, phenylsulfonamide group, naphthylsulfonamide group and the like include, for example, methylcarbonylamino group, ethylcarbonylamino group, i-propylcarbonylamino group, t-butylcarbonyl Examples of alkylamino groups such as amino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, i-propylamino group, n-butylamino Examples of the arylamino group such as a group and an octylamino group include an anilino group and a naphthylamino group.
Each group represented by these R ₁ to R ₈ include those having a substituent, the alkyl group as the substituent represented by e.g. R ₁ to R ₈ or alkyl group represented by R ₁ to R _8, The above-mentioned groups exemplified as the substituents are exemplified.

R ₇ and R ₈ can be bonded to each other to form a heterocyclic ring, for example, pyrazolotriazole,
Examples include pyrazoloimidazole, pyrazolotetrazole, pyrazolobenzimidazole, pyrazolopyrimidine, pyrazoloquinazoline, pyrazoloquinazolin-5-one, and pyrazolopteridine.

[0020] Each of these heterocycles include those having a substituent, examples of the substituent group mentioned as substituents for the alkyl group represented by alkyl group or R ₁ to R _8, represented by R ₁ to R ₈ And the aforementioned groups.

The methine groups represented by L ₁ , L ₂ and L ₃ include those having a substituent. Examples of the substituent include an alkyl group (eg, methyl, ethyl, 3-hydroxypropyl, benzyl, etc.) and a halogen atom ( Examples include a fluorine, chlorine, bromine atom, etc.), an aryl group (eg, phenyl group), an alkoxy group (eg, methoxy, ethoxy, etc.), and these groups include those further having a substituent. Is an alkyl group represented by R _{1 to} R ₈ , or R ₁ to
The groups described above as substituents of the alkyl group represented by R ₈ can be mentioned.

The compound represented by the general formula [I] of the present invention is preferably contained in the photosensitive material as a solid fine particle dispersion. In this case, the compound represented by the general formula [I] contains a carboxyl group, It is preferable to use a compound having at least one of a sulfonamide group and an aminosulfonyl group.

The following are specific examples of the compound of the present invention, but the present invention is not limited to these.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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Hereinafter, specific synthetic examples of the compound of the present invention will be shown. Other compounds can be easily synthesized by the same method.

Synthesis Example 1 Synthesis of Exemplified Compound (25) 6-ethoxycarbonyl-3- (4-carboxyphenyl) -1H
-Pyrazolo [3,2-C] -s-triazole 30.0 g, 3-formyl
A mixture of 21.7 g of -7-dimethylaminocoumarin, 2 ml of piperidine, 1 ml of glacial acetic acid and 300 ml of ethanol was stirred while heating under reflux for 5 hours. After allowing the reaction mixture to cool, the product was collected by filtration. The product was slurried in ethanol at reflux and purified by filtration. This treatment was repeated to obtain 16.0 g of compound (25).

The structure of the compound was determined by NMR, IR and MASS.
Confirmed by spectrum.

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

The method for adding the solid fine particle dispersion of the compound of the present invention to a light-sensitive material is not particularly limited, and examples thereof include a method described in US Pat. No. 4,857,446.

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

The compounds of the present invention are preferably contained in the non-photosensitive layer, it is preferable to particularly contained 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.

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as a 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 hardly soluble synthetic polymer.

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

Further, the development accelerator, the bleaching accelerator, the developer, the silver halide solvent, the toning agent, and the hardening agent are coupled with a colored coupler having a color correcting effect, a competitive coupler, and an oxidized form of the developing agent. Compounds that release photographically useful fragments such as filming agents, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and sensitizers are used.

The light-sensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an anti-irradiation layer. Dyes to be washed or bleached may be included.

The light-sensitive material can contain 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.

As a support for 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.

[0058]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these examples.

Example 1 In all of the following examples, the amount added in a silver halide photographic light-sensitive material indicates the 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: Antihalation 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 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 (mole / silver 1 mol) Sensitizing dye (S─3) 0.5 × 10 ^-4 (mole / 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 Fourth layer: High-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3) 2.0 Sensitizing dye (S─1) 2.0 × 10 ^-4 (mol / silver 1 mol) 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 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 ) 5.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S # 5) 1.0 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M # 1) 0.5 Colored magenta coupler (CM # 1) 0.01 DIR compound (D # 3) 0.02 DIR compound (D # 4 ) 0.02 High boiling point solution Medium (Oil # 2) 0.3 Gelatin 1.0 Seventh layer: Intermediate layer (IL-3) Gelatin 0.8 Eighth layer: High-sensitivity red-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) 1.3 increase 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) 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 Ninth 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) 7.0 × 10 ^-4 (mol / mole of silver) yellow coupler (Y─ ) 0.5 Yellow coupler (Y # 2) 0.1 DIR compound (D # 2) 0.01 High boiling point 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) 1.0 × 10 ^-4 (mol / silver 1 mol) sensitizing dye (S─10) 3.0 × 10 ^-4 (mol / (1 mol of silver) 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, AgI 2mol%) 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 (S u-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 addition to the above composition, each layer has a coating aid Su-2, a dispersing aid Su-3, a hardener H-1 (40 mg / g gelatin), a stabilizer Stab-1 and an antifoggant. Agent AF-1 was added. Em-1 Average grain size 0.46 μm, average silver iodide content 7.0%, monodisperse surface low silver iodide-containing 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

[0062]

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[0070]

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(Preparation of Sample 1-2) Instead of the yellow colloidal silver of the ninth layer, the dyes shown in Table 1 were used in a high boiling solvent (Oi).
1-3), a color stain inhibitor (SC-1) and a surfactant alkanol XC (alkyl naphthalene-sulfonate,
A multilayer color photographic element 1-2 was prepared in the same manner as in Sample 1-1, except that the resultant was dissolved in ethyl acetate together with Dupont Co., Ltd. and dispersed and coated with gelatin.

(Preparation of Samples 1-3 to 1-10) For the samples 1-3 to 1-10 shown in Table 1, the dyes used in each of them 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, the respective dyes were added, zirconium oxide beads were added, 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. Sample 1-1
Sample 1 except that this coating liquid was used as the ninth layer in
In the same manner as in Example 1, multilayer color photographic elements 1-3 to 1-10 were prepared. In Samples 1-1 to 1-10, the amounts of the dyes used were each set to 0.3 g / m ² .

[0075]

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Each of the samples 1-1 to 1 thus prepared
After wedge exposure of each of -10 using white light, the following development processing was performed.

Processing step A (38 ° C.) Processing time 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 Drying The composition of the processing solution used in each processing step is as follows.

[Color developing solution] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.75 g Sodium sulfite anhydrous 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 liter.

[Bleaching Solution] Iron ammonium diaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Add water to make 1 liter, and adjust the pH to 6.0 using aqueous ammonia. .

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

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

Further, a processing solution was prepared by removing 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline / sulfate from the color developing solution in the above-mentioned processing step. Color development, then bleaching, fixing,
Stabilization treatment was applied. The evaluation of the effect of the dye on the fog (referred to as processing step B) was performed as follows.

(Effect of 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 1-10) 80% at 55 ° C to evaluate
Treated as described above step A after the forced storage for 3 days at a relative humidity were compared showed a decrease in the sensitivity of blue-sensitive emulsion layer in [Delta] S _B.

[0084]

(Equation 1)

Here, the sensitivity of the blue-sensitive emulsion layer is represented by the reciprocal of the exposure at the density of (minimum density + 0.3). Table 1 shows the obtained results.

[0086]

[Table 1]

As shown in Table 1, the sample of the present invention has improved fog in the blue-sensitive layer as compared with the case where yellow colloidal silver is used. On the other hand, Comparative Dye 1, 2 or 3 (Sample 1-2)
In (1-4), a decrease in the sensitivity of the blue-sensitive layer due to storage is observed. 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.

The effect of the present invention was also confirmed for each of the samples in which (49) and (52) were used in place of the compound (3) of the present invention in the sample 1-5.

Example 2 Samples 2-1 were prepared as comparative samples of a multilayer color photographic material by sequentially applying each layer having the following composition from a support side on a triacetyl cellulose film support which had been subjected to a subbing process.
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 point solvent (Oil-1) 0.2 Gelatin 1.0 Third layer (Low sensitivity red-sensitive silver halide emulsion layer) Red sensitizing dye (S- AgBrI spectrally sensitized by 1, S-11) (AgI 4.0 mol%, average particle size 0.25 μ) 0.5 Coupler (C-5) 0.1 mol High boiling solvent (Oil-3) 0.6 Gelatin 1.3 Fourth layer (High Sensitive red-sensitive silver halide emulsion layer) AgBrI (AgI 2.0 mol%, average particle diameter 0.6 μ) spectrally sensitized by a red sensitizing dye (S-1, S-11) 0.8 Coupler (C-5) 0.2 mol High boiling point solvent (Oil-3) 1.2 Gelatin 1.8 Fifth layer (intermediate layer) 2,5-di-t-octylhydride Quinone 0.1 High boiling point solvent (Oil-4) 0.2 Gelatin 0.9 6th layer (Low sensitivity green-sensitive silver halide emulsion layer) AgBrI (AgI 4.0) spectrally sensitized by green sensitizing dyes (S-12 and S-13) Mol%, average particle size 0.25μ) 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 (high sensitive green-sensitive silver halide emulsion layer) AgBrI spectrally sensitized by green sensitizing dyes (S-12 and S-13) (AgI 2.0 mol%, average particle size 0.6 μ) 0.9 Coupler (M-4) 0.10 mol Coupler (M-5) 0.02 mol High boiling point 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 point Solvent (Oil-4) 0.2 10th layer (low-sensitivity blue-sensitive silver halide emulsion layer) Blue AgBrI spectrally sensitized by the dye (S-14) (AgI 4.0 mol%, average particle size 0.35 μm) 0.6 Coupler (Y-2) 0.3 mol High boiling solvent (Oil-1) 0.6 Gelatin 1.3 Layer 11 ( High-sensitivity blue-sensitive silver halide emulsion layer) AgBrI (AgI 2.0 mol%, average particle size 0.9 μm) spectrally sensitized by a blue sensitizing dye (S-14) 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 absorber (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 Non-photosensitive fine grain silver halide emulsion composed of silver iodobromide containing 0.08 µm in average grain size and 1 mol% of silver iodide Silver content 0.8 Polymethyl methacrylate grains ( Surfactant (Su-1) Gelatin 0.7 In addition to the above composition, Chin curing agent (H-
1) and a surfactant were added.

[0091]

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[0092]

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(Preparation of Sample 2-2) Next, instead of the yellow colloidal silver in the ninth layer, the dyes shown in Table 2 were added to ethyl acetate together with a high boiling point solvent (Oil-4) and 2,5-dioctylhydroquinone. Multilayer color photographic element 2-2 in the same manner as in Sample 2-1 except that it was dissolved, dispersed together with gelatin, and coated.
Was prepared.

(Preparation of Samples 2-3 to 2-10) For each of Samples 2-3 to 2-10 shown in Table 2, the dyes used in each were dispersed in a ball mill solid fine particle according to the following procedure.

Water and a surfactant alkanol XC (alkylnaphthalene-sulfonate, manufactured by Dupont) were placed in a ball mill container, the respective dyes were added, zirconium oxide beads were added, 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. Sample 2-1
Sample 2 except that this coating solution was used as the ninth layer in
In the same manner as in Example 1, multilayer color photographic elements 2-3 to 2-10 were prepared.

In Samples 2-1 to 2-10, the amounts of the dyes used were each adjusted to 0.3 g / m ² .

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

Processing step Processing time Processing temperature First development 6 minutes 38 ° C. Rinse 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. Fixing 4 minutes 38 ° C Rinse for 4 minutes 38 ° C Stable 1 minute Room temperature Drying The composition of the processing solution used in the above process 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 Thiocyan Potassium acid salt 1.2g Potassium iodide (0.1% solution) 2ml Add water 1000ml Reversal liquid Nitrilotrimethylenephosphonic acid hexasodium salt 3g Stannous chloride (dihydrate) 1g p-Aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid 15ml Add water 1000ml Color developing solution Sodium tetrapolyphosphate 3g Sodium sulfite 7g Sodium tertiary phosphate (dihydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90ml Sodium hydroxide 8g Citrazinic acid 1.5g N -Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline / sulfate 11g 2,2-ethylenedithiodieta 1 g of water to adjust to 1000 ml Adjustment liquid sodium sulfite 12 g sodium ethylenediaminetetraacetate (dihydrate) 8 g thioglycerin 0.4 ml glacial acetic acid 3 ml Add water 1000 ml bleaching liquid sodium ethylenediaminetetraacetate (dihydrate) 2 g ethylenediaminetetrahydrate Ammonium iron (III) acetate (dihydrate) 120g Ammonium bromide 100g Add water 1000ml Settled solution Ammonium thiosulfate 80g Sodium sulfite 5g Sodium bisulfite 5g Add water 1000ml Stabilized solution Formalin (37 wt%) 5ml Conidax (Konica Co., Ltd.) 5 ml of water was added and 1000 ml of each developed sample was measured for maximum density (Dmax) and minimum density (Dmin) with blue light. In addition, each sample was
° C., subjected to the exposure and processing after storage for 4 days at 80% relative humidity, showed a decrease in the sensitivity of blue-sensitive emulsion layer in [Delta] S _B,
Compared.

[0101]

(Equation 2)

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.

[0104]

[Table 2]

As shown in Table 2, the maximum density of the sample of the present invention was higher than that in the case where yellow colloidal silver was used. or,
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. And the storage stability was also good.

The effect of the present invention was also confirmed in each of the samples 2-5 in which the compound (4) of the present invention was replaced with (55).

Example 3 (Preparation of Coating Solution for Emulsion Layer) Solution A 9.7 L Sodium chloride 20 g Gelatin 105 g Solution B Water 3.8 L Sodium chloride 365 g Gelatin 94 g Potassium bromide 450 g 0.01% aqueous solution of potassium hexachloroiridate salt 28 mL 1.0% aqueous solution of potassium salt of xabromorhodate acid 1.0ml solution C water 3.8l silver nitrate 1.700g The above solution B and solution C were simultaneously functionalized while keeping pH3 and pAg 7.7 in the above solution A kept at 40 ° C. The mixture was added over 60 minutes, and the mixture was further stirred for 10 minutes. After that, the pH was adjusted to 6.0 with an aqueous solution of sodium carbonate, 2 liters of an aqueous solution of 20% magnesium sulfate and a 2.5% aqueous solution of polynaphthalenesulfonic acid were added.
Add 5 l, flocculate the emulsion at 40 ° C., decant and wash with water to remove excess aqueous salts. Then 3.7 l of water was added to it and dispersed, again 20
Similarly, 0.9 l of an aqueous solution of magnesium sulfate is added to remove excess aqueous salts. Add 3.7 l of water and 141 g of gelatin thereto and disperse at 55 ° C. for 30 minutes.

As a result, grains having a silver bromide content of 38 mol% and silver chloride content of 62 mol% and an average monodispersity of 0.25 μm 9 were obtained. 140 ml of an aqueous solution of 1% citric acid, 5% potassium bromide
Was added, and 70 ml of a 0.1% aqueous solution of sodium thiosulfate was added, followed by aging at 58 ° C. for 70 minutes.

4-Hydroxyl was added as a stabilizer to the obtained emulsion.
10 g of -6-methyl-1,3,3a, 7-tetrazaindene and 1600 ml of a 20% aqueous solution of gelatin were added to stop ripening, and then 3.5 g of the following sensitizing dye (a) and 3.5 g of (b) 1 g, 1 g of (C), 7 g of compound (d) as a contrasting agent, and 10 g of sodium p-dodecylbenzenesulfonate as a spreading agent.
g, saponin 30g, butyl acrylate, acrylic acid and styrene copolymer as polymer latex 120g, pAg
A coating solution for an emulsion layer was prepared by adding 3 g of potassium bromide as a regulator, 20 g of a styrene-maleic anhydride copolymer as a thickener, and formalin and glyoxal as hardeners.

[0110]

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(Preparation of Coating Solution for Protective Layer)
After dissolving in 7.5 l of water, the following compound (e) is used as a spreading agent
15 g, 10 g of silica having an average particle size of 3.5 μm as a matting agent,
Formalin was added as a hardening agent to prepare a coating solution for a protective layer.

[0112]

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(Preparation of Coating Solution for Backing Lower Layer) After dissolving 650 g of gelatin in 10 l of water, the compounds shown in Table 3 were dispersed in the form of solid fine particles in the same manner as in Example 1 so that the concentration became 0.2 g / m ^2. 30 g of saponin as a spreading agent, 30 g of a copolymer of butyl acrylate and vinylidene chloride as a polymer latex, 150 g of colloidal silica as a coating property improver, and 3 g of a styrene-maleic anhydride copolymer as a thickener. Then, 2.5 g of glyoxal was added as a hardening agent to prepare a backing lower layer coating solution.

(Preparation of Coating Solution for Backing Upper Layer) After 400 g of gelatin was dissolved in 600 ml of water, 20 g of polymethyl methacrylate having an average particle size of 4 μm was used as a matting agent, and bis- (2-ethylhexyl) sulfosuccinate was used as a spreading agent. 3 g of sodium salt and glyoxal as a hardener were added to prepare a coating solution for the backing upper layer.

(Preparation of Sample) Thickness 10 after Subbing Process
A backing lower layer and an upper layer were simultaneously overcoated on a 0 μm polyethylene terephthalate film base, and then an emulsion layer and a protective layer were simultaneously overcoated on the side opposite to the backing layer. Silver coverage 4.2 g / m ^2, the amount with gelatin 1.95 g / m ² is emulsion layer, a protective layer is 1.2 g / m ² Backing underlayer 2.7g
/ m ² and the backing upper layer was 1.0 g / m ² .

The obtained sample was processed with an automatic developing machine GR-27 (manufactured by Konica Corporation) using a developing solution and a fixing solution having the following formulation, and the dot quality and storage stability were evaluated. Table 3 summarizes the results.

(Dot Quality) After performing halftone exposure so as to have a dot area of 90%, processing was performed, and the dot quality was evaluated in 10 levels. The best halftone dot quality was 10, 1 was an extremely bad level, and 5 or more was a practical level.

(Storage stability) The obtained sample was stored at 23 ° C. and 50% RH.
Then, the emulsion surface side and both sides of the backing were brought into contact with each other, and the layers were sealed. This sample was stored under the conditions of 50 ° C. and 20% RH for 5 days, and the sensitivity of the sample after storage was determined by setting the sensitivity of the sample before storage to 100.

Here, the reciprocal of the exposure necessary for obtaining a density of 2.5 was used as the sensitivity.

Development conditions (process) (Temperature) (Time) Current image 28 ° C. 30 seconds Fixed 28 ° C. Approx. 20 seconds Rinse at room temperature Approx. 20 seconds Dry 45 ° C. 20 seconds Developer composition (Composition A) Pure water ( Ion-exchanged water) 150 ml disodium ethylenediaminetetraacetate 2 g diethylene glycol 50 g potassium sulfite (55% w / v aqueous solution) 100 ml potassium carbonate 50 g hydroquinone 15 g 5-methylbenzotriazole 200 mg 1-phenyl-5-mercaptotetrazole 30 mg potassium bromide 4.5 g water Aqueous solution of potassium oxide to adjust pH to 10.4 (Composition B) Pure water (ion-exchanged water) 3 mg Diethylene glycol 50 g Disodium ethylenediaminetetraacetate 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg l-phenyl-3-pyrazolidone When using a 500 mg developing solution, the above composition A and composition B were dissolved in 500 ml of water in that order, and used after finishing to 1 liter.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240ml Sodium sulfite 17g Sodium acetate / trihydrate 6.5g Sodium citrate / dihydrate 2g Boric acid 6g Acetic acid (90% W / V aqueous solution) 13.6 ml (Composition B) Pure water (ion-exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulfate 26.5 g (Al ₂ O ₃ conversion content 8.1% W / V aqueous solution) Use of fixing solution At times, the above composition A and composition B were dissolved in 500 ml of water in this order, and finished to 1 liter.

The fixing solution had a pH of about 4.3.

[0123]

[Table 3]

As apparent from Table 3, the sample 3 of the present invention
3 to 3-8 show that the dot quality is good and the storage stability is also excellent.

Example 4 In this example, a silver halide photographic material was prepared as follows.

First, an emulsion was prepared as follows.

(A) Preparation of Monodispersed Emulsion Iodine containing 2 mol% of silver iodide having an average grain size of 0.3 μm by a double jet method while maintaining the conditions of a reaction vessel at 60 ° C., pAg = 8 and pH = 2. A monodispersed cubic silver bromide emulsion was obtained. According to electron microscopic observation, the twin generation rate was 1% or less in number. This emulsion was used as a seed crystal and further grown as follows.

The above-mentioned seed crystal was added while maintaining the aqueous gelatin solution at 40 ° C. in the reactor, and further, ammonia water and acetic acid were added to add p.
H was adjusted to 9.5.

After adjusting the pAg to 7.3 with an ammoniacal silver ion solution, a solution containing ammoniacal silver ions, potassium iodide and potassium bromide was added by a double jet method while maintaining the pH and pAg constant. A silver iodobromide layer containing 30 mol% of silver was formed.

Using acetic acid and silver bromide, pH = 9, pAg = 9.0.
After the addition, an ammonium silver ion solution and potassium bromide were added at the same time, and the resultant was grown to 90% of the grain size after growth. At this time, the pH was gradually lowered from 9.0 to 8.20.

After adding potassium bromide solution to make pAg = 11, ammonium silver ion solution and potassium bromide were further added.
Grow while gradually lowering pH to pH 8, and average particle size
A silver iodobromide emulsion containing 0.7 μm and 2 mol% of silver iodide was obtained.

In preparing the emulsion, 300 mg of the following sensitizing dye (A) and 15 mg of the sensitizing dye (B) were added per 1 mol of silver in the emulsion to obtain an emulsion.

[0133]

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Next, as shown below, a desalting step for removing excess salts was performed.

The silver halide emulsion solution was kept at 40 ° C., and the following compound (a) (exemplary compound II-1 shown in JP-A-58-140322) was added to precipitate silver halide grains. After discharging the supernatant, pure water at 40 ° C. was further added. Then, magnesium sulfate is added, and the silver halide grains are precipitated again, and the supernatant is removed. This was repeated once more, and gelatin was added to obtain an emulsion having a pH of 6.0 and a pAg of 8.5.

[0136]

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The emulsion thus obtained was kept at 55 ° C., sensitized with chloroauric acid and hypo, and added with 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. A photosensitive emulsion was obtained. This is designated as emulsion (A).

As an additive to the photosensitive emulsion of the above (A), 400 mg of t-butyl-catechol per mol of silver halide 1.0 g of polyvinylpyrrolidone (molecular weight 10,000) 1.0 g of styrene-maleic anhydride copolymer 2.5 g of trimethylolpropane 10.0 g Diethylene glycol 5.0 g Nitrophenyl-triphenylphosphonium chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 4.0 g 2-mercaptobenzimidazole-5-sodium sulfonate 5.0 mg

[0139]

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[0140]

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Matting agent composed of polymethyl methacrylate having an average particle diameter of 7 μm 7 mg Colloidal silica having an average particle diameter of 0.013 μm 70 mg 2-Hydroxy-4,6-dichlorotriazine sodium 30 mg Sample 4 as shown below using each of the above coating solutions. -1 was created.

Sample 4-1 The undercoat liquid was 50 wt% glycidyl methacrylate, 10 wt% methyl methacrylate, 40 wt% butyl methacrylate.
% Of the copolymer was used so as to have a concentration of 10 wt%, and an aqueous dispersion of the copolymer was applied to the both sides of the dispersion to obtain an undercoated support. Then, the emulsion layer was coated on the support so that the amount of silver on one side was 3.2 g / m ² , the protective layer was adjusted so that the amount of gelatin on one side was 0.98 g / m ^2, and both sides were coated simultaneously at a coating speed of 140 m / min.

Sample 4-2 Sample 4-1 was coated such that a crossover cut layer containing a dye shown in Table 4 was inserted between the emulsion layer and the undercoat layer. The dye was added by dissolving the dye in methanol containing a small amount of triethylamine and then adding the resulting solution to an aqueous gelatin solution to adjust the pH to 6.0 to obtain a coating solution.

Samples 4-3 to 4-10 As in the case of Sample 4-2, coating was performed so as to insert a crossover cut layer. However, as for the method of adding the dye, the same solid fine particle dispersion as in Example 1 was performed, and the dye was added. The amount of the dye added to Samples 4-2 to 4-10 was adjusted to 50 mg / m ² per 1 m ^{2 on} both sides.

The following evaluation was performed on the obtained sample.

(Measurement of Sensitometry) Using standard light B described in "New Edition, Illumination Data Book" as a light source, an exposure time of 0.1 second, 3.2 cms and a non-filter so that the same amount of light is applied to both sides of the film. Exposure. The above sample is SRX
Using a -501 automatic developing machine (manufactured by Konica Corporation), processing was carried out with an XD-SR developer for 45 seconds, followed by fixing and drying, and the sensitivity of each sample was determined. The sensitivity was obtained by calculating the reciprocal of the amount of light required for increasing the blackening density by 1.0, and expressing the sensitivity in the case of sample 4-1 in Table 4 as 100 relative sensitivity.

(Evaluation of MTF) The MTF chart containing a rectangular wave of 0.5 to 10 lines / mm made of lead was converted to a fluorescent screen KO-
250 (made by Konica Corporation)
The film surface was irradiated with X-rays so that the density of the portion not shielded by the lead chart was about 1.0 on both sides.

After the sample irradiated with X-rays as described above was subjected to the same development processing as described above, the recorded rectangular wave pattern was analyzed using a Sakura Micro Densitometer Model M-5 (manufactured by Konica Corporation). Used and measured. The aperture size at this time was 300 μm in the parallel direction of the rectangular wave and 25 μm in the perpendicular direction.
μm, and the magnification was 20 times. MTF obtained
The value is represented by a value of a spatial frequency of 2.0 lines / mm.

[0149]

[Table 4]

[0150]

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As described above, the sample of the present invention has improved sharpness in spite of less decrease in sensitivity than the comparative sample.

On the other hand, the following polydisperse emulsion (B) and tabular grains (C) were prepared in place of the monodisperse emulsion (A).

(B) Preparation of polydisperse emulsion The following four kinds of solutions were prepared by a forward mixing method.

Solution A 100g silver nitrate 100g ammonia water (28%) 78cc Add water 240cc Solution B Ossein gelatin 8g Potassium bromide 80g Potassium iodide
1.3 g water was added and 550 cc solution C ammonia water 6 cc glacial acetic acid 10 cc water 34 cc solution D glacial acetic acid 226 cc water was added and 400 cc solution B and solution C were poured into a reaction vessel for emulsion preparation, and the rotation speed was increased.
Stir with a propeller-type stirrer at 300 revolutions / min.
It was kept at 5 ° C.

Next, the solution A was divided into 1 volume: 2 volume ratios,
One volume, 100 ml, was charged over one minute. Ten
After stirring for 2 minutes, add 200 ml of the remaining 2 volumes of solution A to 1
Charged over 0 minutes. Stirring was continued for another 30 minutes. Then, solution D was added to adjust the pH of the solution in the reaction vessel to 6.0 to stop the reaction.

The average particle size of the silver halide grains was 0.56 μm, and the degree of dispersion was 0.32. The silver iodide content is 1.2
Mole%.

(C) Preparation of Tabular Grains 10.5 g of KBr in 1 liter of water and a thioether compound [HO (CH ₂ ) ₂ S
(CH ₂ ) ₂ S (CH ₂ ) ₂₀ H] 10 cc of 0.5 wt% aqueous solution and gelatin 30
g was added to dissolve and kept at 70 ° C. While stirring, 30 ml of an aqueous silver nitrate solution (0.88 mol / l)
And potassium iodide and potassium bromide (molar ratio 3.5: 96.5)
30 ml of an aqueous solution (0.88 mol / l) of the above was added by the double jet method, and the average particle size was 0.60 μm and the silver iodide content was
3.5 mol% of particles were obtained. 40 ° C after completion of addition of the mixed solution
The temperature dropped until. 24.6 g / AgX of condensate of sodium naphthalenesulfonate and formalin and MgSO ₄
1 mol was added, the pH was lowered to 4.0, and desalting was performed.
An emulsion was prepared by adding 15 g of gelatin / 1 mol of AgX.

With respect to the emulsions obtained in the above (B) and (C),
Chemical sensitization was performed. That is, ammonium thiocyanate, chloroauric acid and hypo were added, and gold-sulfur sensitization was performed.

After completion of the chemical sensitization, 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added. Thereafter, 150 mg of potassium iodide / 1 mol of AgX and sensitizing dyes (A) and (B) were added in the same amount as in emulsion (A), and spectral sensitization was performed. The emulsions thus obtained are referred to as emulsions (B) and (C), respectively.

Additives similar to (A) were added to the photosensitive emulsions (B) and (C) to give emulsion coating solutions. Using these coating liquids and the above-mentioned protective layer liquid, dispersion of solid fine particles was performed using the dye of the present invention in the same manner as in Example 3, and coating was performed so as to insert a crossover cut layer. Similarly, a sample with a small decrease in sensitivity and improved sharpness was obtained.

[0161]

As described in detail above, by containing a dispersion of the solid fine particles of the compound of the present invention, a silver halide having less fogging, improved storage stability over time, and excellent photographic properties is provided. A photographic light-sensitive material is provided.

Claims (4)

(57) [Claims] 1. A photosensitive layer and a non-photosensitive layer on a support
Silver halide photographic materials having
The silver halide photographic light-sensitive material at least compound in more represented by the following general formula (I), wherein the benzalkonium be contained in the form of a solid fine particle dispersion of the layer. Embedded image (R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ represent a hydrogen atom or a substituent. R ₇ and R ₈ are bonded to each other,
A hetero ring may be formed. L ₁ , L ₂ and L ₃ represent a methine group, and m represents 0, 1 and 2. ) 2. A silver halide photographic material as claimed in claim 1, wherein the non-photosensitive layer has a filter layer der Rukoto. 3. The non-photosensitive layer is a crossover cut layer.
2. The silver halide photograph according to claim 1, wherein
Photosensitive material. 4. The method according to claim 1, wherein the non-photosensitive layer is a backing layer.
The silver halide photographic light-sensitive material according to claim 1, wherein: