JPH04114149A - Silver halide photographic sensitive material containing solid fine particle dispersion - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material which contains a material functioning as a novel dye having an excellent decoloring property in particular and which decreases densensitization and after-colors by incorporating at least one kind of solid fine particle dispersions of specific compds. into this photosensitive material. CONSTITUTION:At least one kind of the solid fine particle dispersions of the compds. expressed by formula I are incorporated into this photosensitive material. In the formula I, R<1> denotes an aryl group or arom. heterocyclic group; R<2> denotes a hydrogen atom, alkyl group, aryl group, alkenyl group, cycloalkyl group, alkinyl group, or heterocyclic group; R<3> denotes an electron-withdrawing group; L1 to L3 denote a methine group; X, Y denote an oxygen atom, sulfur atom, selenium atom or tellurium atom but there is no case both X and Y being simultaneously the oxygen atom; (m) denotes zero or 1 to 3 integer. The photographic dye which contains the material functioning as the novel dye having the excellent decoloring property in particular and which decreases the desensitization and after-colors is obtd. in this way.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material containing a solid fine particle dispersion, and particularly to a silver halide photographic material containing a solid fine particle dispersion that functions as a novel dye. The present invention relates to photographic materials.The present invention provides a silver halide photographic material that has excellent decolorizing properties and is less prone to fogging and desensitization.

[Conventional technology]

It is well known that dyes are incorporated into silver halide photographic materials, and are used for the purposes of preventing haley silane, irradiation, light absorption filters, and adjusting the sensitivity of light-sensitive emulsion layers. There is.

Depending on the intended use, the dyes used for these purposes must (i) have a good absorption spectrum;
ii) Do not diffuse from the colored layer to other layers, (in
) stable in silver halide photosensitive materials, (iv) no photographic effects on silver halide emulsions, (V) easy addition, (vi) no color remaining after post-processing. These things are required as its nature.

In order to achieve the above-mentioned object, methods of coloring silver halide photographic materials using water-soluble dyes have been conventionally used.For example, U.S. Pat.
, No. 150.695, No. 2,274.782, No. 3,
No. 094゜418, No. 3,933,798, No. 4,1
87.225, 4,234゜677, 4,28
No. 8.534, No. 4,266.014, No. 4,379
Pyrazolone oxonol dyes typified by US Pat. 2,298.73
No. 1, No. 3 247.127, No. 3,468.883
No. 3,469,985, No. 3.480.436, No. 3.540.888, No. 3.398.145,
3゜417.084, 3,440,051, 4,042,397, British Patent No. 1.077.049
No. 1,265.485, No. 506,385, No. 1,424,515, Research Disclosure (hereinafter referred to as RD) No. 14416; 3.637,676, 3,681,08
No. 1, No. 3゜540.888, No. 4,232.115
Oxonol dyes with other skeletons, such as those represented by Belgian Patent No. 780.011 and U.S. Patent No. 2.53
No. 8.008, No. 3,497.502, No. 3,540
．． No. 888, No. 3,544゜325, No. 4,042,
No. 397, No. 4,420.555, Special Publication No. 31-10
No. 578, No. 51-3623, No. 56-49953, No. 57-46778, No. 59-26940, No. 5
Benzylidene and cinnamylidene type dyes represented by No. 9-37303, etc.; U.S. Pat.
No. 4, No. 4゜232.115, British Patent No. 369,7
No. 21, No. 506, No. 385, Special Publication No. 31-5920
Styryl-type dyes represented by U.S. Patent Nos. 48-27927, 57-46056, and 59-28898;
No. 3, No. 2゜646, No. 409, No. 3,125.448
No. 3.148.187, No. 3.469.985, No. 3,540,888, No. 4,232.115,
Belgian Patent No. 739.874, British Patent No. 2.08
Merocyanine dyes represented by U.S. Pat. No. 3.241, etc.; U.S. Pat.
No. 4, No. 2゜322, 006, No. 2,390.707
No. 2,464.785, No. 2゜503.717, No. 2,527.583, No. 2.956.879,
Typical water-soluble dyes include azo dyes such as No. 4.276.373.

These water-soluble dyes require water,
A common method is to dissolve the dye in another water-soluble organic solvent and add it to the photographic material, but because the dye is water-soluble, it does not remain in the desired layer and diffuses into the gold layer of the photographic material. Therefore, in order to achieve the original purpose, it is necessary to add more dye (dye) as it diffuses into other layers, which may cause undesirable effects on both the added layer and other layers, such as desensitization and fogging. Normally, this would occur.In order to avoid this, if the amount used is reduced, the original effect will no longer be obtained.

In order to improve this drawback, diffusion-resistant dyes have been proposed. Yellow colloidal silver substitute dye (hereinafter referred to as Yc dye) used in color photosensitive materials is a typical compound.

In silver halide color photographic light-sensitive materials, blue-absorbing materials are sometimes used.
A yellow colloidal silver called ea 5ilver is used. This colloidal silver absorbs blue light during exposure,
Although it is removed during processing, it absorbs not only blue light but also some long-wavelength light, so it has the drawbacks of desensitizing other emulsion layers and increasing fog in other emulsion layers. have.

In order to improve this drawback, diffusion-resistant YC dyes have been proposed. For example, U.S. Pat.
JP 61-204630, JP 61-205934, JP 62-56958, JP 62-92949, JP 6
No. 2-222248, No. 62-32460, No. 63-
No. 40143, No. 63-184749, No. 63-31
No. 6852 is a typical example, but these compounds still do not have a sufficient light absorption region and desensitize other emulsion layers, and as described in these patent documents. The usual method of addition is to dissolve the compound in a solvent and add it with a repolymer added as oil droplets, or to dissolve it in a water-soluble organic solvent and add it directly to the emulsion, so that it is sufficiently bleached after processing and does not flow out and the color becomes cloudy. It had the disadvantage that it caused

Furthermore, a method using solid fine particles is known as a method for making dyes resistant to diffusion. For example, W 088/4,794, JP 63-197943, JP 64-40827, JP 1-155341, JP 1-172828, JP 2-
No. 1838, No. 2-1839, No. 2-110453, U.S. Patent No. 4.904゜565, U.S. Patent No. 4,923.7
This is the compound described in No. 88 and the like. It is true that these compounds are added in the form of solid fine particles, but when they are added in the solid state, they have the major disadvantage of insufficient decolorizing properties, which is the biggest bottleneck, and residual color remains after photographic post-processing.

[Object of the Invention] The object of the present invention is to provide a silver halide photographic light-sensitive material with less fog, desensitization, and residual color, which contains a substance that functions as a novel dye that has good properties as a photographic dye, especially excellent decolorization properties. Our goal is to provide the following.

(Structure of the Invention) The object of the present invention is to obtain a compound represented by the following general formula CI (
This has been achieved using a silver halide photographic material characterized by containing at least one solid fine particle dispersion of a compound of the present invention (hereinafter also referred to as the "compound of the present invention").

General formula (1) In the formula, R' represents an aryl group or an aromatic heterocyclic group, and R'' represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, an alkynyl group, or a heterocyclic group. represents a group.

R3 represents an electron-withdrawing group, L3 represents a methine group, X and Y represent an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom, provided that X and Y are both oxygen atoms. Never.

m represents zero or an integer of 1 to 3.

In general formula (I), R1 represents an aryl group or an aromatic heterocycle, and examples of the aryl group include a phenyl group and a naphthyl group.

These groups include halogen atoms (e.g. fluorine, chlorine, bromine, iodine, etc.), hydroxyl groups, alkoxy groups (e.g. methoxy, ethoxy, t-butoxy, dodecyloxy, etc.), aryloxy groups (e.g. phenoxy, p-tolyloxy, naphthyloxy, etc.), cyano group, carbamoyl group (e.g. carbamoyl, N-methylcarbamoyl, N
-phenylcarbamoyl, N,N-dimethylcarbamoyl, etc.), sulfamoyl group (e.g. sulfamoyl,
N-pentylsulfamoyl, N-pentyl-N-methylsulfamoyl, N-phenylsulfamoyl, etc.),
Sulfonyl groups (e.g. methylsulfonyl, butylsulfonyl, octadecylsulfonyl, etc.), alkoxycarbonyl groups (e.g. ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), nitro groups, aryl groups (e.g. phenyl, naphthyl, etc.), amide groups (e.g. acetylamino, etc.), sulfonamido groups (e.g. methylsulfonylamino, propylsulfonylamino, butylsulfonylamino, etc.), acyl groups (e.g. acetyl, propyl,
benzoyl, etc.), alkyl groups (such as methyl, ethyl,
propyl, i-butyl, t-butyl, octyl, etc.), alkylthio groups (e.g. methylthio, propylthio, t-
octylthio, etc.), arylthio groups (e.g. phenylthio, naphthylthio, etc.), heterocyclic thio groups (benzthiazolyl-2-thio, etc.), heterocyclic oxy groups (e.g. benzoxacylyl-2-oxy, etc.), acyloxy groups (e.g. acetoxy, octylthio, etc.), decanoyl, etc.), carbamoyloxy groups (e.g. N-methylcarbamoyloxy, N-phenylcarbamoyloxy, etc.), sulfonyloxy groups (
(e.g., phenylsulfonyloxy, dodecylsulfonyloxy, etc.), amino groups (e.g., dimethylamino, amino, etc.), ureido groups (e.g., methylureido, phenylureido, etc.), imide groups (e.g., N-succinimide, 3
-penzylhydantoinyl, etc.), alkoxycarbonylamino groups (e.g., ethoxycarbonylamino, etc.), aryloxycarbonylamino groups (e.g., phenyloxycarbonylamino, etc.), sulfinyl groups (e.g., octylsulfinyl, phenylsulfinyl, etc.), aryloxycarbonyl groups (e.g. phenoxycarbonyl, etc.)
, a heterocyclic group (for example, 2-pyridyl, 2-benzthiazolyl, furyl, thienyl, etc.), a carboxyl group, etc. as a substituent.

The aromatic heterocyclic group represented by R1 includes a thienyl group, a furyl group, a pyranyl group, a pyrrolyl group, an imidazolyl group, a pyridyl group, a thiazolyl group, an oxasilyl group, a selenazolyl group, a pyrimidinyl group, an isoxasilyl group, and an isothiazolyl group. Examples include groups. These groups can have the same group as the aryl group represented by R1 as a substituent.

-a Formula CI), R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, an alkynyl group, and examples of the alkenyl group include vinyl, 1-
Examples include multiple groups such as propenyl and 1-octenyl, and examples of the cycloalkyl group include multiple groups such as cyclopropyl, cyclopentyl, and cyclohexyl. Examples of the alkynyl group include ethynyl, 1-propynyl, 1-octenyl, and the like.

These groups can have the same substituents as the aryl group and aromatic heterocyclic group represented by R1.

Examples of the alkyl group represented by R2 include methyl group,
Ethyl group, propyl group, isopropyl group, t-butyl group, n-hexyl group, n-octyl group, n-dodecyl group,
Represents a 2-ethylhexyl group, etc.

These groups can have the same group as the aryl group represented by R1 as a substituent.

The aryl group represented by R2 represents the same group as the aryl group represented by R1.

At least one of the substituents represented by Rr, Rz, and Rs has at least one of a sulfonamide group, a sulfamoyl group, and a carboxyl group. Represents a similar meaning.

R3 represents an electron-withdrawing group, and an electron-withdrawing group is defined by "Structure-Activity Relationship of Drugs - Guidelines for Drug Design and Mechanism Research," Chemistry Special Edition (Nankodo) No. 122, Structure-Activity Relationship Meeting Gold. Line, P, 96 to 103, electronic parameters shown in Table 1, σ, values greater than zero, such as cyano group, carbamoyl group (e.g. methylcarbamoyl, propylcarbamoyl, octylcarbamoyl, phenylcarbamoyl, etc.), alkyl Oxycarbonyl group (
(e.g., methyloxycarbonyl, ethyloxycarbonyl, octyloxycarbonyl, etc.), aryloxycarbonyl groups (e.g., phenyloxycarbonyl, naphthyloxycarbonyl, etc.), acyl groups (e.g., acetyl group, benzoyl group, etc.), phenyl groups (e.g., P-nitrocarbonyl, etc.), phenyl group, 0-cyanophenyl group, n-carboxyphenyl group, P-methylsulfonylphenyl group, etc.), alkylsulfonyl group (e.g. methylsulfonyl group, propylsulfonyl group, octylsulfonyl group, etc.), arylsulfonyl group (e.g. phenylsulfonyl group) , naphthylsulfonyl, etc.), a nitro group, a sulfamoyl group (eg, methylsulfamoyl, propylsulfamoyl, octylsulfamoyl, phenylsulfamoyl, etc.), and a nitroso group.

Specific examples of the compounds of the present invention will be shown below, and the compounds of the present invention can be easily synthesized, for example, by the method shown in US Pat. No. 4,923,788.

Specific synthesis examples of the compounds of the present invention are shown below, but other compounds can also be synthesized by similar methods.

Synthesis Example 1> Synthesis of Exemplified Compound 2 24.1 g of 4-(butylsulfonylamino)benzaldehyde, 4-
(4-(butylsulfonylamino)phenyl)-3-
35.2 g of 2-thousand ions of cyanothiophene in 100 g of acetic acid
After adding 16.4 g of added sodium acetate in 60
The reaction was carried out at ~70°C for 2 hours.

After the reaction is complete, cool the reaction solution to room temperature and add 10% of the reaction solution to water.
00m! added inside.

The desired product was obtained by filtering, washing with water, and drying the solid that was added and precipitated. The target product was confirmed by NMR and IR, and a parent peak was obtained by mass spectrum (yield: 38.6 g, yield: 67%).

(Synthesis Example 2) Synthesis of Exemplified Compound 11 2-formylthiophene 11.2 g, 4-(4-(butylsulfonylamino)phenyl)-3-cyanothiophene-2-
Add 35.2 g of 1,000 on, 16.4 g of sodium acetate, and 150 d of dimethylformamide, and heat at 50 to 60°C for 1.
The reaction was carried out for 5 hours. After the reaction was completed, the reaction solution was mixed with 100 (l) of water.
d ~ Acetic acid 15011! The desired product was obtained by washing the precipitated solid with ethanol and drying it. The target is NM
Confirmed with R and IR, and obtained parent peak with mass spectrum (
Yield: 31.7 g, yield: 70%).

The compound represented by the general formula [I] can be contained in any photographic constituent layer of the light-sensitive material of the present invention, and the photographic constituent layers include, in addition to the silver halide emulsion layer, an antihalation layer and an intermediate layer. , a protective layer, and a non-photosensitive layer such as a filter layer. Among these, particularly preferred are the intermediate layer and the filter layer.

The compound represented by the general formula [I] according to the present invention is particularly useful as a photographic dye, and is useful as a photosensitive silver halide emulsion layer, other non-photosensitive layers (protective layer, intermediate layer, filter layer, anti-oxidant layer, etc.). (halation layer, etc.) as a solid fine particle dispersion.

In the present invention, typical methods for obtaining a solid fine particle dispersion include the precipitation method and mechanical crushing method described below.

(1) As a precipitation method, if the compound to be made into a solid fine particle dispersion is base-soluble, the compound is dissolved in basic water and added to an acidic solution for dispersion; if the compound is organic solvent-soluble, the compound is A method of dissolving the compound in a water-miscible organic solvent and adding it to water for dispersion, or a method of dissolving the compound in a water-immiscible low-boiling organic solvent to form an oil-in-water dispersion,
There is a method of removing the solvent by volatilization.

(2) As a mechanical pulverization method, the compound is made into a fine powder using high energy such as ultrasonic waves, and then added to a hydrophilic colloid solution and dispersed, in the presence of a dispersion aid, There is a method of moistening it with water or a poor solvent and dispersing it into fine particles using a mill.

In the present invention, the solid fine particle dispersion of the compound of the present invention preferably has a narrow distribution.

In the present invention, a preferred method for obtaining a solid fine particle dispersion with a narrow distribution is as follows: (1) As a precipitation method, (1) the compound is dissolved in a basic hydrophilic colloid solution containing a dispersion aid, and the acid is gradually added. (2) A method of obtaining a dispersion by dissolving the compound in a basic aqueous solution and gradually adding it to a neutral or acidic hydrophilic colloid solution containing a dispersion aid; 1ard spear, 'Gordo
Homogeneous precipitation method in which crystals are gradually precipitated from a homogeneous solution by n et al.; ■ A method in which a compound is dissolved in a water-miscible organic solvent and added to a hydrophilic colloid solution containing a dispersion aid for dispersion;
■Dissolve the compound in a water-miscible organic solvent containing a dispersion aid,
Method of adding and dispersing in a hydrophilic colloid solution: ■ Dissolving the compound in a water-immiscible organic solvent, mixing it with the hydrophilic colloid solution to form a water-in-oil dispersion, and then dispersing it in water by the so-called phase inversion method. There is a method in which a water-immiscible organic solvent is removed by volatilization as an oil droplet dispersion. (2) Mechanical pulverization methods include a method in which the compound is wetted with water or a poor solvent, and fine particles are dispersed in a mill using media with a narrow particle size distribution in the presence of a dispersion aid and/or a hydrophilic colloid. There is.

The water-miscible organic solvent is not particularly limited as long as it can dissolve the photographic reagent without decomposing it and is miscible with water. Typical examples include alcohols (e.g. methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, diacetone alcohol, ethylene glycol monobutyl ether, etc.), glycols (e.g. ethylene glycol, diethylene glycol, propylene glycol, etc.) , cyclic ethers (e.g., dioxane, tetrahydrofuran, etc.), nitriles (e.g., acetonitrile, etc.), amides (e.g., dimethylformamide, etc.), and N-methyl-2-pyrrolidone. -Propyl alcohol is preferred.

In the present invention, a particularly preferred method for obtaining a solid fine particle dispersion with a narrow particle size distribution is to wet the compound with water or a poor solvent, and then use a medium with a narrow particle size distribution in the presence of a dispersion aid and/or a hydrophilic colloid. This is a method in which fine particles are dispersed at high temperature in a mill (pulverizer) using (grinding media).

In the present invention, devices for dispersing solid fine particles include ball mills, roll mills, sand mills, etc.
A sand mill is preferred. Commercially available sand mills are widely available.

Materials for the media used in the present invention include glass,
Examples include alumina, zirconia, agate, stainless steel, and nylon, with glass, zirconia, and alumina being preferred. When glass is used, it is particularly preferable to use glass containing 60% by weight or more of silicon dioxide.

The media is preferably spherical, and the particle size is not particularly limited, but is usually 0.1 mmφ to 20 mm, preferably 0.2 mm to 1 mm.
0maφ, particularly preferably 0.5mφ to 5. It is OWφ.

Specifically, examples of the glass media include Prite Glass Peas manufactured by Bright Seisaku Kogyo Co., Ltd.

In the present invention, when solid fine particle dispersion of the compound of the present invention is carried out in a sand mill, a solid fine particle dispersion with a narrow particle size distribution can be obtained by using a medium with a narrow particle size distribution.

The particle size distribution of the media is 30% or less, preferably 25% or less, particularly preferably 20% or less in terms of the width of the distribution defined below.

<Definition of width of distribution> Particle size standard deviation x 100/average particle size = width of distribution (%) When performing solid fine particle dispersion of photographic organic additives using the narrow distribution media described above, the dispersion should be By carrying out the process at a high temperature, it is possible to obtain a solid fine particle dispersion of a photographic organic additive with a narrower distribution. The temperature during dispersion is usually 30°C or higher, preferably 40°C or higher, particularly preferably 50°C or higher and 80°C or lower. Temperatures higher than 80°C are not preferred because aggregates may occur or the compound may deteriorate.

In the present invention, a solid fine particle dispersion refers to an average particle size of 1 μm or less, preferably 0.7 μm or less.
am or more, particularly preferably 0.4 am or less 0. O1μ
m or more.

The particle size referred to here is the diameter when a projected image of the particle is converted into a circular image with the same area.

The average particle size here means the frequency ni of particles having the particle size d.
The particle size d when the product ni Xd4' of and d% is maximum
, is defined as (3 significant figures, minimum digit is 4 to 5 people) The particle size can be determined by, for example, magnifying the particle 10,000 to 50,000 times with an electron microscope and projecting it, and then calculating the particle diameter on the print or the time of projection. It can be obtained by actually measuring the area of . (
The number of particles to be measured is assumed to be 1000 or more indiscriminately. ) Here, the particle size measurement method shall follow the measurement method described above,
The average particle size is a simple average.

In the present invention, the effect is exhibited when the degree of dispersion of the solid fine particle dispersion is 30% or less, preferably 25% or less, particularly preferably 20% or less in the width of the distribution defined below.

<Definition of width of distribution> Particle size standard deviation x 100/average particle size = width of distribution (%)
In the present invention, the solid fine particle dispersion of the compound of the present invention may be added to a photosensitive layer containing photosensitive silver halide, or may be added to a non-photosensitive layer not containing photosensitive silver halide. Good too.

In the present invention, known surfactants can be used as the dispersion aid for preparing the solid fine particle dispersion, and anionic, nonionic, and betaine type surfactants are preferred.

Anionic surfactants preferably used as dispersants for the compounds of the present invention include the following general formulas CIA) to (VI
Examples include those represented by A''l, and these are particularly preferably used.

General formula [IA] In the formula, R represents a hydrogen atom or a methyl group, R1m and Rem each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, which may be the same or different, and W is 1000 M, -503M, represents OPO(OM) z, and M represents a hydrogen atom or a cation. ml represents an integer of 0 to 50, and n represents an integer of 0 to 4.

General formula (IIA) represents on. m2 represents an integer from 0 to 50, and n2 represents 0 to 50.
a represents an integer of 4, and a represents an integer of 0 or 1.

General formula (I[[A) In the formula, R4m and Rsa each have 6 to 18 carbon atoms.
represents an alkyl group, and M represents a hydrogen atom or a cation.

General formula (TVA) In the formula, R represents a hydrogen atom or a methyl group, R″″ represents an alkyl group or alkenyl group having 6 to 20 carbon atoms, and W represents -COOM, -503M, OPO(OM)!
M represents a hydrogen atom or in the formula, R6m represents an alkyl group having 6 to 20 carbon atoms, and R? '' represents an alkyl group having 1 to 4 carbon atoms, X represents -COOM or -503M, and M represents a hydrogen atom or a cation. n represents an integer of 1 to 4.

In the formula, R1111 and 39m each represent an alkyl group having 6 to 20 carbon atoms, and M represents a hydrogen atom or a cation.

General formula [VIA] The group includes those having a substituent, and in this case, the number of carbon atoms does not include the substituent. Examples of cations include sodium ions, potassium ions, ammonium ions, and the like.

Among those represented by general formulas (IA) to (VIA), particularly preferred are general formula [IA] and general formula (I[
A) and general formula (VA).

Next, specific examples of compounds are listed below. In these limited formulas, R
10 hatake R11+1 and RIh each have 1 carbon atom
~16 alkyl group, and M represents a hydrogen atom or a cation.

Each alkyl a l2H2S 0(CHzCHzOhSO:+Na CIIH2:l C 0(CHzCHzOhSO3Na C+ zHz s -0(CH, COzo'h-(CO
zhso sKCI&H330(CHzCHzO甐CH
zhSOsNaC+ JtsO3O3Na C2H.

■ CtJszOP(ONa)z Nonionic surfactants preferably used as a dispersant for the compound of the present invention include those that have an HLB value of 1 to 7 according to Griffin and are substantially insoluble in water, that is, hydrophobic. A nonionic surfactant with an HLB value of 8 to 20, which is a combination of a substantially water-soluble or hydrophilic surfactant, and in particular, a nonionic surfactant with an HLB value of 1 to 7 and 8 to 20, respectively. The formula structure is not particularly limited as long as it falls within these ranges. Further, it is particularly preferable that the surfactant is in a liquid state at 25°C, but even if it is solid at 25°C, any surfactant that becomes liquid in a dispersed state can be used within the scope of the present invention. be able to. If the HLB value exceeds 20, it is not only impossible to obtain good dispersibility but also economically unfavorable.

Specific compounds are listed as preferred nonionic surfactants used in the present invention, but the ones listed here are:
This is an example of the most preferable one, and the present invention is not limited thereto.

First, specific examples of nonionic surfactants having an ILB of 1 to 7 will be given.

N-1 Sorbitan monolaurate N-2 Sorbitan monooleate N-3 Sorbitandole oil fatty acid ester N-4 Sorbitan castor oil fatty acid ester N-5 Polyoxyethylene oleate N-6 Among polyoxyethylene olive oil fatty acid esters, ethylene Glyceryl monocaprylate Glyceryl monooleate Glyceryl monoisostearate Diglyceryl monooleate Polyoxyethylene glyceryl monooleate (n=1
~6) Polyoxyethylene nonylphenyl ether (n-2~
6) Polyoxyethylene oleyl ether (n=2-6) Polyoxyethylene sorbitol fatty acid-1O ester (n=2-6) N-15 Glyceryl monoalkyl ether (alkyl group has 8-18 carbon atoms) N- 16 Polypropylene oxide N-17 Oxyethylene/oxypropylene block polymer (ethylene oxide weight% 5%) Next, specific examples of nonionic surfactants having an HLB of 8 to 20 will be given.

n I C+. Hi70 (CHZC820
hHn 2 C+sHitOiCHzCH
zOh-Ilf(n 3 CIJzsO(
CHzCHzOh-LHn 4 C+Jz
s1MCHzCHzO)ydlC++HzsCOO(C
HzCHzOhnHC+ J! sCOO(CHzCHz
O)-rll) 1 polyoxyethylene sorbitan monolaurate (n=20) C+! HzsCON [ICHzCHzOh-5H]
t-Oxyethylene/oxypropylene block polymer (ethylene oxide weight%: 40%) The surfactant used as a dispersant for the coupler according to the present invention is used in an amount of 0.1 to 15% by weight based on the coupler.

Particularly preferred activators include those having three or more ethyleneoxy groups and a hydrocarbon moiety having 6 to 24 carbon atoms, with anionic activators being particularly preferred. The most preferred surfactants include di-alkali metal salts of half esters of sulfosuccinic acid and alkoxy alcohols or aryloxy alcohols, especially sulfosuccinic acid and alkoxy (preferably alkoxy having 10 to 12 carbon atoms).
The disodium salt of the half-ester with alcohol is preferred.

Particularly preferred surfactants are illustrated below.

f: 10-12, m: 3-5 Aerosol A102 (manufactured by Cyanamid) m: 5-10 Aerosol A103 (manufactured by Cyanamid) CIJzsO (
CHzCHzO)'rksOJa polystep B23(
(manufactured by Stepan Chemical Co.) In the present invention, hydrophilic colloids used in preparing the solid fine particle dispersion of photographic organic additives include gelatin, gelatin derivatives, albumin, casein, gum arabic, poly-N-vinylpyrrolidone, Although hydroxymethylcellulose, polyacrylamide, polyacrylic acid, etc. can be used, gelatin is preferred in the precipitation method, and poly-N-vinylpyrrolidone is preferred in the mechanical grinding method.

In the present invention, a small amount of an acid, especially an organic acid, such as acetic acid, citric acid, oxalic acid, tartaric acid, etc., is added to the solid fine particle dispersion or hydrophilic colloid solution of the organic additive for photography.
It is preferably adjusted to be neutral or acidic.

In the present invention, the compound of the present invention is substantially insoluble in neutral and acidic (pH 7 or less) water, and basic (
It is preferable to use one that dissolves in water with a pH of 9 or higher, that is, in most developing processing solutions. “Substantially insoluble” here means 2.
Solubility in distilled water at 5°C is 1% by weight or less,
Preferably 0.5% by weight or less, particularly preferably 0.2M
% or less.

Preferred organic dyes as compounds of the present invention are organic dyes having at least one carboxyl group, sulfamoyl group, or sulfonamide group.

In the present invention, the amount added of the solid fine particle dispersion of the compound of the present invention varies depending on the purpose of use and is not particularly limited, but is usually preferably 0.0001 g/n? ~5.0
g/bo, more preferably 0.005 g/bo to 1.
0 g/M, particularly preferably 0.001 g/M to 0
．． It is 5g/I.

In the silver halide color light-sensitive material of the present invention, two or more types of solid fine particle dispersions of the compound of the present invention may be used in combination, and depending on the purpose, dispersions of other hydrophobic dyes or water-soluble dyes may be used. May be used in combination with

In the present invention, the layer to which the solid fine particle dispersion of the compound of the present invention is added may be a photosensitive layer containing photosensitive silver halide or a non-photosensitive layer containing no photosensitive silver halide. A photosensitive layer is preferred. Specific examples of the non-photosensitive layer include an undercoat layer, an antihalation layer, an intermediate layer, a yellow filter layer, an ultraviolet absorbing layer, a colloidal silver-containing layer, a protective layer, and the like.

In the present invention, the solid fine particle dispersion of the compound of the present invention is water-insoluble and stably exists in the silver halide color photographic material, but it becomes water-soluble by being treated with a photographic developer (pH 9 or higher). It dissolves and flows out, but
Most of the silver halide color material disappears from the silver halide color light-sensitive material by chemical decolorization and/or chemical reaction.

In the present invention, if the distribution of the solid fine particle dispersion of the compound of the present invention is narrowed, the rate of dissolution and outflow and/or chemical reaction decolorization is faster and the residual amount is small, so that the color of the silver halide color light-sensitive material can be improved. By effectively preventing contamination and suppressing light scattering that occurs during exposure of silver halide color light-sensitive materials, it is possible to more effectively exhibit the effect of improving sharpness while minimizing a decrease in sensitivity.

The compound according to the present invention preferably has an optical density of 0.05 to
3.0 range.

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

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

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

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

Furthermore, by coupling with a colored coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, Compounds that release photographically useful fragments such as fogging agents, anti-capri agents, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer.

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

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

A dye image can be obtained using the light-sensitive material of the present invention by means of commonly known color photographic processing after exposure.

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

In the following examples, the amount added in the silver halide photographic material is expressed in grams per 1 unless otherwise specified.

Note that silver halide and colloidal silver are shown in terms of silver.

Example 1 (Preparation of coating solution for protective layer) After dissolving 500 g of gelatin in 7.52 g of water, 10 g of coating aid (Su-1) and silica with an average particle size of 3.5 μm were added.
A hardening agent (H-1) was added to prepare a protective layer coating solution.

(Preparation of coating solution for photosensitive emulsion layer) Sodium thiosulfate and chloroauric acid were added to a monodisperse cubic silver chlorobromide emulsion containing 38 mol% silver bromide and having an average grain size of 0.25 μm. Optimal chemical ripening was carried out at 58°C.

On the other hand, the following composition was subjected to sand mill dispersion using a dyno mill manufactured by Shinmaru Enterprises, Inc. using exemplary compounds of the compounds of the present invention or comparative dyes (see Table 1). However, the media used was selected from Bright Glass Peas MK-5GXO manufactured by Bright Label Industry Co., Ltd. so that the breadth of the particle size distribution was 20% or less.

The disc rotation speed of the mill was 3.300 rpra, and the temperature of the dispersion in the vessel was adjusted to 35°C.

Surfactant B Aerosol A102 (manufactured by Cyanamid Co., Ltd.) The above silver halide emulsion and this dispersion were mixed and dissolved to have the following composition, and a coating aid (Su-1) and a hardening agent (H-1) were added. was added to prepare a photosensitive emulsion layer coating solution.

(Preparation of Samples) A photosensitive emulsion layer and a protective layer were simultaneously coated in multiple layers using each of the above coating solutions on a 100 μm polyethylene terephthalate film base subjected to latex undercoating described in JP-A-59-19941. Sample 1-1 was prepared by drying. The amount of coated silver is 4.0g/po, the amount of dye applied is 3X10-
'It was mole/bo.

In the same manner, samples were prepared by replacing the compounds used in Sample 1-1 with the compounds shown in Table 1, and each of these samples was added to Sample 1.
-2 to 1-52.

The following margins Comparative Dye A Comparative Dye B Comparative Dye G (Processing/Evaluation) Each of these samples was exposed through a wedge, and then processed into an automatic processor GR-27 (manufactured by Konica Corporation) using a developer and fixer with the following composition. Processing was performed.

Processing (process) (temperature) (time) Development 28
Fix for 30 seconds at ℃ Wash with water for about 20 seconds at 28℃
Room temperature for about 20 seconds Comparative dye C Comparative dye E Comparative dye E Finish υi Drying at 45°C for 20 seconds <Developer composition> (Composition A) Pure water (ion-exchanged water> 150d Disodium ethylenediaminetetraacetate 2g Diethylene glycol 50g Potassium sulfite (55%)
III/ν aqueous solution) 10 (ld potassium carbonate
50g hydroquinone
15g 5-methylbenzotriazole
200 dl-phenyl-5-mercaptotetrazole 30■ Potassium bromide 4.5 g Potassium hydroxide Amount to adjust pH of working solution to 10.4 (composition) Pure water (ion-exchanged water) 311I.

Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25■ Acetic acid (90% aqueous solution > 0.311
5-nitroindazole 110Jdl-
Phenyl-3-pyrazolidone 500■ When using a developer, dissolve in water 500% in the order of composition A and composition,
1! It was finished and used.

<Fixer formulation> (Composition A) Ammonium thiosulfate (72.5%-/V aqueous solution) 40
d Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g sodium citrate dihydrate 2g acetic acid (90%-/V aqueous solution>
13.6d (composition) Pure water (ion exchange water > 17d sulfuric acid (
50%-/V aqueous solution) 4.7g aluminum sulfate 26.5g (Alzo3
Converted content: 8.1%-/V aqueous solution) When using a fixer, dissolve the above composition A in 500 Id of water,
1 and used it.

The pH of the second fixer was about 4.3.

The presence or absence of residual color staining after treatment was evaluated using the following method. The visible spectrum of the unexposed area of each sample after treatment was measured, and the decolorization rate was determined from the difference between the absorbance at the absorption maximum (E2) and the following E1 using the following formula.

E+ (E represents the absorbance at the absorption maximum of a sample prepared in the same manner except for the silver halide.) Table 1 shows the evaluation results of photographic properties and decolorization rate. Here, gamma represents the slope of a straight line between densities 0.5 and 4.0. Capri is the density of the unexposed area.

Table 1 (Continued 1) Table 1 (Continued 2) As is clear from the results in Table 1, the compounds of the present invention exhibit better decolorization properties than the comparative compounds, and are effective against photosensitive silver halide. However, it is found that it is inert and does not affect photographic properties.

Example 2 Multilayer color photographic element sample 2-1 was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

Sample 2-1 (comparison) 1st layer: antihalation layer (HC-1) black colloidal silver 0.20 ultraviolet absorber (UV-1)
0.20 colored coupler (CC-1) 0.
05 Colored coupler (CM-2) 0.05 High boiling point solvent (Oil-2) 0.20 Gelatin
1.5 2nd layer: Intermediate layer (IL-1) Ultraviolet absorber (UV-1) 0.01 High boiling point solvent (Oil-2) 0.01 Gelatin
1.5 Third layer: Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-2-1) Silver iodobromide emulsion (Em-22) Sensitizing dye (S-1) 2.5X10- ' Sensitizing dye (S-2) 2.5X10-' Sensitizing dye (S-3) 0.5X10-' (mol/silver l) Cyan coupler (C-1) Cyan coupler (C-2) Colored coupler (CC -1) DIR compound (D-1) High boiling point solvent (Oil-2) Gelatin 4th layer: High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-2-3) Sensitizing dye (S- 1) 2.0X10-' Sensitizing dye (S-2) (Mole/1 mole of silver) (Mole/1 mole of silver) (Mole/1 mole of silver) 1.0 0.5 mole) 0.8 0.2 0.05 0.002 0.5 1.5 2.0 2.0X10-' (mol/silver 1 mol) Sensitizing dye (S-
3) 0, lX10-' (mol/silver 1 mol) Cyan coupler (C-3) 0.25 Colored coupler (CC-
1) 0.015DIR compound (D-2)
0.05 High boiling point solvent (Oil-2) 0.5 Gelatin i, s 5th layer: Intermediate layer (IL-2) Gelatin 0.5 6th layer: Low sensitivity green-sensitive emulsion layer (GL) Silver iodobromide Emulsion (Em-2-1) 1.0 Sensitizing dye (S
-4) 5.0X10-' (mol/silver 1 mol) sensitizing dye (S-
5) 1.0X10-' (mol/mol of silver) Magenta coupler (M-1) 0.4 colored coupler (CM-1
) 0.05DIR compound (D-3) 0
．． 015DIR compound (D-4>0.02
0 High boiling point solvent (Oil-3) 0.5 Gelatin 1.0 7th layer: Intermediate layer (IL-3) Gelatin 0.8 High boiling point solvent (Oil-2) 0.2 8th layer: High sensitivity green sensitivity Opalescent layer (GH) Silver iodobromide emulsion (Em-2-3) 1.3 Sensitizing dye (S
-6) 1.5X10-' (mol/silver 1 mol) sensitizing dye (S-
7) 2.5X10-' (mol/silver 1 mol) sensitizing dye (S-
8) 0.5X10-' (mol/1 mole of silver) magenta coupler (M-2) 0.05 magenta coupler (M-3
) 0.15 Colored Turnip'y -(CM-2)
0.05DIR compound (D-3) 0.0
1 High boiling point solvent (Oil-1) 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 point solvent (
Oil-1) 0.1 gelatin
0.8 10th layer: Low sensitivity blue-sensitive emulsion layer (BL) silver iodobromide emulsion (
Em-2-1) 0.25 silver iodobromide emulsion (Em-2
-2) 0.25 sensitizing dye (S-10) 7X10-' (mol/silver 1 mol) Yellow coupler (Y-1) 0.5 yellow coupler (Y-2) 0.1 DIR compound (D-2)
0.01 High boiling point solvent (Oil-1) 0
．． 15 Gelatin 1.0 11th layer: Highly sensitive blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (
Em-2-4) 0.50 silver iodobromide emulsion (Em-
2-1) 0.20 sensitizing dye (S-9) 1.0X10-' (mol/silver 1 mol) sensitizing dye (S-
10) 3.0X10-' (mol/mol of silver) yellow coupler (Y-1) 0.30 yellow coupler (, Y-
2) 0.05 high boiling point solvent (Oil-1)
0.07 Gelatin 1.1 12th layer: 1st protective layer (PRO-1) Fine grain silver iodobromide emulsion 0.4 (Average grain size 0.08 μm, Agl 2 mol%) Ultraviolet absorber (UV-1) 0.10 UV absorber (U
V-2) 0.05 high boiling point solvent (Oil-2
) 0.1 High boiling point solvent (Oil-4) 0
．． 1 Formalin scavenger (H3-1) 0.5 Formalin scavenger (MS-2) 0.2 Gelatin 1.0 13th layer: 2nd protective layer (PRO-2) Surfactant (Su-3) 0.005 Alkali-soluble matting agent (average particle size 2 μm) 0.10 Cyan dye (AI C-1) 0.005 Magenta dye (AIM-1) 0.01 Slip agent (WA
X-1) 0.04 gelatin
0.6 In addition to the above composition, each layer contains coating aid 5u-4, dispersion aid 5u-2, hardening agents H-1 and H-2, and antifungal agent DI.
-1, stabilizer 5tab-1, antifoggant AF-1,A
F-2 was added.

Em-2-1 Average grain size 0.46 μm, average silver iodide content 7.5%, monodisperse silver iodobromide emulsion Em-2-2 Average grain size 0.32 μm, average silver iodide content 2.0%, monodisperse silver iodobromide emulsion Em-2-3 Average grain size: 0.78 μm, average silver iodide content: 6.0%, monodisperse silver iodobromide emulsion Em-2- 4 Average grain size 0.9577 m, average silver iodide content 8.0%, monodisperse surface S-8 Low silver iodide-containing silver iodobromide emulsion (I'+2) 3503': l I' ll M-1 C-1 M-1 IJ M-2 I S-1 υ S-2 υ CHi=CH5OzCHzOCHzSOtCH=CHz
shizIIS IJ V-1 V-2 zHs F-1 F-2 Su NaO,S CHCOOCsH+t CHiCOOCsH+q C-1 AX-1 AIC~1 υ■ CHtCOOGHz (CFtCh) sHIM-1 Next, the 9th layer of sample 2-1 Instead of yellow colloidal silver,
A multilayer photosensitive material was prepared in the same manner as Sample 2-1 except that comparative dye A was dispersed and added using the dispersion method shown in Example 1, and was designated as Sample 2-2.

In addition, instead of comparative dye A in the 9th layer of sample 2-2,
Samples 2-3 to 2-32 were prepared in the same manner as sample 2-2 except that the compound shown in 2 was used. The amount of dye applied was 3 x 10-' mol/Po.

After wedge exposure of Samples 2-1 to 2-14, the development treatment described below was performed, and the sensitivity of the blue-sensitive emulsion layer and the green-sensitive emulsion layer and the fog of the green-sensitive emulsion layer of each sample were measured.

(For sensitivity, a relative value was used with Sample 2-1 as 100.)
In addition, in order to evaluate the decolorizing property of the dye, 4-amino-3-methyl-N-ethyl-N
-After processing in the same manner except that β-hydroxyethylaniline/sulfate was removed, the difference between each yellow density of sample 2-1-14 and the yellow density of sample 2-1 (ΔD ”5 in)
was measured.

The results are shown in Table-2.

Processing steps (38°C) Color development Bleaching Water Washing Fixation Water loading Washing Stabilization Drying Drying The composition of the processing solution used in each processing step is as follows.

(Color developer) 4-amino-3-methyl-N-ethyl-3 minutes 15 seconds 6 minutes 30 seconds 3 minutes 15 seconds 6 minutes 30 seconds 3 minutes 15 seconds 1 minute 30 seconds Droxyethylaniline・ N-β-hi sulfate anhydrous sodium sulfite Hydroxylamine % sulfate Anhydrous potassium carbonate sodium bromide Nitrilotriacetic acid trisodium salt (monohydrate salt) potassium hydroxide Add water to make 11.

<Bleach solution> Iron ethylenediaminetetraacetate ammonium salt Ethylenediaminetetraacetic acid 2 ammonium salt ammonium bromide glacial acetic acid Add water to make 11, p) Adjust to I = 6.0.

<Fixer> 10.0 g 150.0g 10.0 m using ammonia water 4.75g 4.25g 2.0g 37.5 g 1.3g 2.5g 1.0g 100.0g 175.0 g 8.5g 2.3g pH=6.0 using acetic acid ammonium thiosulfate anhydrous sodium sulfite sodium metasulfite Add water to make 11, Adjust to.

<Stabilizer> Formalin (37% aqueous solution) Konidax (manufactured by Konica Corporation) Add water to make 11.

1.5 m 7.5 d Table 2 (Continued) From the results in Table 2, the samples containing the compound of the present invention exhibit less unnecessary absorption in the green-sensitive region compared to colloidal silver and comparative dyes, so the green It can be seen that the relative sensitivity of the sensitive emulsion layer is higher than that of the sample containing the comparative yellow colloidal silver and the comparative dye compound, and the degree of fog is lower. Furthermore, since it did not diffuse from the additive layer to other layers, it did not reduce the sensitivity of the blue-sensitive emulsion layer, and its decolorizing properties were clearly superior to the comparative dye compounds.

Example 3 Comparative sample 101 of a multilayer color light-sensitive material was prepared by sequentially coating each layer having the following composition on a subbed cellulose triacetate film support from the support side. The coating amount of each component is expressed in g/'nf; however, for silver halide, the coating amount is expressed in terms of silver.

1st layer (Haley silane prevention layer) Black colloidal silver 0.24 Ultraviolet absorber U-10,14 Ultraviolet absorber U -20,072 Ultraviolet absorber U -30,072 Ultraviolet absorber U -40,072 High boiling point solvent 0 -1 0.31 High boiling point melt 0-2 0.098 PolyN vinylpyrrolidone 0.15 Gelatin
2.02 2nd layer (intermediate layer) High boiling point solvent 0-3 0.011 Gelatin 1.17 3rd layer (low sensitivity red-sensitive layer) Spectral sensitized with red sensitizing dyes S-1 and S-2 Silver iodobromide emulsion (silver iodide 3.0 mol%, 0.57 μm) 0.
056 Red Sensitizing Dye S-1. Silver iodobromide emulsion spectrally sensitized with S-2 (3.0 mol% silver iodide, 0.27 μm) 0.
504 Coupler C-10,37 High boiling point solvent 0-2 0.093 PolyN
Vinylpyrrolidone 0.074 gelatin
1.35 Fourth layer (high sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes S-1 and S-2 (silver iodide 3.0 mol%, 0.57 μm) 0 ．．
71 coupler C-10,85 High boiling point solvent 0-2 0.21 PolyN
Vinylpyrrolidone 0.093 gelatin
1.56 5th layer (intermediate layer) Color mixing prevention agent A S -10,20 High boiling point solvent 0-3 0.25 Matting agent M A -10,0091 Gelatin
1.35 6th layer (low sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dyes S-3 and S-4 (silver iodide 3.0 mol%, 0.60 μm) 0 ．．
056 Green Sensitizing Dye S-3. Silver iodobromide emulsion spectrally sensitized with S-4 (3.0 mol% silver iodide, 0.27 μm) 0.
51 Coupler-M-10,31 Coupler M-20,076 High boiling point solvent 0-3 0.059 PolyN vinylpyrrolidone 0.074 Gelatin 1.29 7th layer (high sensitivity green sensitive layer) Green sensitizing dye S -3, Silver iodobromide emulsion spectrally sensitized with S-4 (3.0 mol% silver iodide, 0.60 μm) 0.
83 Green Sensitizing Dye S-3. Silver iodobromide emulsion spectrally sensitized with S-4 (3.0 mol% silver iodide, 0.27 μm) 0.
092 Coupler M-10,80 Coupler M-20,19 Color mixing inhibitor A S-10,055 High boiling point solvent
0-3 0.16 polyN vinylpyrrolidone 0.12 gelatin
1.91 8th layer (middle layer) Gelatin 0.90 9th layer (
Yellow filter layer) Yellow colloidal silver 0.11 Color mixing inhibitor A S-10,068 High boiling point solvent 0-3
'0.085 Matte agent MA-1
0,012 Gelatin 0.68 10th layer (low sensitivity blue sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dyes S-5 and S-6 (silver iodide 3.0 mol%, 0 .85μm) 0.
24 Blue Sensitizing Dye S-5. Silver iodobromide emulsion spectrally sensitized with S-6 (silver iodide 3. (1 mol%, 0.42 μm) 0
．． 30 Blue sensitizing dye S-5. Silver iodobromide emulsion spectrally sensitized with S-6 (3.0 mol% silver iodide, 0.27 μm) 0.
060 coupler Y-10,86 Image stabilizer G -10,012 High boiling point solvent 0-3 0.22 PolyN vinylpyrrolidone 0.078 Compound
F -10,020 Compound F -20,040 Gelatin 1.50 No. 11
Layer (high sensitivity blue sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dyes S-5 and S-6 (silver iodide 3.0 mol%, 0.85 μm) 0.
79 Coupler Y-11,24 Image stabilizer G -10,017 High boiling point solvent 0-3 0.31 PolyN
Vinylpyrrolidone 0. lO compound
F -10,039 Compound F -20,077 Gelatin 1.73 12th layer (protective layer-1) Non-photosensitive fine grain silver iodobromide (silver iodide 1.0 mol%, 0.08 μm) 0.
075 Ultraviolet absorber U-10,048 Ultraviolet absorber U -20,024 Ultraviolet absorber U -30,024 Ultraviolet absorber U -40,024 Ultraviolet absorber U -50,064 Ultraviolet absorber U-60,13 High Boiling point solvent 0-1 0.13 High boiling point solvent 0-2 0.13 Compound
F -10,075 Compound F -20,15 Gelatin 1.2 13th layer (
Protective layer-2) Slip agent WA X-10,041 Matte agent
MA-20,0090 Matte agent MA-30
,051 Surfactant S U -10,0036 Gelatin
0.55 (Note: The average molecular weight of polyN vinyl pyrrolidone used in each layer is 350.00.
It is 0. ) In addition to the above composition, this sample contains:
Gelatin dura side H-1, H-2, H-3, water-soluble dye A
1-1, Al-2, Al-3, antifungal agent DI-1, stabilizer 5T-1, and antifoggant AF-1 were added as appropriate.

The silver halide emulsion used in each photosensitive layer was JP-A-59-1
It was prepared with reference to the method of Example 1 of No. 78447.

All were monodisperse emulsions with a distribution width of 20% or less.

After each emulsion was desalted and washed with water, it was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid, and ammonium thiocyanate. , 7-chitrazaindene, and 1-phenyl-5-mercaptotetrazole were added.

Margin below S-2 coupler> Compound matting agent> A-1 Colloidal silica particles (average particle size 3.5μm) (Average particle size 3.0μm) A CH.

CH3 CH.

High boiling point solvent><Ultravioletabsorber> G2 Ethylhexyl phthalate di-butyl phthalate tricresyl phosphate H -C4H9(t) <Color mixing prevention side> CaHq(t) CJq(t) H S-1 C4Hq(t) ) CHff C1 CJq(t) CaHq(t) C1 (2:;:) <Image stabilizer><Duralside> [(C)! ! =CH5O□CL) 5ccHzs(h
(CHz) zl tN (CHx) tsOJ〈Slip agent〉 AX-1〈Water-soluble dye〉l-1 (Average molecular weight: 30,000) Surface active side〉 5U, K) 38LH! <Stabilizer> T-1 Antifogging side><Moldproofingagent> I-1 Dispersion of comparative dye A shown in Example 2 instead of colloidal silver of Sample 3-1 Sample 3- except that it was added according to the method and amount added.
A multilayer photosensitive material was prepared in the same manner as in Example 1 and designated as Sample 3-2.

Samples were prepared in the same manner using the compounds shown in Table 3 and designated as 3-3 to 3-27, respectively.

Samples 3-1 to 3-27 were exposed to white light through a step wedge for sensitometric measurement, and the following development treatments were performed.

Processing process Processing time Processing temperature First development
6 minutes 38°C water washing 2 minutes
38℃ inversion 2 minutes 3
8°C color development 6 minutes 38°C tone
Bleach at 38°C for 2 minutes.
6 minutes 38℃ fixing 4 minutes 38℃ water washing 4 minutes
Stable at 38°C for 1 minute Dry at room temperature The composition of the treatment liquid used in the above treatment step is as follows.

<First developer> Sodium tetrapolyphosphate 2g Sodium sulfite, 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl-4-methyl-4-hydroxymethyl-3
- Pyrazolidone Potassium bromide Potassium thiocyanate Potassium iodide (0.1% solution) Add water (pH 9,60) <Reverse solution> Nitrilotrimethylenephosphonic acid, hexasodium salt, stannous chloride (dihydrate) P -Add sodium aminophenol hydroxide and ice acetic acid water (pH 5,75) <Color developer> Sodium tetrapolyphosphate Sodium sulfite Sodium tertiary phosphate (dihydrate) Potassium bromide Potassium iodide (0.1% solution ) Sodium hydroxide g 2.5g 1.2g d 100(ld g g 0.1g g 5d 000d g g 6g g 0M1 g Citrazic acid 1.5gN-ethyl-N-β-methanesulfonamidoethyl-3-methyl- Add 4-aminoaniline sulfate 11g2.2-ethylenedithiogetanol 1g water (pH 1
1,70) 1000d <Adjustment solution> Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) g O,4jd Id 000id Add thioglycerin glacial acetic acid water (pH 6,15) <Bleach solution> Sodium ethylenediaminetetraacetate (2 Iron (II) ethylenediaminetetraacetate Ammonium (dihydrate) Add ammonium bromide water (pH 5,65) g 20 g 00g 1000, d <Fixer> Ammonium thiosulfate Sodium sulfite Add sodium bisulfite water (pH 6,60) <Stabilizer> Formalin (37% by weight) Konidax (manufactured by Konica Corporation) 0g g g 000ad d Table (Continued) From the results in Table 3, the compounds of the present invention are suitable for green-sensitive emulsion layers. It can be seen that the relative sensitivity is not adversely affected and the fog is low.

In addition, the decolorizing property was also superior to that of comparative dyes.

〔Effect of the invention〕

As mentioned above, the silver halide photographic light-sensitive material of the present invention contains a substance that functions as a novel dye that has good properties as a photographic dye, particularly excellent decolorization properties, and is free from fogging, desensitization, and residual color. This has the effect of reducing the amount of

Claims (1)

[Scope of Claims] 1. A silver halide photographic material containing at least one solid fine particle dispersion of a compound represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 represents an aryl group or an aromatic heterocyclic group, and R^2 represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, Represents a cycloalkyl group, an alkynyl group, or a heterocyclic group. R^3 represents an electron-withdrawing group, L_1 to L_3 represent a methine group, and X and Y represent an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom, provided that X and Y are both oxygen atoms. There isn't. m represents zero or an integer of 1 to 3. 2. In the general formula [I], R^1, R^2, R^3
2. The silver halide photographic material according to claim 1, wherein at least one of the silver halide photosensitive materials has at least one of a sulfonamide group, a sulfamoyl group, and a carboxyl group.