JPH11193352A - Silver halide photographic material, method for treating same, compound useful for same, and solid microdispersion thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photographic material having reduced fogging, high sensitivity and improved long-term stability by forming on a support a photosensitive hydrophilic colloid layer containing a specified solid microdispersion compound and a non-photosensitive hydrophilic colloid layer. SOLUTION: A photosensitive hydrophilic colloid layer and a non- photosensitive hydrophilic layer are formed on a support to obtain a photographic material, wherein at least either of the layers contains ]-1,000 mg, desirably, 3-500 mg, per m<2> of the material, of solid microemulsion compound of any one of formulas I to IV (wherein A is an acid nucleus residue; L1 and L3 are each methine; n is 0, 1, or 2; Z is a group of nonmetallic atoms necessary to form a heterocyclic residue when combined with the N in the formula; Y is a heterocylic residue; R and R1 to R3 are each H or an alkyl; EWG is an electron-attracting substituent having a Hammet substituent constant σp of 0.3 or above, and when the nitrogen-containing heterocyclic ring formed when Z is bonded to the N is an indole ring, R1 and R2 are each an alkyl).

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 material having a dyed hydrophilic colloid layer (hereinafter also simply referred to as a "photosensitive material"). The present invention relates to a novel non-diffusible dye which is low in sensitivity and does not cause a decrease in sensitivity, and a silver halide photographic material containing the same.

[0002]

2. Description of the Related Art In recent years, demands for improving performance of silver halide photographic materials have become increasingly severe, and higher levels of demands have been made for high image quality characteristics such as excellent sharpness and color reproducibility.

In recent years, in order to counter the immediate nature of competing electrophotographic materials, further reduction in processing time, that is, ultra-rapid processing suitability has been required. In order to realize the high image quality characteristics and ultra-rapid processing characteristics required for such photographic materials, the industry has made efforts to further reduce the thickness of the photographic materials and to optimize silver halide and additives. Have been.

In general, it is well known that a dye is contained in a silver halide photographic light-sensitive material for the purpose of improving image quality and adjusting the sensitivity of a light-sensitive emulsion. Used in light absorption filters. Recently, dyes for replacing yellow colloidal silver in color photographic materials (hereinafter referred to as YC dyes), dyes for crossover cut layers in X-ray photographic materials, non-photosensitive materials in printed photographic materials, The use of dyes for dyeing emulsion layers is widespread.

[0005] Dyes used for such purposes not only have good absorption spectrum characteristics according to the purpose of use, but also, for example, are completely decolorized during development processing and easily eluted from the photosensitive material during development processing. After processing, no residual color contamination due to the dye occurs, no adverse effects such as fogging and desensitization on other photosensitive emulsions, and no diffusion from the colored layer to other layers. ,
Further, it must be excellent in stability over time in a photographic material or an emulsion coating solution and satisfy various conditions such as not causing discoloration.

Numerous dyes have been proposed for the purpose of satisfying these conditions. For example, azo dyes, British Patent No. 506,385, and JP-B-39 can be used.
U.S. Pat. No. 2,220,692 discloses oxonol dyes.
No. 493,747 discloses merocyanine dyes,
No. 5,404 proposes styryl dyes and the like.

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. However, when the dyes are water-soluble, they remain in the layer to be dyed. However, there is a problem that the metal is diffused to all layers without using the same. Therefore, in order to achieve the original purpose, it is necessary to add a large amount of dye to the extent that the dye diffuses to the other layer, and undesired phenomena such as a decrease in sensitivity, gradation variation, and fog abnormality are caused in both the own layer and the other layer. It was clear that it would appear. Especially,
When a photographic light-sensitive material is stored over time, fogging and desensitization are remarkable, and if the amount used is reduced to avoid these, the original light absorption effect cannot be sufficiently obtained. In order to solve such a problem, a dye having a low diffusibility for dyeing a specific layer is known. For example, US Pat. Nos. 2,538,008 and 2,538,
009, 4,420,555, 4,940,6
No. 54, JP-A-61-204630, and JP-A-61-204630.
1-205934, 62-32460, 62-
No. 56958, No. 62-92949, No. 62-222
No. 248, No. 63-40143, No. 63-18474
No. 9, 63-316852, JP-A-1-179904
No. 2, No. 3-75632, No. 3-109535, No. 3-144438, No. 3-179441, No. 4-3
No. 62634, No. 5-53241, No. 5-86056
Nos. 5,209,133, 5-289239, 5-296848 describe oil-soluble disperse dyes.

Further, a method of making a dye resistant to diffusion using solid fine particles of a dye insoluble in water is disclosed in WO 88 / 4,794.
No. 4,904,565, U.S. Pat.
No. 788, JP-A-63-197943 and JP-A-64-40.
No. 827, JP-A-1-155341 and 1-1728.
No. 28, No. 2-1839, No. 2-110453, No. 3-23341, No. 3-206443, No. 3-21
No. 6644, No. 3-216645, No. 3-21664
No. 6, No. 3-217838, No. 3-231241,
4-37740, 4-37841, 4-44
No. 033, No. 4-116548, No. 4-296848
Nos. 5,197,079 and 6,110,155.

However, these compounds are insufficient in the decoloring property in the processing step and have the disadvantage of leaving color stain after the processing, speeding up the processing, improving the composition of the processing solution, or improving the photographic emulsion composition. If there are changes in various factors such as improvement of the color, the decolorization and diffusion resistance are not sufficient, and it diffuses to other layers during storage and adversely affects photographic performance such as sensitivity and fog. I was

[0010]

Accordingly, an object of the present invention is to provide a dye which has been made resistant to diffusion, which satisfies the above requirements,
An object of the present invention is to provide a silver halide photographic light-sensitive material which is less sensitive to fog, has high sensitivity, and has improved stability over time.

[0011]

The above objects of the present invention have been attained by the following constitutions.

1) Solid fine particles having a photosensitive hydrophilic colloid layer and a non-photosensitive hydrophilic colloid layer on a support, and at least one layer represented by any of the following formulas (1) to (4) A silver halide photographic light-sensitive material comprising at least one kind of dispersed compound.

[0013]

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(In the above general formula (1) or (2), A represents an acidic nucleus residue, L ₁ , L ₂ and L ₃ represent a methine group, n represents 0, 1 or 2, and Z represents (N represents a group of nonmetal atoms necessary for forming a heterocyclic residue by bonding to the nitrogen atom shown in the formula, Y represents a heterocyclic residue, and R represents a hydrogen atom or an alkyl group.)

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(In the above general formula (3) or (4), A represents an acidic nucleus residue, L ₁ , L ₂ and L ₃ represent a methine group, n represents 0, 1, or 2; Represents a group of nonmetallic atoms necessary to form a heterocyclic residue by bonding to the nitrogen atom shown in the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom or an alkyl group, and EWG represents Hammett. Represents an electron-withdrawing substituent having a substituent constant σp of 0.3 or more.
However, when the nitrogen-containing heterocyclic ring formed by combining Z with a nitrogen atom is an indole ring, R ₁ and R ₂ represent an alkyl group. 2) The silver halide photograph as described in 1 above, wherein the solid fine particle-dispersed compound represented by any one of the general formulas (1) to (4) is contained in a non-photosensitive hydrophilic colloid layer. Photosensitive material.

(3) The silver halide photographic material as described in (1) or (2) above, wherein the compound represented by any one of formulas (1) to (4) has at least one carboxyl group in its molecular structure.

(4) The silver halide photographic material as described in (1), (2) or (3) above, wherein A in the general formulas (1) to (4) is a residue of 2-pyrazolin-5-one.

(5) The silver halide photographic light-sensitive material as described in (1), (2), (3) or (4) above, wherein n in formulas (1) to (4) is 0.

(6) The silver halide photographic material as described in (1), (2), (3), (4) or (5) above, wherein in formula (1) or (2), Y is a cyclic sulfone, a cyclic sulfoxide or a lactone.

7) The particles of the solid fine particles of the compound represented by the above general formulas (1) to (4) have a particle size of 0.3 to 0.3.
The above 1, 2, 3, characterized in that it is 0.01 μm.
4. The silver halide photographic light-sensitive material according to 4 or 5.

(8) The above (1), (2) or (2), which comprises at least one type of 2-equivalent magenta color coupler.
3. The silver halide photographic material as described in 3, 4, 5, 6 or 7.

9) The silver halide photographic light-sensitive material described in 1, 2, 3, 4, 5, 6, 7, or 8 is subjected to color development within 200 seconds. Material treatment method.

10) The above 1, 2, 3, 4, 5, 6, 7
Or a method for processing a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material is subjected to color development processing within 120 seconds.

11) A solid fine particle dispersion of the compound represented by any of formulas (1) to (4).

12) A compound represented by the above general formula (1).

13) A compound represented by the above general formula (2).

14) A compound represented by the above general formula (3).

15) A compound represented by the above general formula (4).

Hereinafter, the present invention will be described more specifically.

The acidic nucleus represented by A in the general formulas (1) to (4) is preferably 2-pyrazolin-5-one,
Examples include barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolone, isoxazolone, indandione, hydroxypyridone, pyrazolopyridone and the like, and preferably 2-pyrazolin-5-one.

Further, L ₁ and L _{2 in} the general formulas (1) to (4)
And the methine group represented by L ₃ include those having a substituent, such as an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a hexyl group, etc.), an aryl group ( For example, phenyl group, tolyl group, 4-
Hydroxyphenyl group, etc., aralkyl group (eg, benzyl group, phenethyl group, etc.), heterocyclic group (eg, pyridyl group, furyl group, thienyl group, etc.), substituted amino group (eg, dimethylamino group, diethylamino group, anilino group, etc.) An alkylthio group (eg, methylthio group), an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, 2-hydroxyethoxycarbonyl group, etc.), a carbamoyl group (eg, carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, 2-hydroxyethylcarbamoyl) Group, dimethylcarbamoyl group, 4
-Carboxyphenylcarbamoyl group).

In the general formulas (1) to (4), examples of the heterocyclic ring formed by Z together with a nitrogen atom include pyrrole, pyrazole, imidazole, triazole and tetrazole. The heterocycle may be condensed with a benzene ring, and examples of such a heterocycle include indole, indazole, benzimidazole, and benztriazole. The heterocyclic ring may be substituted by a monovalent organic group such as an alkyl group, an aryl group, an acyl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, and a cyano group.

Examples of the heterocycle represented by Y in the general formula (1) or (2) include lactones (for example, γ-butyrolactone, γ-valerolactone, δ-valerolactone,
Coumarin, isocoumarin), lactam (eg, 4-butanelactam, 6-hexanelactam), cyclic sulfone (eg, tetrahydrothiophen-1,1-dioxide), cyclic sulfoxide (eg, tetramethylene sulfoxide), nitrogen-containing heterocycle (eg, morpholine) , Pyrazine, pyridine, pyrazole, pyrazoline, imidazolidine, isoindole), preferably sulfone, cyclic sulfone, and cyclic sulfoxide.

R in the general formula (2) and R ₁ , R ₂ and R ₃ in the general formula (3) or (4) are a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, Examples include a propyl group, a butyl group, a pentyl group, and an octyl group, and a methyl group and an ethyl group are preferable.

In Formulas (3) and (4), the electron-withdrawing group represented by EWG is represented by a σp value of a substituent constant Hammett (edited by Toshio Fujita, “Structural-Activity Relationship of Drugs, No. 122,“ Chemical Region Special Issue No. 122 ”), 96 to 103 (1979) Nankodo, etc.) are groups of 0.3 or more, for example, a cyano group, a trifluoromethyl group, an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group). Group, octyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenoxycarbonyl group, 4-hydroxyphenoxycarbonyl group), carbamoyl group (for example, carbamoyl group,
A methylcarbamoyl group, an ethylcarbamoyl group, a butylcarbamoyl group, a dimethylcarbamoyl group, a phenylcarbamoyl group, a 4-carboxyphenylcarbamoyl group, an acyl group (for example, a methylcarbonyl group, an ethylcarbonyl group, a butylcarbonyl group, a phenylcarbonyl group, -Ethylsulfonamidophenylcarbonyl group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, octylsulfonyl group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, etc.), etc. And preferably an alkoxycarbonyl group, an alkylsulfonamide group, a trifluoromethyl group, a cyano group and the like.

Specific examples of the compound of the present invention and the 2-equivalent magenta color coupler described in the above item 8 are shown below, but the present invention is not limited to these.

[0038]

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[0039]

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[0042]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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The compounds used in the present invention are described, for example, in JP-A-52-92716, JP-A-55-120030, and JP-A-5-120030.
5-155350, 55-155351, 56
-12639, 63-197943, JP-A-2-
No. 1838, No. 2-1839, world patent 88/04
No. 794, U.S. Pat.
No. 0,586, EP 489,973 and the like. A specific synthesis example is shown below.

Synthesis Example 1

[0060]

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(1) Dissolve 6.88 g of ethyl α-bromoisobutyrate and 2.50 g of indole-3-aldehyde in 20 ml of N, N-dimethylformamide, add 3.80 g of potassium carbonate and heat to 70 ° C. Stirred. 3
After continuing stirring for an hour, the mixture was allowed to cool, the reaction mixture was poured into water, and organic matter was extracted with ethyl acetate. The separated organic layer was washed with water, dried over magnesium sulfate, concentrated, and then generated by column chromatography to obtain 3.66 g of Intermediate 1 as a light brown oily substance. The structure of the product was confirmed by NMR spectrum, IR spectrum and mass spectrum.

(2) 3.5 g of Intermediate 1 and 2.7 g of 1- (4-carboxyphenyl) -3-amino-2-pyrazolin-5-one were dissolved in 30 ml of N, N-dimethylformamide. Was heated to 90 ° C. and stirred. After continuing the reaction for 3 hours, the mixture was allowed to cool, and the insoluble material was filtered off to remove a small amount of N, N
-Washed with dimethylformamide. 200 m of water in the filtrate
The precipitated crystals were collected by filtration to obtain 3.3 g of Exemplified Compound 1. The structure of the product is NMR spectrum, IR
Confirmed by spectrum and mass spectrum.

Synthesis Example 2

[0064]

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(1) 5.92 g of indole-3-aldehyde and 12.1 g of sulfolene were dissolved in 50 ml of N, N-dimethylformamide, and 6.92 of potassium carbonate was dissolved.
g was added and heated to 80 ° C. with stirring. After the reaction was continued for 8 hours, the mixture was allowed to cool, and the reaction mixture was poured into water and stirred. The precipitated solid was collected by filtration, washed with stirring while heating in methanol, and 6.8 g of Intermediate 2 yellow crystals were obtained. The structure of the product was confirmed by NMR spectrum, IR spectrum and mass spectrum.

(2) 5.80 g of intermediate 2 and 1- (4-carboxyphenyl) -3-amino-2-pyrazoline-5 in 150 ml of N, N-dimethylformamide
6.42 g of ON was dissolved and heated to 80 ° C. with stirring.
After continuing the reaction for 4 hours, the insolubles were filtered off, and the filtrate was washed with water 5
00 ml was poured, and the precipitated crystals were collected by filtration. 6.0 g of an orange-yellow crystal of Exemplified Compound 2 was obtained. The structure of the product is NMR
Confirmed by spectrum, IR spectrum and mass spectrum.

The compound according to the present invention can be dissolved in an appropriate organic solvent and added to the hydrophilic colloid solution, but a desirable method is to add it as a solid fine particle dispersion. As a method for producing a solid fine particle dispersion, JP-A-52-92716 and JP-A-55-15553 are known.
No. 50, No. 55-155351, No. 63-19794
No. 3, JP-A-3-182743, world patent WO88 /
No. 04794, etc. can be used. Specifically, using a surfactant, for example, ball mill, vibration mill, planetary mill, sand mill, roller mill,
It can be prepared using a fine dispersing machine such as a jet mill or a disk impeller mill. Further, after dissolving the compound in a weakly alkaline aqueous solution, a method of precipitating fine solid particles by lowering the pH to weakly acidic or a weakly alkaline solution of the compound and an acidic aqueous solution are simultaneously mixed while adjusting the pH. A dispersion of the compound can be obtained by a method for producing a particulate solid. The compounds may be used alone or as a mixture of two or more. 2
When a mixture of more than one species is used, they may be dispersed separately and then mixed, or they may be dispersed simultaneously.

The compound dispersed in the form of solid fine particles according to the present invention is preferably dispersed such that the average particle diameter is 1 μm or less, more preferably 0.01 μm to 0.1 μm.
3 μm, particularly preferably 0.10 μm to 0.25
μm. The dispersion coefficient of the particle size distribution is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. Here, the variation coefficient of the particle size distribution is a value represented by the following equation.

(Standard deviation of particle size) / (Average value of particle size) × 100 A surfactant may be used when producing a solid particulate dispersion of the compound, and the surfactant may be an anion. Any of amphoteric surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used. Preferably, for example, alkyl sulfonates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates Anionic surfactants such as esters, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, N-acyl-N-alkyltaurines and, for example, saponins, alkylene oxide derivatives, alkyl esters of sugars, etc. It is a nonionic surfactant.

The surfactant may be added at any position before, during or after dispersion, but is preferably added before the start of dispersion of the compound. If necessary, it may be further added to the compound dispersion after the dispersion is completed. These anionic surfactants and / or nonionic surfactants may be used alone, respectively, or two or more kinds may be used in combination, or both may be used in combination. . The amount of the anionic surfactant and / or the nonionic surfactant used varies depending on the kind of the activator or the conditions of the dispersion of the compound, but is usually 0.1 to 2 per gram of the compound.
000 mg, preferably 0.5 to 1000 mg, more preferably 1 to 500 mg. The concentration of the compound in the dispersion is 0.01 to 10% by weight, preferably 0.1 to 5% by weight.

Before the start of dispersion or after the end of dispersion, a hydrophilic colloid used as a binder for a photographic component layer can be added to the compound dispersion of the present invention. As the hydrophilic colloid, it is advantageous to use gelatin,
In addition, for example, phenylcarbamylated gelatin, acylated gelatin, gelatin derivatives such as phthalated gelatin,
Graft polymer of gelatin with a monomer having a polymerizable ethylene group, cellulose derivatives such as carboxymethylcellulose, hydroxymethylcellulose, cellulose sulfate, polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N-dimethylacrylamide And synthetic hydrophilic polymers such as poly-N-vinylpyrrolidone and polymethacrylic acid, agar, gum arabic, alginic acid, albumin, casein and the like. These may be used in combination of two or more.

The dispersion of the compound of the present invention may be used in the light-sensitive emulsion layer among the layers constituting the photographic light-sensitive material, such as the upper layer of the emulsion layer, the lower layer of the emulsion layer, the protective layer, the undercoat layer of the support and the backing layer. It can also be used for a photosensitive hydrophilic colloid layer. The preferred use amount of the compound is not uniform depending on the type of the compound, the characteristics of the photographic light-sensitive material, and the like, but is used in the photographic light-sensitive material so that the optical density is 0.05 to 3.0 depending on the purpose. photographic light-sensitive material 1m ² per 1mg~1000m
g, more preferably 3 mg to 500 mg,
Particularly preferably, it is 5 mg to 100 mg.

In the photographic light-sensitive material of the present invention, the solid fine particle dispersion of the compound may be contained in at least one photosensitive hydrophilic colloid layer or non-photosensitive hydrophilic colloid layer. Gelatin is preferred as the hydrophilic colloid,
The coating amount is preferably 0.01 g / m ^2-
2.0 g / m ² , more preferably 0.1 g / m ² to
1.7 g / m ² , particularly preferably 0.2 g / m ^2-
1.4 g / m ² .

The gelatin used in the photographic light-sensitive material of the present invention is generally produced from cow bone, cow skin, pig skin, etc., and in the production process from collagen, alkali-processed gelatin accompanied by treatment with lime or the like, hydrochloric acid, etc. There is an acid-processed gelatin accompanied by the above-mentioned treatment, and any gelatin used in the present invention may be used. For details of the production methods and properties of these gelatins, see, for example, Arthur V.
eis, "The Macromolecular C
hemistry of Gelatin ", 187-
217 (1964) (Academic Pres)
s), T.I. H. James "The Theory"
of the photographicProces
s "4th. ed, p. 55 (1977) (Macmil)
lan), "Niwa and Gelatin", published by Nippon Niwa Gelatin Industrial Association (1987), "Basics of Photographic Engineering, Silver Salt Photography", pp. 119-124 (Corona). The jelly strength of gelatin (based on the PAGI method) is preferably at least 250 g. The calcium content (according to the PAGI method) of the gelatin of the present invention is preferably 400
It is 0 ppm or less, particularly preferably 3000 ppm or less.

Further, gelatin is hardened by a hardener, and the swelling ratio and film strength of the coated film can be adjusted by the amount of the hardener in the photographic light-sensitive material. Examples of the hardening agent include aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), mucohalogenic acids (mucochloric acid, mucophenoxycyclolic acid, etc.), epoxy compounds, active halogen compounds (2,4-dichloro-6-hydroxy-s). -Triazine, etc.), active vinyl derivatives (1,3,5-triacryloylhexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis (β- (vinylsulfonyl (propionamide)
Organic hardeners such as ethyleneimines, carbodiimides, methanesulfonic acid esters, and isoxazoles; inorganic hardeners such as chrome alum; US Patent No. 3,05
7,723, 3,396,029, 4,16
Polymer hardeners described in 1,407 and the like can be used, and they are used alone or in combination. In the photographic light-sensitive material of the present invention, the swelling ratio of the coating film during the development processing is preferably 150 to 250%, and the film thickness after expansion is 70 μm.
m or less is preferable. The swelling ratio is obtained by calculating the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, dividing the difference by the film thickness before processing and multiplying by 100.
If it exceeds 0%, poor drying occurs, and if the swelling ratio is less than 150%, development unevenness and residual color tend to deteriorate during development.

Another silver halide emulsion used in the present invention is Research Disclosure (referred to as RD).
308119 can be used.

The places to be described are shown below.

Item RD308119 Iodine texture Item 993IA-A Manufacturing method Item 993IA-A and 994E Crystal habit Normal crystal 994E Crystal habit Twin crystal 994E Epitaxial 994E Halogen composition Uniform 993IB-halogen composition 1 No difference 993I-B Halogen conversion 994I-C Halogen substitution 994I-C Metal-containing 999I-D Monodispersion 999I-F Solvent addition 999IF-F Latent image forming position Surface 995I-G Latent image forming position Inner surface Item 995I-G Applicable light-sensitive material Negative 995I-H Applicable light-sensitive material Positive (including internal fog particles) Item 995I-H Emulsion is mixed and used 995I-J Item Desalting 995II-A In the present invention, a silver halide emulsion is used. An emulsion subjected to physical ripening, chemical ripening according to the present invention, and spectral sensitization is used. RD1764 is an additive used in such a process.
3, 18716 and 308119.
The places to be described are shown below.

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[Table 1]

Various couplers can be used in the present invention, and specific examples are described in the above RD. The relevant sections are described below.

[0081]

[Table 2]

The photographic light-sensitive material of the present invention may have at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer on one surface of a support. The support may have the emulsion layer and the colloid layer on both surfaces. Examples of photographic materials include color negative photographic materials, color reversal photographic materials, color photographic paper photographic materials, medical X-ray photographic materials, printing plate making photographic materials, direct positive photographic materials, and heat developing photographic materials. And photographic materials for diffusion transfer type color.

In the silver halide photographic light-sensitive material of the present invention, various techniques and additives known in the art can be used, if necessary. For example, in addition to a photosensitive silver halide emulsion layer, a protective layer, an intermediate layer, a filter layer, an antihalation layer,
A photographic component layer such as a crossover light cut layer and a backing layer can be provided. In these layers, a supersensitizer, a coupler, a high boiling solvent, an antifoggant, a stabilizer, a development inhibitor, a bleach Accelerators, fixing accelerators, color mixture inhibitors, formalin scavengers, color tones, hardeners, surfactants,
A thickener, a plasticizer, a sliding agent, an ultraviolet absorber, a polymer latex, an antistatic agent, a matting agent, etc. are added to RD30811.
It can be contained by various methods such as the dispersion method described in 9XIV.

The support which can be used in the silver halide photographic light-sensitive material of the present invention includes polyesters such as cellulose triacetate, cellulose nitrate, polyethylene naphthalate and polyethylene terephthalate, polyolefins such as polyethylene, polystyrene and baryta paper. ,
Paper, glass, metal, or the like on which polyethylene or the like is laminated can also be used. The surface of these supports may be provided with a subbing layer to improve the adhesion of the coating layer, corona discharge,
Underlay processing is performed as necessary, such as irradiation with ultraviolet rays.

The light-sensitive material of the present invention includes, for example, the type and serial number of the photographic light-sensitive material, the name of the manufacturer, the emulsion No. Various information on photographic photosensitive materials such as shooting date / time, aperture, exposure time, lighting conditions, filters used, weather, shooting frame size, shooting machine model, use of anamorphic lens, etc. Various information required when printing, such as the number of prints, selection of filters, customer's color preference, size of trimming frame, etc., required for printing, such as the number of prints, selection of filters, customer's color A magnetic recording layer may be provided in order to input various information obtained at the time of printing, such as the preference of the user, the size of the trimming frame, and other customer information.

In the present invention, the magnetic recording layer is preferably applied to the support on the side opposite to the photographic component layer, and the undercoat layer, the antistatic layer (conductive layer), It is preferable that a magnetic recording layer and a slip layer are formed.

The light-sensitive material of the present invention can be processed by a known method. For example, any of various methods and various processing solutions described in RD17643 can be used.

[0088]

EXAMPLES The present invention will be described below with reference to examples, but embodiments of the present invention are not limited to the examples.

Example 1 A multilayer color photographic light-sensitive material sample 101 was prepared by sequentially forming layers having the following compositions from the support side on a triacetyl cellulose film support provided with an undercoat layer.

The amount of addition indicates the number of grams per 1 m ² unless otherwise specified. Silver halide and colloidal silver were expressed in terms of silver, and sensitizing dyes were expressed in moles per mole of silver.

First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling organic solvent (Oil-1) 0.12 Gelatin 1.53 Second layer: Intermediate layer Antifouling agent (SC-1) 0.06 High-boiling organic solvent (Oil-2) 0.08 Gelatin 0.80 Third layer: Low-sensitivity red-sensitive layer Silver iodobromide emulsion (average particle size 0.38 μm, iodine Silver iodide content (average grain size: 0.27 μm, silver iodide content: 2.0 mol%) 0.15 Sensitizing dye (SD-1) 8 × 10 ^-4 sensitizing dye (SD-2) 1.9 × 10 ^-4 sensitizing dye (SD-3) 1.9 × 10 ^-4 sensitizing dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.56 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.025 High boiling point solvent (Oil-1) 0.49 Gelatin 1.14 Fourth layer: middle-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size: 0.52 μm, silver iodide content: 8.0 mol%) 89 silver iodobromide emulsion (average grain size: 0.38 μm, silver iodide content: 8.0 mol%) 0.22 sensitizing dye (SD-1) 2.3 × 10 ^-4 sensitizing dye (SD-2) 1.2 × 10 ^-4 sensitizing dye (SD-3) 1.6 × 10 ^-4 cyan coupler (C-1) 0.45 colored cyan coupler (CC-1) 0.038 DIR compound (D-1) 0.017 High boiling point solvent (Oil-1) 0.39 Gelatin 1.01 Fifth layer: Highly sensitive red-sensitive layer Silver iodobromide emulsion (average grain size: 1.00 μm, silver iodide content: 8.0 mol) %) 1.27 sensitizing dye (SD-1) 1.3 × 10 -4 sensitizing dye (SD-2) 1.3 × 10 -4 sensitizing dye (SD-3) 1. × 10 ^-4 Cyan coupler (C-2) 0.20 Colored cyan coupler (CC-1) 0.034 DIR compound (D-3) 0.001 High boiling solvent (Oil-1) 0.57 Gelatin 1.10 6th layer: intermediate layer Color stain inhibitor (SC-1) 0.075 High boiling organic solvent (Oil-2) 0.095 gelatin 1.00 7th layer: intermediate layer gelatin 0.45 8th layer: low sensitivity Green-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.64 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2. 0.21 Sensitizing dye (SD-4) 7.4 × 10 ^-4 Sensitizing dye (SD-5) 6.6 × 10 ^-4 Magenta coupler (C-3) 0.20 Magenta coupler ( C-4) 0.48 Colored magenta coupler (CM-1) 0.12 High boiling point solution (Oil-2) 0.81 Gelatin 1.89 Ninth layer: Medium-sensitive green-sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.76 sensitization Dye (SD-6) 1.5 × 10 ^-4 sensitizing dye (SD-7) 1.6 × 10 ^-4 sensitizing dye (SD-8) 1.5 × 10 ^-4 magenta coupler (C-3) 0.043 Magenta coupler (C-4) 0.1 Colored magenta coupler (CM-2) 0.039 DIR compound (D-2) 0.021 DIR compound (D-3) 0.002 High boiling solvent (Oil- 2) 0.37 gelatin 0.76 10th layer: high-sensitivity green-sensitive layer Silver iodobromide emulsion (average grain size: 1.00 μm, silver iodide content: 8.0 mol%) 1.46 sensitizing dye (SD -6) 0.93 × 10 ^-4 sensitizing dye (SD-7) 0.97 × 10 -4 sensitizing dye (SD-8) 0.9 × 10 ^-4 Magenta coupler (C-3) 0.085 Magenta coupler (C-4) 0.128 Colored magenta coupler (CM-1) 0.014 High boiling solvent (Oil-1) 0.15 High boiling solvent ( Oil-2) 0.42 gelatin 1.08 11th layer: yellow filter layer yellow colloidal silver 0.07 color stain inhibitor (SC-1) 0.18 formalin scavenger (HS-1) 0.14 high boiling point solvent ( Oil-2) 0.21 gelatin 0.73 12th layer: intermediate layer Formalin scavenger (HS-1) 0.18 gelatin 0.60 13th layer: low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0 0.059 μm, silver iodide content: 8.0 mol%) 0.073 silver iodobromide emulsion (average grain size: 0.38 μm, silver iodide content: 3.0 mol%) 0.16 silver iodobromide emulsion ( Average grain 0.27 [mu] m, silver iodide content 2.0 mol%) 0.20 Sensitizing dye (SD-9) 2.1 × 10 -4 Sensitizing dye (SD-10) 2.8 × 10 -4 Yellow coupler (C-5) 0.89 DIR compound (D-4) 0.008 High boiling solvent (Oil-2) 0.37 Gelatin 1.51 14th layer: Highly sensitive blue-sensitive layer Silver iodobromide emulsion (average grain Diameter 1.00 μm, silver iodide content 8.0 mol%) 0.95 Sensitizing dye (SD-9) 7.3 × 10 ^-4 Sensitizing dye (SD-10) 2.8 × 10 ^-4 yellow Coupler (C-5) 0.16 High boiling point solvent (Oil-2) 0.093 Gelatin 0.80 15th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.05 μm, silver iodide content 3.00 mol%) 0.30 UV absorber (UV-1) 0.094 UV absorber (UV-2) 0.10 Formalin ska Janger (HS-1) 0.38 High boiling point solvent (Oil-1) 0.10 Gelatin 1.44 Sixteenth layer: Second protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethyl methacrylate (average) 0.04 Slip agent (WAX-1) 0.02 Gelatin 0.55 In addition to the above composition, a coating aid SU-1, a dispersion aid SU-2, a viscosity adjuster, and a stabilizer Agent ST-1, Dye AI-
1, AI-2, antifoggant AF-1, weight average molecular weight: 10,000 and weight average molecular weight: 100,000
Of polyvinylpyrrolidone (AF-2), preservative DI-1 and hardener. The amount of DI-1 added was 9.4 mg / m ² .

The structure of the compound used in the sample is shown below.

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[0094]

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[0097]

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[0098]

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[0099]

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Further, solid fine particle dispersions of the compounds shown in Table 3 were added to the eleventh layer of the sample 101 in place of the yellow colloidal silver, to prepare samples 102 to 115. The solid fine particle dispersion was prepared according to the method described below, and the amount of addition was an amount showing the same absorbance as the yellow colloidal silver added to Sample 101.

(Preparation Method of Solid Fine Particle Dispersion) A solid fine particle dispersion of a dye was prepared according to the method described in World Patent No. 88/04794. That is, 21.7 ml of water and surfactant T were placed in a 60 ml screw cap container.
2.65 g of a 6.7% solution of riton X-200 (manufactured by Rohm & Haas) were added, and 1.0 g of the powdered dye in a mortar was added to this solution, and 40 ml of zirconium oxide beads (2 mm diameter) was added. did. Close the cap, place on a ball mill, disperse at room temperature for 4 days,
8.0 g of a 12.5% gelatin aqueous solution was added and mixed well, and zirconium oxide beads were removed by filtration to obtain a solid fine particle dispersion of a dye.

The sample prepared as described above was used as a fresh sample, subjected to wedge exposure with white light, and subjected to the following color development treatment to evaluate the effect of the dye on the sensitivity SG of the green photosensitive layer. did. The sensitivity was represented by the reciprocal of the exposure amount giving a density of fog + 0.3. Also measure the minimum yellow density of the samples were compared as the fog D _B of blue-sensitive layer.

A sample prepared in the same manner as the above-mentioned fresh sample was stored at a temperature of 50 ° C. and a relative humidity of 80% for 3 days, and then exposed and color-developed in the same manner as the fresh sample. The decrease in sensitivity of the blue-sensitive layer due to the above was indicated by ΔSB and compared. Here, ΔSB is a value defined below.

ΔSB = (blue-sensitive layer sensitivity of stored sample) /
(Sensitivity of blue-sensitive layer of fresh sample) × 100 The color development was performed in the following manner.

(Processing step) Process Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2. 0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 60 seconds 55 ± 5.0 ° C.-* The replenishing amount is a value per 1 m ² of the photosensitive material.

The composition of the color developing solution is shown below.

<Preparation of Processing Agent> (Composition of Color Developer) Water 800 ml Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Make up to liters and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

(Composition of color developing replenisher) Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl -N- (β-hydroxyethyl) aniline sulfate 6.3 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 2.0 g Water was added to make up to 1.0 liter, and the pH was adjusted to 10 using potassium hydroxide or 20% sulfuric acid. Adjust to 18.

(Composition of bleaching solution) Water 700 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Adjust to pH 4.4 with water or glacial acetic acid.

(Composition of bleaching replenisher) Water 700 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g Adjust to pH 4.4 using aqueous ammonia or glacial acetic acid.

(Formulation of Fixing Solution) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Add water to make up to 1.0 liter, and adjust to pH 6.2 using aqueous ammonia or glacial acetic acid.

(Formulation of Fixing Replenisher) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Add water to make up to 1.0 liter, and adjust to pH 6.5 using aqueous ammonia or glacial acetic acid. .

(Preparation of Stabilizing Solution and Stabilizing Replenishing Solution) Water 900 ml p-octylphenol / ethylene oxide / 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml Add water to make up to 1.0 liter, and adjust the pH to 8.5 using ammonia water or 50% sulfuric acid.

The results of the evaluation are shown in Table 3 below.

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[Table 3]

As is evident from the results shown in Table 3, the dye dispersion of the present invention in place of the yellow colloidal silver contained:
It can be seen that the fog of the blue-sensitive layer and the undesirable fluctuation of the sensitivity of the blue-sensitive layer during storage of the photosensitive material are improved as compared with conventionally known dyes.

It can also be seen that the light-sensitive material using the dye dispersion of the present invention has high green sensitivity. This indicates that the decrease in green sensitivity caused by yellow colloidal silver absorbing light on the longer wavelength side than the blue light region is improved.

Example 2 In addition, magenta contained in the eighth, ninth, and tenth layers of the sample 101 (low-sensitive green photosensitive layer, medium-sensitive green photosensitive layer, and high-sensitive green photosensitive layer, respectively) Samples 201 to 201 in which the color-forming coupler was changed to the magenta color-forming coupler shown in the compound examples
215 were prepared, and the sensitivity of the green photosensitive layer, the change in the sensitivity of the blue photosensitive layer over time, and the fog of the blue photosensitive layer were evaluated in the same manner as described above. The results are shown in Table 4 below.

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[Table 4]

As is evident from the results shown in Table 4, it was found that the effect of the compound of the present invention was further improved by using a 2-equivalent magenta color coupler in combination.

Example 3 A solid fine particle dispersion of a dye was prepared according to the method of Example 1 except that the dispersion time was changed, and the average particle size of each of these fine particle dispersions was determined using a Malvern Instrument (Malvern Instrument). (Instrument) 4700. Further, the prepared fine dye particle dispersion was mixed with an aqueous gelatin solution, and this was coated on a triacetylcellulose film support provided with an undercoat layer to prepare samples 302 to 3 containing 0.3 g of dye per m ^2.
20 were produced.

Samples 302 to 320 were immersed in a color developing solution having the same composition as that used in Example 1 at a liquid temperature of 37 ° C. for 1 minute, and the visible spectrum of each sample was measured before and after immersion. Then, the decolorization rate was determined from the difference in absorbance at the absorption maximum wavelength. Here, the decolorization rate is a numerical value defined by the following equation.

Decolorization ratio = ((E1−E2) / E1) × 100 (E1 is the absorbance before immersion in the developer, and E2 represents the absorbance after immersion in the developer.) The sample was immersed in a buffer solution of No. 0 at a liquid temperature of 37 ° C. for 90 seconds, and the immobilization ratio was determined from the change in absorbance before and after immersion. Here, the immobilization ratio is a value serving as an index of the diffusion resistance of the dye, and is a numerical value defined by the following equation.

Fixation ratio = (E4 / E3) × 100 (E3 is the absorbance before immersion in the developer, and E4 is the absorbance after immersion in the developer.) The average of the fine particle dispersion obtained as described above. The particle diameter, the immobilization rate and the decolorization rate of the prepared sample were measured for samples 302 to 320.
Are shown in Table 5 together with the relative absorbance ABS500 at 500 nm when the maximum spectral absorption wavelength λmax and the maximum absorbance are set to 1.

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[Table 5]

As is evident from the results in Table 5, the dyes of the present invention exhibit better decolorization and excellent diffusion resistance than the comparative dyes, and their spectral absorption is in the spectral sensitivity range of the green photosensitive emulsion. It can be seen that the overlap is small and the sensitivity of the green photosensitive layer is hardly reduced. Further, it can be seen that the effect of the present invention is remarkably exhibited particularly in a fine particle dispersion having an average particle diameter of 300 nm or less.

Example 4 A sample having the same constitution as that of the light-sensitive material in Example 1 of the present invention was prepared in the same manner as in Example 1, except that the color developing step in the processing step was 1 minute and 30 seconds and the temperature of the color developing solution was 45 ° C. Except for the above, the treatment was performed in the same manner as in Example 1 of the present invention.

[0130]

As described above, a dye having excellent diffusion resistance can be provided, and a silver halide photographic light-sensitive material having reduced fog, high sensitivity and improved stability over time can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 7/407 G03C 7/407

Claims (15)

[Claims] 1. A solid fine particle having a photosensitive hydrophilic colloid layer and a non-photosensitive hydrophilic colloid layer on a support, wherein at least one layer is represented by any of the following general formulas (1) to (4): A silver halide photographic light-sensitive material comprising at least one kind of dispersed compound. Embedded image (In the above general formula (1) or (2), A represents an acidic nucleus residue, L ₁ , L ₂ and L ₃ represent a methine group, n represents 0, 1 or 2, and Z represents (N represents a group of nonmetallic atoms necessary to form a heterocyclic residue by bonding to the indicated nitrogen atom, Y represents a heterocyclic residue, and R represents a hydrogen atom or an alkyl group.) (In the above general formula (3) or (4), A represents an acidic nucleus residue, L ₁ , L ₂ and L ₃ represent a methine group, n represents 0, 1, or 2, and Z represents And R ₁ , R ₂ and R ₃ represent a hydrogen atom or an alkyl group, and EWG represents a substituent of Hammett. Represents an electron-withdrawing substituent having a constant σp of 0.3 or more, provided that Z
And R ₁ and R ₂ represent an alkyl group when the nitrogen-containing heterocyclic ring formed by bonding to a nitrogen atom is an indole ring. ) 2. The halogen according to claim 1, wherein the non-photosensitive hydrophilic colloid layer contains a compound dispersed in solid fine particles represented by any one of the general formulas (1) to (4). Silver halide photographic material. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the compound represented by any one of formulas (1) to (4) has at least one carboxyl group in its molecular structure. material. 4. In the above general formulas (1) to (4), A
Is a residue of 2-pyrazolin-5-one. 4. A silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein 5. In the above general formulas (1) to (4), n
5. The silver halide photographic light-sensitive material according to claim 1, wherein 0 is 0. 6. The compound according to claim 1, wherein Y is a cyclic sulfone, a cyclic sulfoxide or a lactone in the general formula (1) or (2). The silver halide photographic light-sensitive material as described above. 7. The compound represented by any one of the above general formulas (1) to (4)
The particle diameter of the solid fine particles of the compound represented by 0.3 to 0.0
6. The silver halide photographic light-sensitive material according to claim 1, wherein the thickness is 1 [mu] m. 8. The method according to claim 1, wherein the composition contains at least one two-equivalent magenta color coupler. Silver halide photographic material. 9. The silver halide photographic light-sensitive material according to claim 1, 2, 3, 4, 5, 6, 7, or 8 can be used within 200 seconds. A method for processing a silver halide photographic light-sensitive material, comprising performing color development processing. 10. The silver halide photographic material according to claim 1, claim 2, claim 3, claim 3, claim 4, claim 5, claim 6, claim 7, or claim 8 within 120 seconds. A method for processing a silver halide photographic light-sensitive material, comprising performing color development processing. 11. A solid fine particle dispersion of a compound represented by any one of formulas (1) to (4). 12. A compound represented by the general formula (1). 13. A compound represented by the general formula (2). 14. A compound represented by the general formula (3). 15. A compound represented by the general formula (4).