JPH09152673A - Silver halide pohtographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain stable sensitivity and to ameliorate the pressure fogging in rapid processing, silver color tones and unequal gloss by providing silver halide emulsion layers with layers into which ultrafiltered silver halide emulsions are incorporated and specific dextrin or dextran is incorporated. SOLUTION: This photosensitive material has the silver halide emulsion layers and hydrophilic colloidal layers on a base. The silver halide emulsion layers have the layers contg. the ultrafiltered silver halide emulsions and contg. 500 to 20000 dextrin or dextran. The ultrafiltration is a method of refining the colloidal particles larger than holes of a membrane by pressing a colloidal soln. under pressurization to the membrane, thereby passing the material having the grain size smaller than the holes of the membrane. At this time, the selection of the size of the colloidal particles to be refined is made possible by selecting the size of the holes of the membrane. The efficiency in refining the colloidal particles is improved by repetitively passing the colloidal soln. through the ultrafiltration membrane while washing the colloidal soln. by adding water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material capable of obtaining stable sensitivity and having improved pressure fog, silver tone and uneven gloss even in rapid processing.

[0002]

2. Description of the Related Art There is a strong demand for stable performance of silver halide photographic light-sensitive materials (hereinafter, simply referred to as light-sensitive materials). In particular, medical light-sensitive materials are highly demanded because they lead to misdiagnosis. It is generally known that silver halide grains used in a light-sensitive material form a large amount of soluble salts harmful to photographic performance during grain formation, and a precipitation method is one of the methods for removing them. It is a method of separating and removing a solid layer containing silver halide grains and a liquid layer containing soluble salts by using a precipitant.
However, the precipitation method has poor reproducibility of the impurity level in the final product, and it is difficult to obtain stable performance (especially sensitivity). Further, when silver halide grains purified by the precipitation method are used, the silver color tone after development processing deteriorates.

Further, there has been an increasing demand for rapid processing of photosensitive materials. Therefore, the improvement of the drying property of the light-sensitive material becomes an important issue, and the reduction of the binder amount becomes indispensable. However, if the amount of the binder is reduced, the fog failure due to the pressure applied during the development process or the handling deteriorates. As a technique for improving fog failure due to pressure, a technique using latexes is disclosed in US Pat. No. 2,376,005.
No. 3,325,386, Japanese Patent Publication No. 45-5331
And No. 46-2506, and JP-A-51-130217. As a result, although the pressure fog is improved to some extent, there is a drawback in that the glossiness of the film after processing occurs and the obtained image is difficult to see.

Further, increasing the amount of the hardener added to the protective layer of the light-sensitive material instead of decreasing the amount of the binder to increase the degree of hardening also contributes to the improvement of the drying property. And other hardening agents cause uneven gloss after processing.

[0005]

SUMMARY OF THE INVENTION In contrast to the above problems, the object of the present invention is to provide a light-sensitive material which has stable sensitivity and has improved pressure fog, silver tone and uneven gloss even in rapid processing. To provide.

[0006]

The above object of the present invention is achieved by the following means.

In a silver halide photographic light-sensitive material having a silver halide emulsion layer and a hydrophilic colloid layer on a support, the silver halide emulsion layer contains an ultrafiltered silver halide emulsion and has a molecular weight of A silver halide photographic light-sensitive material having a layer containing 500 to 20,000 dextrin or dextran.

In a silver halide photographic light-sensitive material having a silver halide emulsion layer and a hydrophilic colloid layer on a support, the silver halide emulsion layer contains an ultrafiltered silver halide emulsion, and The silver halide emulsion layer and / or the hydrophilic colloid layer are represented by the general formula [HI]
~ A silver halide photographic light-sensitive material characterized by being hardened with at least one hardener among the hardeners represented by [H-VIII].

The silver halide emulsion layer has a molecular weight of 50.
The silver halide photographic light-sensitive material as described in the above item, which contains 0 to 20,000 dextrin or dextran.

Hereinafter, the present invention will be described specifically.

In the present invention, ultrafiltration refers to pressing a colloidal solution against a membrane under pressure to pass a substance having a particle size smaller than the pores of the membrane and purifying colloidal particles larger than the pores of the membrane. Is the way to do. By selecting the size of the pores of the membrane, the size of the colloidal particles to be purified can be selected. The efficiency of purification of colloidal particles can be improved by repeatedly passing the colloidal solution through the ultrafiltration membrane while washing with water. Further, when ultrafiltration is performed while applying voltage to the electrodes on both sides of the membrane, the colloid particles can be purified more efficiently. For example, in the case of ultrafiltration of silver halide, unnecessary inorganic salts are passed through the membrane to obtain a residue composed of silver halide grains and a deflocculant.

A method of using the ultrafiltration unit will be described.

FIG. 1 is a conceptual diagram showing an example of desalination by the ultrafiltration device (ultrafiltration membrane) used in the present invention.

In FIG. 1, the silver halide emulsion after completion of physical ripening in the reaction vessel 1 is sent to the ultrafiltration device 5 by the pump 3 through the valve 2 and the inorganic ions and the like by the ultrafiltration membrane 6. Part of this is separated and removed as waste liquid and desalted. The waste liquid is discharged through a waste liquid outlet 7.

As shown in FIG. 1, a circulation loop is formed by the ultrafiltration device 5 and the conduits 4, 8, 9 and the emulsion flow in the circulation loop is advanced by the pump 3. As the emulsion repeatedly passes through the ultrafiltration apparatus, the degree of desalination increases.

Further, by adjusting the flow rate of the pump 3, the pressure in contact with the ultrafiltration membrane 6 of the emulsion can be adjusted, and this pressure can be monitored by the pressure gauges 10 and 11. To terminate the desalting and return the emulsion to the reaction tank, the control valve 13 is a three-way valve, which is adjusted so that the emulsion returns to the reaction tank without passing through the conduit 9. Whether the emulsion returned to the reaction tank has a desired salt concentration can be confirmed by the conductivity meter 12. The stirring device 14 is used during physical ripening of the emulsion or during re-dispersion after desalting.

Ultrafiltration is carried out by circulating the dispersion liquid in the reaction vessel while contacting with the semipermeable ultrafiltration membrane so that a pressure difference is generated across the semipermeable ultrafiltration membrane. preferable. Membranes that are permeable to only molecules of a particular size or smaller, and that contain pores sized to retain larger molecules and silver halide grains in the dispersion, have a density of about 500 to 300, 000 or more, preferably those exhibiting a transmission cutoff in the molecular weight range of about 500 to 50,000.

The membrane used for ultrafiltration typically uses a very thin layer with a very fine porous structure, and the pressure of the dispersion in contact with the ultrafiltration membrane can vary over a wide range. Typically, the pressure in the reaction vessel contacting the ultrafiltration membrane is about 7.03k.
g / cm ² , the outlet pressure of the retentate is about 0.703 k
It is g / cm ² or less. The pressure differential across the membrane is typically about 2.81~4.22kg / cm ^2. Of course, it is within the skill of the artisan to operate at pressures outside these ranges depending on the structure of the reaction vessel and ultrafiltration membrane, the viscosity of the dispersion, the concentration of retentate and the desired purity of the retentate. . There is an anisotropic film supported and included on a thicker porous structure layer.

These useful membranes include various polymeric materials such as polyvinyl chloride, polyvinyl carboxylate, polyvinyl formate, polyvinyl acetate, polyvinyl alcohol, polysulfone, polyvinyl ether, polyacrylamide,
Polyacrylonitrile, polymethacrylamide, polyimides, polyesters, polyfluoroalkylenes such as polytetrafluoroethylene, and polyvinylidene fluoride, and cellulosic polymers such as cellulose and cellulose esters such as cellulose acetate, cellulose butyrate and cellulose acetate butyrate. Can be

The molecular weight of the dextrin and dextran of the present invention is 500 to 20,000, and 5 is particularly preferable.
00 to 5000.

The added amount of dextrin and dextran of the present invention is preferably 0.01 to ² g / m ² ,
More preferably, it is 0.05 to 1 g / m ² . More preferably, it is 0.1 to 0.5 g / m ² . Further, the layer to be added is preferably an emulsion layer, but if necessary, it may be added to other hydrophilic colloid layers in a necessary amount and may be used alone, or may be used in combination of two or more kinds if necessary. It doesn't matter. Further, it is contained in the light-sensitive material in an amount of 10% or more, preferably 10% or more and 30% or less based on the total weight of the light-sensitive material.

The dextrin used in the present invention is α-
It is a polymer of 1,4-linked D-glucose and generally refers to a general term for various degradation products from hydrolysis of starch to maltose. Except for some that are scientifically important, they have no particular structural features, and their molecular weights are not constant, except for some that have chemical structural features. There are many types, depending on the method and application of hydrolysis, from high molecular weight ones obtained by slightly hydrolyzing starch to low molecular weight ones which do not exhibit iodine starch reaction.

Specific examples of dextrins are trade names such as LLD from Meito Sangyo Co., Ltd., trade names such as Amycor 1 and Dextrin 102S from Nitto Kagaku Co., Ltd., and Towa Kasei Kogyo Strains] are commercially available under the trade name of PEO.

Examples of the hardener in the present invention include the compounds represented by the general formulas [HI] to [H-VIII].

Hereinafter, these compounds will be described in detail.

In the general formula [HI], R ¹ and R ² are each an alkyl group (eg, methyl group, ethyl group, benzyl group, phenethyl group, 2-ethylhexyl group, etc.) or aryl group (eg, phenyl group, naphthyl group). Groups, etc.) and are bonded to each other to form a heterocycle with a nitrogen atom. Examples of the ring include a pyrrolidine ring, a piperazine ring, a morpholine ring and the like.

R ³ is a substituent such as —NR ⁴ R ⁵ (R ⁴ and R ⁵ are synonymous with R ¹ and R ² ), a halogen atom, a carbamoyl group, a sulfo group, a ureido group, an alkoxy group, an alkyl group and the like. Represent R ³ includes those having a substituent, and examples of the substituent include a halogen atom, an alkyl group, a carbamoyl group, a sulfo group, a sulfooxy group and a ureido group.

M represents 0 to 5, and when m ≧ 2, a plurality of R ^3's may be the same or different from each other.

X ⁻ represents an anion, and preferable examples thereof include halide ion, sulfate ion, sulfonate ion, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ^{− and the} like.

L represents 0 or 1, n represents 0 to 2, and n is 0 when forming an intramolecular salt.

In the general formula [H-II], R ²¹ and R ²² are cycloalkyl group (eg cyclohexyl group) or alkyl group (eg methyl group, ethyl group, 2-ethylhexyl group) and methoxyethyl group. Groups such as alkoxyalkyl groups, benzyl groups, phenethyl groups and other aralkyl groups, —R ²³ —N ⁺ (R ²⁴ ) (R ²⁵ ) (R ²⁶ ) (X ⁻ ) _m
Represents a group represented by

Here, R ²³ is an alkylene group (for example, ethylene group, propylene group, trimethylene group, etc.), R ²⁴ ,
R ²⁵ and R ²⁶ represent an alkyl group (eg, methyl group, ethyl group, etc.), and two of R ²⁴ , R ^26, and R ²⁶ are bonded to each other to form a heterocycle (eg, pyrrolidine ring, piperazine ring, morpholine) together with a nitrogen atom. Ring and the like) and having a substituent.

Preferred examples of the substituent include a carbamoyl group such as diethylcarbamoyl and piperidinocarbonyl, and a sulfo group. m represents 0 or 1. X ^- is [H
-1]. Further, when forming an intramolecular salt, m is 0.

In the general formula [H-III], R ³¹ is an alkyl group (for example, a methyl group, an ethyl group, a butyl group, etc., or an aralkyl group such as a benzyl group, a phenethyl group, etc.) or an aryl group (for example, a phenyl group, Naphthyl group).
These groups include those further having a substituent, and examples of the substituent include a carbamoyl group, a sulfamoyl group and a sulfo group. R ³² and R ³³ are a hydrogen atom or a substituent,
For example, halogen atom, acylamido group, nitro group, carbamoyl group, ureido group, alkoxy group, alkyl group,
Represents an alkenyl group, an aryl group, an aralkyl group, or the like,
It is also preferable that R ³² and R ³³ are bonded to each other to form a condensed ring together with the pyridinium ring skeleton.

Y ₁ represents a group capable of leaving when the compound represented by the general formula [H-III] reacts with a nucleophile. Preferred halogen atoms Examples, a sulfonyloxy group, a group represented by a sulfo group or a _{^{-OPO (OR 34) 2 (R}} 34 represents an alkyl group or an aryl group).

When Y ₁ represents a sulfonyloxy group, it is also preferred that Y ₁ and R ³¹ are bonded.

M represents 0 or 1. X ⁻ has the same meaning as that of [H-1]. When forming an inner salt, m is 0.
It is.

In the formula [H-IV], the definitions of R ⁴¹ and R ⁴² are exactly the same as the definitions of R ¹ and R ² in the formula [HI], and R ⁴³ is an alkyl group (eg methyl group). Group ethyl group,
In addition to a butyl group, it represents a benzyl group, an aralkyl group such as a phenethyl group) or an aryl group (for example, a phenyl group, a naphthyl group, etc.).

X ^- has the same meaning as that of [H-1].

In the general formula [HV], R ⁵¹ , R ⁵² and R
The definitions of ⁵³ and R ⁵⁴ are exactly the same as the definitions of R ¹ and R ² in the formula [HI], and R ⁵¹ and R ⁵³ may form a ring.

Y ₂ represents a group which can be eliminated upon reaction with a nucleophile, and is preferably a halogen atom, a sulfonyloxy group (preferably alkylsulfonyloxy or arylsulfonyloxy), a 1-pyridinium group or an imidyloxy group (for example, Phthalimidyloxy, succinimidyloxy, glutarimidyloxy), azolyloxy group,
An ammonio group is mentioned.

X ^- has the same meaning as that of [H-1].

In the general formula [H-VI], R ⁶¹ and R ⁶² are an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group or —NR ⁶³ R ⁶⁴ (R ⁶³ and R ⁶⁴ are It represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an aromatic heterocyclic group, and also includes a group in which R ⁶³ and R ⁶⁴ are bonded to form a ring. Y ₂ is represented by the general formula [H-
V] is the same as the definition of Y ₂ .

In the formula [H-VII], R ⁷¹ , R ⁷² and R ⁷³ , R ⁷⁴ and R ⁷⁵ , R ⁷⁶ have the same definition as R ¹ and R ² in the formula [HI]. And Y ₂ is represented by the general formula [H-
V ₂ ] is Y ₂ and X ⁻ are X in the general formula [HI].
^- is the same as that of the definition.

In the general formula [H-VIII], R ⁸¹ represents an aryl group, Z represents a non-metal atom group necessary for forming an aromatic heterocycle, and the ring formed by R ⁸¹ and Z is substituted. Including those having a group.

X ^- has the same meaning as that of [H-1], and m
Represents 0 or 1, and when forming an inner salt, m is 0.

Examples of the carboxyl group-activating type hardener used in the present invention include those represented by the above general formulas [HI] to [H-VIII].
In addition to the compound represented by
No. 52-93470, No. 56-43353, No. 58-113929, JP-A-1-178959, JP-A-3-213849, and JP-A-4-323648.
The compounds described in US Pat. No. 3,321,313 are also preferably used.

Specific examples of the carboxyl group-activating type hardener used in the present invention include, for example, JP-A-3-21.
HI-1 to HI-15 described in JP-A-3849 and examples 1-1 of the general formula [I] described in JP-A-4-323648.
No. 7, compound H-II- described in JP-A-3-213849
1-H-II-7, H-III-1 to H-III-6, H-IV-
1-H-IV-3, H-V-1 to H-V-12, H-VI-
1-H-VI-5, H-VII-1 to H-VII-3, H-VIII
The compounds of -1 to H-VIII-4 can be preferably used.

Typical compounds among these are shown below, but the present invention is not limited thereto.

[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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The silver halide grains used in the present invention include silver halides such as silver chloride, silver iodochloride, silver chloroiodobromide, silver chlorobromide, silver bromide and silver iodobromide. When silver iodochloride, silver chloroiodobromide or silver iodobromide is used, the silver iodide content is preferably 1.0 mol% or less as the average silver iodide content in the entire silver halide grains, but 0 It is more preferably at most 0.7 mol%.

The average grain size of the silver halide grains used in the present invention is preferably 0.15 to 5.0 μm,
The thickness is more preferably 0.4 to 3.0 μm, and most preferably 0.4 to 2.0 μm.

The crystal habit of the silver halide grains used in the present invention may be any crystal habit such as cubic, octahedral and twin planes, but tabular silver halide grains are preferred. Is. The tabular silver halide grain is a grain having two parallel main planes facing each other. What can be used in the present invention is that the (111) plane is the main plane and the (100) plane is the main plane. It may be flat or either.

When tabular silver halide grains are used in the present invention, the ratio of the average projected area diameter to the average grain thickness (hereinafter referred to as the aspect ratio) is 3 or more, preferably 3.0 or more. It is less than 15.0. It is particularly preferably 3 or more and less than 10. The projected area grain size is represented by the diameter of a circle having the same area as the projected area.

When tabular silver halide grains are used in the present invention, the average thickness is preferably 0.01 to 1.0 μm, more preferably 0.02 to 0.40 μm, and further preferably 0.02. Is about 0.30 μm.

The silver halide grains used in the present invention are preferably monodisperse emulsions having a narrow grain size distribution, specifically, (standard deviation of grain size / average grain size) × 100 = width of grain size distribution (% When the breadth of distribution is defined by (), it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

The silver halide grains used in the present invention may have dislocations. Dislocations are described in F. Hami
lton, Photo. Sci. Eng, 57 (196
7) and T. Shiozawa, J .; Soc. Pho
t. Sci. Japan, 35, 213 (1972) and can be observed by a direct method using a low-temperature transmission electron microscope. In other words, the silver halide grains taken out so as not to apply enough pressure to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscopic observation, and the sample is prepared so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for the electron beam to pass therethrough.
(0 KV or more) can be observed more clearly by using an electron microscope.

As the halogen particles used in the present invention, tabular grains having (100) as a main plane can also be used. The shape of the main plane of the tabular silver halide grain having (100) as the main plane is a right-angled parallelogram or a right-angled parallelogram with rounded corners. The adjacent side ratio of the right-angled parallelogram is less than 10, preferably less than 5, and more preferably less than 2. In addition, the length of a side when the corner is rounded is represented by a distance between an intersection of a line extending the straight part of the side and the straight part of the adjacent side.

Gelatin is preferably used as a dispersion medium for the protective colloid of silver halide grains used in the present invention, and as a binder in the emulsion layer and other hydrophilic colloid layers. As the gelatin, alkali-treated gelatin or acid-treated gelatin is used. Modified gelatin such as gelatin, low molecular weight gelatin (molecular weight: 20,000 to 100,000), and phthalated gelatin is used. Other hydrophilic colloids can also be used.

The silver halide grains used in the present invention can be chemically ripened. There are no particular restrictions on the conditions of the chemical aging step, such as pH, pAg, temperature, time, etc., and the conditions generally used in the art can be used. For chemical sensitization, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a selenium sensitization method using a selenium compound, a tellurium sensitization method using a tellurium compound, or a reducing substance is used. The reduction sensitization method to be used, gold or other, and the noble metal sensitization method using a noble metal can be used alone or in combination, and above all, the sulfur sensitization method,
Selenium sensitization, tellurium sensitization, reduction sensitization, and the like are preferably used.

In the case of selenium sensitization, the selenium sensitizer used comprises a wide variety of selenium compounds. Examples of useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N,
N, N'-triethylselenourea, N, N, N-trimethyl-N'-heptafluoroselenourea, N, N, N '
-Trimethyl-N'-heptafluoropropylcarbonyl selenourea, N, N, N'-trimethyl-N'-4-
Nitrophenylcarbonyl selenourea etc.), selenoketones (eg selenoacetone, selenoacetophenone etc.), selenoamides (eg selenoacetamide,
N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophos) And selenides (such as triphenylphosphine selenide, diethyl selenide and diethyl diselenide). Particularly preferred selenium sensitizers are selenoureas, selenamides, selenoketones, and selenides.

With respect to tellurium sensitizers and sensitizing methods, various known sensitizers and sensitizing methods are known. Examples of useful tellurium sensitizers include telluroureas (eg N 2 ，
N-dimethyltellurourea, tetramethyltellurourea, N
-Carboxyethyl-N, N'-dimethyl tellurourea,
N, N'-dimethyl-N'phenyltellurourea), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride) ), Telluroamides (e.g., telluroacetamide, N, N-dimethyltellurobenzamide), telluroketones, telluroesters, and isotellurocyanates.

The technique for using the tellurium sensitizer is in accordance with the technique for using the selenium sensitizer.

It is also preferable to carry out so-called reduction sensitization on the grain surface by placing it in an appropriate reducing atmosphere. Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and derivatives thereof.
Other preferable reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like.

The light-sensitive material of the present invention has a total processing time of 3
It is preferable to perform the treatment in 0 seconds or less.

The light-sensitive material of the present invention contains a developing agent such as aminophenol in a layer having an emulsion layer or other layers.
It may include ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone.

The swelling ratio of the light-sensitive material of the present invention is 150.
˜250% is preferable, and the film thickness after swelling is preferably 70 μm or less. If the swelling ratio exceeds 250%, poor drying occurs, and, for example, poor handling tends to occur during automatic processor processing, particularly rapid processing. Further, when the swelling ratio is less than 150%, development unevenness and residual color tend to deteriorate when developed.

Here, the swelling ratio means that the thickness of the hydrophilic colloid layer in the light-sensitive material is measured and
It is immersed in distilled water at 5 ° C. for 1 minute, the difference between the thickness of the hydrophilic colloid layer after the above and the thickness of the hydrophilic colloid layer is determined, and this is divided by the thickness of the hydrophilic colloid layer to obtain 100. Say doubled.

Examples of the support that can be used in the light-sensitive material of the present invention include the above-mentioned RD-17643-2.
8 and RD-308119, page 1009.

A suitable support is a polyethylene terephthalate film or the like, and the surface of these supports may be provided with an undercoat layer, corona discharge or ultraviolet irradiation in order to improve the adhesion of the coating layer.

In the light-sensitive material of the present invention, various additives can be added to the silver halide emulsion according to the purpose.

Next, preferable development processing of a light-sensitive material using the emulsion of the present invention will be described.

Preferred developing solutions for developing a light-sensitive material using the emulsion of the present invention include dihydroxybenzenes such as hydroquinone, para-aminophenols such as p-aminophenol and N-methyl-p-as developing agents.
Aminophenol, 2,4-diaminophenol, etc.
Examples of 3-pyrazolidones include 1-phenyl-3
-Pyrazolidones, 1-phenyl-3-pyrazolidone,
1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone, 5,5-dimethyl-1-phenyl-3
-Pyrazolidone and the like, and ascorbic acids, which are preferably used in combination.

Further, the total number of moles of dihydroxybenzenes, paraaminophenols and 3-pyrazolidones contained in the components of all developing solutions is preferably 0.1 mol / liter or more.

Preservatives may include sulfites such as potassium sulfite, sodium sulfite, reductones such as piperidinohexose reductone,
These are preferably used in an amount of 0.2 to 1 mol / l, more preferably 0.3 to 0.6 mol / l. Also, addition of a large amount of ascorbic acids leads to processing stability.

As the alkaline agent, sodium hydroxide,
PH adjusters such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate and potassium tertiary phosphate are included. In addition, borate, saccharose, acetoxime,
A buffering agent such as 5-sulfosalicylic acid, phosphate or carbonate may be used. The content of these agents is selected so that the pH of the developer is 9.0 to 13, preferably pH 10 to 12.5.

The dissolution aid may include diethylene glycol, triethylene glycols, and their esters, and the sensitizer may include, for example, a quaternary ammonium salt, a development accelerator, a surfactant and the like.

As a silver sludge-preventing agent, JP-A-56-
No. 106244, silver stain inhibitor, JP-A-3-518
The sulfides and disulfide compounds described in No. 44, and the cysteine derivatives or triazine compounds described in Japanese Patent Application No. 4-92947 are preferably used.

As an organic inhibitor, an azole organic antifoggant, for example, an indazole type, an imidazole type, a benzimidazole type, a triazole type, a benztriazo type, a tetrazole type, a thiadiazole type, a mercaptoazole type (for example, 1-phenyl-5- A mercaptotetrazole) compound or the like is used.

As the inorganic inhibitor, sodium bromide, potassium bromide, potassium iodide and the like may be contained.

As the chelating agent for concealing calcium ions mixed in tap water used in the treatment liquid, a chelating agent having a chelate stabilization constant with iron of 8 or more as an organic chelating agent described in JP-A-1-193583 is used. Is preferably used. Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate.

In the present invention, it is preferable to use the hardeners represented by the above formulas [HI] to [H-VIII] as the developing hardener. However, dialdehyde compounds may be used. In this case, glutaraldehyde is preferably used. However, for rapid processing, it is preferable that the hardener is allowed to act in the coating step of the photosensitive material in advance as described above, rather than the hardener is allowed to act in the development processing step.

The processing temperature of a preferable developer for developing a light-sensitive material using the emulsion of the present invention is preferably 25 to 50 ° C.
And more preferably 30 to 40 ° C. Development time is 4
˜90 seconds, more preferably 6 to 60 seconds. The processing time is Dry to Dry, preferably 15 to 21.
It is 0 second, more preferably 30 to 90 seconds.

The replenishment in the present invention replenishes the treatment agent fatigue and the oxidative fatigue equivalent amount, the evaporation amount, and the film carry-out amount. Examples of the replenishment method include replenishment by width and feed speed described in JP-A-55-126243, and JP-A-60-10494.
Area replenishment described in No. 6 or area replenishment controlled by the number of continuously processed sheets described in JP-A-1-149156 may be used, and the preferable replenishment amount is 500 to 80 cc / m ² .

Preferred fixing solutions can include fixing materials commonly used in the art. pH3.
8 or more, preferably 4.2 or more.

As the fixing agent, ammonium thiosulfate,
It is a thiosulfate such as sodium thiosulfate, and ammonium thiosulfate is particularly preferable in terms of fixing speed. The concentration of the ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / l, more preferably in the range of 0.8 to 3 mol / l.

The fixing solution of the present invention may be one that performs acidic hardening. In this case, aluminum ions are preferably used as the hardener. For example, it is preferable to add in the form of aluminum sulfate, aluminum chloride, potassium alum and the like.

Others In the fixing solution of the present invention, if desired, preservatives such as sulfite and bisulfite, pH buffers such as acetic acid and boric acid, mineral acids (sulfuric acid and nitric acid) and organic acids (citric acid and oxalic acid). ,
(Eg, malic acid), various acids such as hydrochloric acid, pH adjusting agents such as metal hydroxides (potassium hydroxide, sodium hydroxide), and chelating agents having a water softening ability.

As the fixing accelerator, for example, Japanese Patent Publication No.
No. 35754, No. 58-122535, No. 58-12
No. 2536, thiourea derivatives, U.S. Pat.
Thioether described in US Pat. No. 6,459.

[0095]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of seed emulsion-1) Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 bromide 841 g of potassium 2825 ml of water D1 1.75 N aqueous solution of potassium bromide The following silver potential control amount: 42 ° C, JP-B-58-58288, 58-5828
The solution B1 was added to the solution A1 using the mixing stirrer shown in No. 9.
Then, 464.3 ml of each of the solution C1 and the solution C1 were added by the simultaneous mixing method over 1.5 minutes to form nuclei.

After stopping the addition of solution B1 and solution C1, it took 60 minutes to raise the temperature of solution A1 to 60 ° C., adjust the pH to 6.0 with 3% KOH, and then re-solution. B1 and solution C1 were each mixed by the simultaneous mixing method at 55.4.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was measured using the solution D1.
It was controlled to be 8 mv and +16 mv.

Immediately after the addition, desalting and washing with water were performed.
In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.064 μm. It was confirmed with an electron microscope that the diameter (in terms of circular diameter) was 0.595 μm. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

(Preparation of Em-1) A tabular silver halide emulsion Em-1 was prepared by using seed emulsion-1 and the following four kinds of solutions.
Was prepared.

A2 ossein gelatin 34.03 g polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 2.25 ml seed emulsion-1 1.218 mol equivalent Equal to 3150 ml with water B2 potassium bromide 1734 g water 3644 ml C2 Silver nitrate 2478 g Finish to 4165 ml with water D2 3% by weight of gelatin and silver iodide grains (average grain size 0.05 μ) Fine grain emulsion (*) Equivalent to 0.080 mol * 0.06 mol iodide 2 liters of an aqueous solution each containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide was added to 6.64 liters of a 5.0 wt% gelatin aqueous solution containing potassium over 10 minutes. During the formation of fine particles, the pH was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

The solution A2 was vigorously stirred in the reaction vessel while maintaining the temperature at 60 ° C., and a part of the solution B2, a part of the solution C2 and half of the solution D2 were added thereto by a double jet method over 5 minutes. Then, half of the remaining amount of the solution B2 and the solution C2 are added over a period of 37 minutes, and a part of the solution B2, a part of the solution C2, and the entire remaining amount of the solution D2 are added over 15 minutes. The total amount of the remaining solutions B2 and C2 was added thereto over 33 minutes. During this time, the pH was 5.8 and the pAg was
It was kept at 8.8 throughout. Here, the addition rates of the solution B2 and the solution C2 were changed as a function of time in accordance with the critical growth rate.

Further, the above solution D2 was added to the total silver amount of 0.
Halogen substitution was carried out by adding 15 mol% equivalent. After the addition was completed, this emulsion was cooled to 40 ° C. and modified with a phenylcarbamoyl group as an aggregating polymer agent (substitution rate 90%).
1800 ml of a 13.8% (weight) modified gelatin aqueous solution was added, and the mixture was stirred for 3 minutes. Then, acetic acid 56% (weight)
The pH of the emulsion was adjusted to 4.6 by adding an aqueous solution, stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then, distilled water at 40 ° C. 9.
0 l was added, and the mixture was left to stir, and the supernatant was drained. Further, 11.25 l of distilled water was added. After stirring and standing, the supernatant was drained. Then, gelatin aqueous solution and sodium carbonate 10%
A (weight) aqueous solution was added to adjust the pH to 5.80, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redispersion, pH was adjusted to 5.80 and pAg was adjusted to 8.06 at 40 ° C.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.11 μ and the average thickness was 0.25.
μ, average aspect ratio about 4.5, width of particle size distribution 18.
It was 1% of tabular silver halide grains. Further, the average distance between twin planes is 0.020 μm, and grains having a ratio of distance between twin planes to a thickness of 5 or more are 9% of all tabular silver halide grains.
7% (number), particles of 10 or more accounted for 49%, and particles of 15 or more accounted for 17%.

(Preparation of Em-2) (Em-2) was prepared in the same manner as in (Preparation of Em-1) except that the desalting method was carried out by ultrafiltration according to the method of the present invention.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.11 μ and the average thickness was 0.25.
μ, average aspect ratio about 4.5, width of particle size distribution 18.
It was 1% of tabular silver halide grains. Further, the average distance between twin planes is 0.020 μm, and grains having a ratio of distance between twin planes to a thickness of 5 or more are 9% of all tabular silver halide grains.
7% (number), particles of 10 or more accounted for 49%, and particles of 15 or more accounted for 17%.

(Chemical sensitization) Obtained Em-1 and Em-
2 to 60 ° C., and after adding the following amounts of sensitizing dyes (A) and (B) as a solid fine particle dispersion, adenine,
A mixed aqueous solution of ammonium thiocyanate, chloroauric acid and sodium thiosulfate and a dispersion liquid of triphenylphosphine selenide were added, and after 30 minutes, a silver iodide fine grain emulsion was added and ripening was carried out for a total of 2 hours. 4-hydroxy-6-methyl-1,3,3a, 7 as a stabilizer at the end of aging
-The appropriate amount of tetrazaindene (TAI) was added.

The above-mentioned additives and their addition amounts (per mol of silver) are shown below.

Sensitizing dye (A) 400 mg Sensitizing dye (B) 4.0 mg Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.2 mg Stabilizer (TAI) Solid fine particle dispersion of 500 mg spectral sensitizing dye is disclosed in JP-A-5-297.
No. 496, prepared by the method according to the method.
That is, it was obtained by adding a predetermined amount of the spectral sensitizing dye to water previously adjusted to 27 ° C. and stirring with a high-speed stirrer (dissolver) at 3.500 rpm for 30 to 120 minutes.

Sensitizing dye (A): 5,5'-dichloro-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine-sodium salt anhydride Sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl- 3,3′-Di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride The above dispersion liquid of triphenylphosphine selenide was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., stirred and completely dissolved. On the other hand, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto.
Was added. Next, these two liquids are mixed to obtain a diameter of 10c.
m with a high-speed stirring type disperser having a dissolver of 50 m.
Dispersion was performed at a dispersion blade peripheral speed of 40 m / sec at 30 ° C. for 30 minutes. Thereafter, ethyl acetate was removed while stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3 wt% or less. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg. A part of the dispersion thus obtained was fractionated and used in the above experiment.

(Preparation of emulsion layer coating solution) The following additives were added to each of the obtained emulsions, and the natural water-soluble polymer of the present invention was further added as shown in Table 1 to prepare emulsion layer coating solutions. The addition amount is indicated by the addition amount per 1 m ^{2 on} one side of the light-sensitive material.

Compound (G) 0.5 mg 1,1-dimethylol-1-bromo-1-nitromethane 70 mg t-butyl-catechol 130 mg 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5- Triazine 5 mg Polyvinylpyrrolidone (molecular weight 10,000) 35 mg Styrene-maleic anhydride copolymer 80 mg Sodium polystyrene sulfonate 80 mg Trimethylolpropane 350 mg Diethylene glycol 50 mg Nitrophenyl-triphenylphosphonium chloride 20 mg 1,3-Dihydroxybenzene-4-sulfonic acid Ammonium 500 mg Colloidal silica (Ludox AM: DuPont, particle size 0.013 μm) 0.5 mg Compound (H) 0.25 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 2-Mercaptobenzimidazole-5-sodium sulfonate 15 mg Compound (M) 5 mg Compound (N) 5 mg Water-soluble polymer or comparative latex Amount shown in Table 1 (Preparation of coating solution for protective layer) ) Next, the following additives were added and prepared as a coating liquid for the protective layer. The addition amount is indicated by the addition amount per 1 m ^{2 on} one side of the silver halide photographic light-sensitive material.

Gelatin 0.8 g Polymethylmethacrylate (matting agent having an area average particle size of 7.0 μm) 50 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 36 mg 2,4-dichloro-6-hydroxy -1,3,5-Triazine sodium salt 10 mg Polyacrylamide (average molecular weight 10000) 0.2 g Sodium polyacrylate 30 mg Compound (SI) 20 mg Compound (I) 12 mg Compound (J) 2 mg Compound (S-1) 7 mg Compound ( K) 15 mg compound (O) 50 mg compound _{(S-2) 5mg C 9} F 19 O (CH 2 CH 2 O) 11 H 3mg C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2 O) _{15 H 2mg C 8 F 17 SO} 2 N (C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 S0 3 Na 1mg ( crossover cut layer Preparation) Copolymer dispersion liquid obtained by diluting the copolymer consisting of three kinds of monomers of 50% by weight of glycidyl methacrylate, 10% by weight of methyl acrylate and 40% by weight of butyl methacrylate to 10% by weight is applied as an undercoat liquid. Thickness 175μ
A crossover cut layer was applied to both surfaces of the m-colored polyethylene terephthalate support so that the coating amount per 1 m ^{2 on} one side would be the following composition to prepare a support sample.

Dye solid fine particle dispersion (AH) 50 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 5 mg Compound (I) 5 mg 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg Colloidal silica ( Average particle diameter 0.014 μm) 10 mg Potassium polystyrene sulfonate 50 mg

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(Coating) Using these coating solutions, two slide hopper type coaters were used so that the coating amount was 1.6 g / m ² per side and the amount with gelatin was 2.5 g / m ^2. Sample No. 2 was coated on the above-mentioned support sample at the speed of 120 m / min by simultaneous coating on both sides with the following layer structure. 1 to No. I got 16.

Layer position Layer type Gelatin amount per side (g / m ² ) Upper layer Protective layer 0.8 Intermediate layer Emulsion layer 1.5 Lower layer Filter layer 0.2 (Evaluation of sample) (1) Reproduction of sensitivity Evaluation of the obtained sample No. 1 to No. 16 was used to evaluate the photographic characteristics. First of all, a sample was prepared from two intensifying screens (KO-25
0), and a tube voltage of 80 kv via an aluminum wedge.
p, tube current 100 mA, X-ray irradiation for 0.05 seconds,
Exposure. Then, using an automatic developing machine (SRX-503), processing was performed with a developing solution and a fixing solution having the following formulations. This was performed 50 times for each sample.

(Developer Solution Formulation) Part-A (for 12 l finishing) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine pentaacetic acid 120 g Sodium bicarbonate 132 g Boric acid 40 g 5-Methylbenzotriazole 1.4 g 5-nitrobenzimidazole 0.4 g 1-phenyl-5-mercaptotetrazole 0.25 g 4-hydroxymethyl-4-methyl-1-phenylpyrazolidone 102 g hydroquinone 390 g Add water to make 6000 ml Part-B (12l finish Glacial acetic acid 70 g 5-nitroindazole 0.6 g N-acetyl-DL-penicillamine 1.2 g (starter) glacial acetic acid 120 g potassium bromide 225 g HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH _{1.0g CH 3 N (C 3 H} 6 NHCONHC 2 HSC 2 H 5) 2 1.0g Water to finish 1.0l and (fixer formulation) Part-A (for 18.3l finish) Ammonium thiosulfate (70 wt / Vol%) 4500 g sodium sulfite 450 g sodium acetate trihydrate 450 g boric acid 110 g tartaric acid 60 g sodium citrate 10 g gluconic acid 70 g 1- (N, N-dimethylamino) -ethyl-5-mercaptotetrazole 18 g glacial acetic acid 330 g aluminum sulfate 62 g of water was added to finish to 7200 ml. To prepare a developing solution, Part A and Part B were simultaneously added to about 5 liters of water, and water was added while stirring and dissolved to 12 liters. The pH was adjusted to 10.53 with glacial acetic acid. This is used as a development replenisher.

20 ml / l of the aforesaid starter was added to 1 liter of this development replenisher to adjust the pH to 10.30 to prepare a working solution.

To prepare the fixing solution, Part A was simultaneously added to about 5 liters of water, water was added while stirring and dissolving to make 18.3 liters, and the pH was adjusted to 4.6 using sulfuric acid and NaOH.
This is used as a fixing replenisher.

(Treatment Step) Process Treatment Temperature (° C.) Treatment Time (sec) Development + Crossover 35 7.2 Fixing + Crossover 33 5.8 Rinsing + Crossover 18 3.8 (Supplying Water 7 l / min) Squeeze 40 2.8 Dry 50 5.4 Total 25.0 (1) Sensitivity measurement After the treatment, the sensitivity was measured. Sensitivity is fog +1.0
Sample No. 1 in 50
The relative sensitivity when the average of the individual sensitivity data was set to 100 was calculated for the average of the 50 individual sensitivity data of each sample (referred to as the average relative sensitivity of each sample). Since the average relative sensitivity of each sample was within the range of 100 to 100.8, the standard deviation of the sensitivity data of each sample was obtained and evaluated as the sensitivity reproducibility. The smaller the number, the smaller the variation in sensitivity.

(2) Evaluation of pressure fog (scratch) 5 g on each unexposed sample with a scratch hardness meter of a needle having a needle head of 0.3
After applying the load, the same development processing as above was performed, and the density of pressure fog generation was measured with a microdensitometer.
The degree of fogging was determined for Sample No. The fog rise of 1 is shown as a relative value when 100 is taken.

(3) Evaluation of silver color tone For the determination of silver color tone, each sample was subjected to the same treatment as in (1) and exposed to X-rays so that the density was 1.2 ± 0.5,
The same process as (1) was performed.

The color tone judgment is based on the following criteria.

A: Pure black tone B: Slight yellowish color C: Yellowish color (4) Gloss evaluation Density after each sample was treated in the same manner as in (1) for gloss evaluation. X-ray exposure so that
The same process as (1) was performed.

The gloss judgment was visually evaluated according to the following criteria.

A: There is slight unevenness in gloss, but there is no problem. B: There is unevenness in gloss, but it is visually endurable. C: The unevenness in gloss is severe and it is not visually endurable. Table 1 shows the obtained results.

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[Table 1]

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From the results in Table 1, it can be seen that there are few variations in sensitivity and scratches, and the silver tone and gloss unevenness are good.

Example 2 In Example 1, the same operations were performed from (seed emulsion-1) to (chemical sensitization).

(Preparation of emulsion layer coating solution) In Example 1 (Preparation of emulsion layer coating solution), the emulsion layer coating solution was prepared in the same manner except that the water-soluble polymer or the comparative latex was removed.

(Preparation of Protective Layer Coating Solution) In (Preparation of Protective Layer Coating Solution) of Example 1, (CH ₂ ═CHSO ₂ C
A protective layer coating solution was prepared in the same manner except that H ₂ ) _2O (hardener) was replaced with the hardener shown in Table 2.

(Crossover cut layer) and (coating) were the same as in Example 1, and the sample No. 26 to No. 52
I got

(Evaluation of Sample) The sample was evaluated in the same manner as in Example 1. However, in the case of (2) evaluation of pressure fog (scratch), the degree of fogging is determined by the sample No. 26
It was shown as a relative value when the fog rise was set to 100. Table 2 shows the results.

[0138]

[Table 2]

Comparative Hardener 1: Glyoxal: Formalin = 60:40 (mol% ratio) Comparative Hardener ₂ : (CH ₂ = CHSO ₂ CH ₂ CH ₂ ) ₂ O From the results of Table 2, the hardener of the present invention When the agent was used, good results were obtained as in Example 1.

[0140]

According to the present invention, stable sensitivity can be obtained,
Further, it was possible to provide a light-sensitive material with improved pressure fog, silver tone and uneven gloss even in rapid processing.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an example of desalination by an ultrafiltration device used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Reaction tank 2 Valve 3 Pump 4 Conduit 5 Ultrafiltration device 6 Ultrafiltration membrane 7 Waste liquid discharge port 8 Conduit 9 Conduit 10 Pressure gauge 11 Pressure gauge 12 Conductivity meter 13 Control valve 14 Stirrer

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having a silver halide emulsion layer and a hydrophilic colloid layer on a support, wherein the silver halide emulsion layer contains an ultrafiltered silver halide emulsion, A silver halide photographic light-sensitive material having a layer containing a dextrin or dextran having a molecular weight of 500 to 20,000. 2. A silver halide photographic light-sensitive material having a silver halide emulsion layer and a hydrophilic colloid layer on a support, wherein the silver halide emulsion layer contains an ultrafiltered silver halide emulsion, The silver halide emulsion layer and / or the hydrophilic colloid layer are represented by the following general formula [HI] to
A silver halide photographic light-sensitive material characterized by being hardened with at least one hardener among the hardeners represented by [H-VIII]. Embedded image In the formula, R ¹ and R ² represent an alkyl group or an aryl group, and it is also preferable that they are bonded to each other to form a heterocycle with a nitrogen atom. R ³ is a substituent, for example, —NR ⁴ R ⁵ (R ⁴ and R ⁵
Is synonymous with R ¹ and R ² , a halogen atom, a carbamoyl group,
It represents a sulfo group, a ureido group, an alkoxy group, an alkyl group or the like. m represents 0 to 5, and when m ≧ 2, a plurality of R ³ may be the same or different from each other. X ⁻ represents an anion, l represents 0 or 1, n represents 0 to 2,
N is 0 when forming an intramolecular salt. Embedded image In the formula, R ²¹ and R ²² are a cycloalkyl group or an alkyl group, an alkoxyalkyl group such as a methoxyethyl group,
Aralkyl groups such as benzyl group and phenethyl group, -R ²³
It represents a group represented by -N ⁺ (R ²⁴ ) (R ²⁵ ) (R ²⁶ ) (X ⁻ ) _m . Here, R ²³ represents an alkylene group, R ²⁴ , R ²⁵ and R ²⁶ represent an alkyl group, and two of R ²⁴ , R ²⁵ and R ²⁶ are bonded to form a heterocycle with a nitrogen atom, Including the case of having a substituent. m is 0 or 1, X ⁻
The X of [H-I] ^- is synonymous. When forming an intramolecular salt, m is 0. Embedded image In the formula, R ³¹ represents an alkyl group or an aryl group. These groups include those having a substituent. R ³² and R ³³ represent a hydrogen atom or a substituent, and it is also preferable that R ³² and R ³³ are bonded to each other to form a condensed ring together with the pyridinium ring skeleton. Y ₁ represents a group capable of leaving when the compound represented by the general formula [H-III] reacts with a nucleophile. When Y ₁ represents a sulfonyloxy group, it is also preferable that Y ₁ and R ³¹ are bonded. X ^- is X of [H-1] ^- it is synonymous. m
Represents 0 or 1, and when forming an intramolecular salt, m is 0. Embedded image In the formula, R ⁴¹ and R ⁴² are defined as R in the general formula [HI].
The definitions of ¹ and R ² are exactly the same, and R ⁴³ represents an alkyl group or an aryl group. X ^- is X of [H-1] ^- it is synonymous. Embedded image In the formula, R ⁵¹ , R ⁵² and R ⁵³ , R ⁵⁴ are defined by the general formula [H-
I], the definition of R ¹ and R ² is exactly the same as
⁵¹ and R ⁵³ may form a ring. Y ₂ represents a group capable of leaving when it reacts with a nucleophile. X ^- is X of [H-1] ^- it is synonymous. [Chemical 6] In the formula, R ⁶¹ and R ⁶² are an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group or —NR ⁶³
R ⁶⁴ (R ⁶³ and R ⁶⁴ represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an aromatic heterocyclic group,
⁶³ and R ⁶⁴ are combined to form a ring).
Y ₂ has the same meaning as Y _{2 in} formula [HV]. Embedded image In the formula, R ⁷¹ , R ⁷² and R ⁷³ , R ⁷⁴ and R ⁷⁵ , R ⁷⁶ have the same definitions as R ¹ and R ² in the general formula [HI].
Y ₂ and Y ₂ in Formula [H-V], X ^- X in Formula [H-I] ^- is synonymous. Embedded image In the formula, R ⁸¹ represents an aryl group, Z represents a nonmetal atom group necessary for forming an aromatic heterocycle, and the ring formed by R ⁸¹ and Z includes those having a substituent. X ^- is [H-
X of I] ^- as synonymous. m represents 0 or 1, and when forming an intramolecular salt, m is 0. 3. The silver halide emulsion layer has a molecular weight of 500.
2. The silver halide photographic light-sensitive material according to claim 1, which contains ˜20,000 dextrin or dextran.