JP2002148746A - Processing method for silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method for a silver halide photosensitive material containing a flat platy silver halide emulsion in which the deterioration of a silver tone and the rise of fog are not caused even when a developing solution using reductones as a developing agent (or a developing solution not containing boric acid) is used over a long period of time. SOLUTION: In the processing method, a silver halide photosensitive material having a silver halide emulsion layer containing flat platy silver halide grains spectrally sensitized with at least one of sensitizing dyes of formulae (I) and (II) on at least one side of the base is processed with a developing solution containing at least one compound of formula (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a method for processing a silver halide photographic light-sensitive material containing specific tabular grains (hereinafter, also simply referred to as a "photosensitive material"). The present invention relates to a processing method for performing development processing with a developer.

[0002]

2. Description of the Related Art In recent years, the preservation of the global environment has been called out as a major social problem, and in the photographic industry, the dumping of photographic processing wastewater into the ocean has been completely banned. This problem is an unavoidable problem. As one technology in consideration of environmental conservation, further reduction in the amount of photographic processing solution used is required, and by reducing the amount of replenishing processing solution, the amount of waste solution is reduced, and by improving the photosensitive material, Development of a processing solution that provides sufficient image performance with a processing liquid is also being performed every day.

[0003] Attention has been paid to a technique for reducing the amount of silver ions and halogen ions released into a processing solution by reducing the amount of coated silver in a photographic material, thereby achieving a reduction in the amount of replenishment. It is well known in the art to use a photographic emulsion using tabular silver halide grains as a means for obtaining a higher optical density with a small amount of silver. Tabular silver halide emulsions are described, for example, in US Pat.
No. 9,520, which is known to be advantageous for spectral sensitization and sharpness.

In addition, since a photosensitive material using tabular grains has the property of achieving high sensitivity while having a small amount of silver, the amount of X-ray exposure to a patient during photography, particularly in the medical field, is high. Because it is possible to reduce
Particularly, it is demanded as a high-sensitivity photosensitive material.

[0005] However, these tabular silver halide grain emulsions have good spectral sensitization, but when subjected to rapid processing, especially rapid processing by an automatic processor, the color tone of the silver image becomes yellowish black. Problems.

On the other hand, focusing on the processing solution, hydroquinone, boric acid, and aldehydes which are harmful to the human body have been used in conventional developing solutions, and a technology for eliminating these harmful substances from the developing solution has been developed. There has been an urgent need, and as one of the technologies, Japanese Patent Application Laid-Open Nos. 7-77781 and 7-110554 discloses a technique using reductons having little effect on the human body.
Issue.

However, in the case of a developing solution using reductones, the above-mentioned deterioration of the silver tone of the image after the development processing is particularly remarkable, and there is a problem that fog rises with long-term use in an automatic developing machine. Have.

[0008] Further, removing boric acid from the developer can also be carried out by
Achieving rapid development from the viewpoint of developing a processing agent that is friendly to the human body and the environment is urgent. However, even when such a developer excluding boric acid is used, deterioration of the silver tone after processing and fog increase due to long-term use This is a major achievement.

[0009]

SUMMARY OF THE INVENTION The present invention has been made based on the above circumstances. That is, the first of the present invention
An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material which does not cause deterioration of silver tone or rise in fog even when a developer using reductones as a developing agent is used for a long period of time. . A second object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material which does not cause deterioration of silver tone or fog even when used for a long period of time, even though it is a developer excluding boric acid. . A third object is that even if a silver halide photographic light-sensitive material containing specific tabular silver halide grains is processed over a long period of time with a developer using reductones, the deterioration of silver tone and fog rise will occur. An object of the present invention is to provide a processing method for a silver halide photographic light-sensitive material which does not occur. A fourth object of the present invention is to provide a silver halide photographic material containing specific tabular silver halide grains, which is a developing solution from which boric acid has been removed, and which can reduce silver tone and fog even after long-term use. An object of the present invention is to provide a processing method for a silver halide photographic light-sensitive material which does not occur.

[0010]

An object of the present invention is to provide a support having a silver halide emulsion layer containing tabular silver halide grains on at least one side of a support, wherein the tabular silver halide grains are formed. The silver halide photographic material spectrally sensitized by at least one of the sensitizing dyes represented by the general formulas (I) and (II) is converted into a compound represented by the general formula (A)
This can be achieved by a method for processing a silver halide photographic light-sensitive material which is processed with a developer containing at least one compound represented by the following formula (2).

In a preferred embodiment, the silver halide photographic light-sensitive material is processed with a developer substantially free of boric acid or a salt thereof.

It is also preferred that the tabular silver halide grains have an average aspect ratio of 2.0 to 20.0 and an average thickness of 0.01 to 1.0 μm.

Hereinafter, the present invention will be described in more detail. First, the sensitizing dyes represented by formulas (I) and (II) will be described in detail.

Examples of the heterocyclic nucleus completed by Z ¹ or Z ^{2 in the} general formula (I) include oxazoles (oxazole, 4-methyloxazole, 4,5-dimethyloxazole, etc.), benzoxazoles ( Benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-methoxybenzoxazole, 5-phenylbenzoxazole, 5,6-dimethylbenzoxazole, etc., naphthoxazoles (naphtho [1,2-d] oxazole) , Naphtho [2,1-
d] oxazole, naphtho [2,3-d] oxazole, etc.), thiazoles, benzothiazoles, naphthothiazoles and the like.

The alkyl group represented by R ¹ and R ^{2 in} the general formula (I) includes methyl, ethyl, propyl, butyl and the like, and the substituted alkyl group includes a hydroxyalkyl group (β-hydroxyalkyl). Groups, specifically 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, etc.), acetoxyalkyl groups (β-acetoxyethyl, γ-acetoxypropyl, etc.), and alkoxyalkyl groups (β-methoxyethyl, γ- Methoxypropyl and the like), alkoxycarbonylalkyl groups (β-methoxycarbonylethyl, γ-methoxycarbonylpropyl,
δ-ethoxycarbonylbutyl, etc.), carboxyalkyl groups (carboxymethyl, β-carboxyethyl, γ-
Carboxypropyl, δ-carboxybutyl, etc.), sulfoalkyl group (β-sulfoethyl, γ-sulfopropyl, γ-sulfobutyl, δ-sulfobutyl, 2- (3-
Sulfopropoxy) ethyl, 2- [2- (3-sulfopropoxy) ethoxy] ethyl, etc.), cyanoalkyl group (β-cyanoethyl, etc.), carbamoylalkyl group (β
Carbamoylethyl, etc.), aralkyl groups (benzyl,
2-phenylethyl, 2- (4-sulfophenyl) ethyl and the like). The alkyl group has 1 to 1 carbon atoms.
8. The substituted alkyl group preferably has 1 to 10 carbon atoms.

The heterocyclic nucleus completed by Z ^{3 in the} general formula (II) includes the same heterocyclic nuclei as Z ¹ and Z ^{2 in} the general formula (I). As for R ³ , the same groups as R ¹ and R ^{2 in} formula (I) can be mentioned.

Examples of the alkyl group represented by R ⁴ in the general formula (II) include groups such as methyl, ethyl, propyl and butyl. Examples of the substituted alkyl group include a sulfoalkyl group (2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, etc.) and a carboxyalkyl group (2-carboxyethyl, 3-carboxypropyl,
-Carboxybutyl, carboxymethyl, etc.), hydroxyalkyl groups (2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, etc.), alkoxyalkyl groups (eg, 2-methoxyethyl, 3-methoxypropyl group, etc.), acyloxy Alkyl group (eg, 2-acetoxyethyl), alkoxycarbonylalkyl group (eg, methoxycarbonylmethyl, 2-methoxycarbonylethyl, 4-ethoxycarbonylbutyl), substituted alkoxyalkyl group (eg, hydroxymethoxymethyl, 2-hydroxyethoxymethyl, (2-hydroxyethoxy)
Ethyl, 2- (2-acetoxyethoxy) ethyl, acetoxymethoxymethyl, etc., dialkylaminoalkyl group (2-dimethylaminoethyl, 2-diethylaminoethyl, 2-piperidinoethyl, 2-morpholinoethyl, etc.), N- (N , N-dialkylaminoalkyl) -carbamoylalkyl group (N- [3- (N, N-dimethylamino) propyl] carbamoylmethyl, N- [2-
(N, N-diethylamino) ethyl] carbamoylmethyl, N- [3- (morpholino) propyl] carbamoylmethyl, N- [3- (piperidino) propyl] carbamoylmethyl, etc., N- (N, N, N-tri Alkyl ammonium alkyl) carbamoyl alkyl group (N- [3
-(N, N, N-trimethylammonium) propyl]
Carbamoylmethyl, N- [3- (N, N, N-triethylammonium) propyl] carbamoylmethyl, N
-[3- (N-methylpiperidinio) propyl] carbamoylmethyl and the like, N, N, N-trialkylammonioalkyl group (N, N-diethyl-N-methylammonioethyl, N, N, N -Triethylammonioethyl, etc.), cyanoalkyl group (2-cyanoethyl, 3-cyanopropyl, etc.), carbamoylalkyl group (2-carbamoylethyl, 3-carbamoylpropyl, etc.), heterocyclic-substituted alkyl group (tetrahydrofurfuryl, Furfuryl, etc.) and aralkyl groups (benzyl, 2-phenylethyl, etc.).

The alkyl group preferably has 1 to 8 carbon atoms, and the substituted alkyl group preferably has 1 to 10 carbon atoms.

The aryl group and substituted aryl group represented by R ⁴ include phenyl, p-chlorophenyl, p-tolyl, p-methoxyphenyl, p-carboxyphenyl,
p-methoxycarbonylphenyl, m-acetylaminophenyl, p-acetylaminophenyl, m-dimethylaminophenyl, p-dimethylaminophenyl, and the like.

As the sensitizing dye used in the present invention, in formula (I), Z ¹ is an oxazole, benzoxazole or naphthoxazole, and Z ² is a thiazole, benzothiazole or naphthothiazole. Sensitizing dyes and sensitizing dyes represented by formula (II) are preferred.

Next, typical specific examples of the sensitizing dyes represented by the general formulas (I) and (II) are shown, but the present invention is not limited thereto.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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The sensitizing dye represented by formula (I) or (II) is a known sensitizing dye and can be easily obtained.
F. M. Hamer, The Chemistr
y of heterocyclic compound
ds; The cyanedies and re
rated compounds ", 1964, Joh
n Wiley Sons (New York, Lon
don), p. 58, p. 536.

The sensitizing dyes represented by formula (I) or (II) may be used alone or in combination. The sensitizing dye may be added in an amount of 5 × 10 ^{−6 to} 5 × per mol of silver halide in the silver halide emulsion layer containing tabular grains.
It is preferably used in the range of 10 ^-3 mol. The addition time is
It may be at any stage during the production of the photosensitive material, but is preferably between the time after the grain formation and the end of the chemical sensitization, and more preferably after the grain formation and before the start of the chemical sensitization.

These sensitizing dyes can be added as a dye solution dissolved in a suitable organic solvent such as methanol, phenoxyethanol, phenylethanol or the like, or a mixed solvent of these organic solvents and water or amines. As a solid particulate dye dispersion dispersed in an aqueous system in which no organic solvent and / or surfactant is present.

Next, the tabular silver halide grains used in the present invention will be described. The average grain size of the tabular silver halide grains is preferably from 0.3 to 3.0 μm, particularly preferably from 0.5 to 1.5 μm.

The tabular silver halide grains according to the present invention include:
The average value (called the average aspect ratio) of the particle diameter / thickness (called the aspect ratio) is preferably 2.0 to 20.0.
And more preferably 2.5 to 10.0. The average thickness of the tabular silver halide grains is 0.01 to 1.0 μm.
Is preferably 0.02 to 0.5 μm, more preferably 0.03 to 0.3 μm.

The advantages of such tabular silver halide grains are:
For example, British Patent No. 2,112,15 discloses that spectral sensitization efficiency, image graininess and sharpness can be improved.
7, U.S. Pat. Nos. 4,439,520 and 4,433,
048, 4,414,310, 4,434,2
No. 26, etc., and emulsions can be prepared by the methods described therein.

In the present invention, the diameter of tabular silver halide grains is defined as the diameter of a circle having an area equal to the projected area of the grains from observation of electron micrographs of the silver halide grains.

In the present invention, the thickness of the tabular silver halide grains is defined as the minimum of the distance between two parallel principal planes constituting the tabular silver halide grains.

The thickness of the tabular silver halide grains can be determined from an electron micrograph with a shadow of the silver halide grains or an electron micrograph of a sample slice obtained by coating a silver halide emulsion on a support and drying. .

To determine the average aspect ratio, at least 100 samples are measured. In the silver halide emulsion of the present invention, the ratio of tabular silver halide grains to all silver halide grains is at least 50%, preferably 60%.
%, Particularly preferably 70% or more.

The tabular silver halide emulsion is preferably monodispersed. Here, the term “monodisperse” means that the coefficient of variation of the particle size (standard deviation of particle size / average particle size × 100) is 25% or less, preferably 20% or less, particularly preferably 15% or less.
Say that:

The silver halide emulsion used in the present invention may have any halogen composition, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodobromide. Silver iodobromide is preferred in terms of sensitivity, and the average silver iodide content is 0.1 to
4.0 mol%, particularly preferably 0.5 to 3.0 mol%.
Mol%. Further, silver chloroiodobromide can be used from the viewpoint of rapid processing.

When silver chloroiodobromide is used, silver chloride may be contained in any part of the grain, but it is particularly preferred to be unevenly distributed on the outermost surface or in the vicinity thereof.

In the tabular silver halide emulsion, the halogen composition may be uniform within the grains and silver iodide may be localized. It is preferably used. Production methods of tabular silver halide emulsions are described in JP-A-58-113926 and JP-A-58-1139.
No. 27, No. 58-113934, No. 62-1855
, European Patents 219,849 and 219,85
No. 0 etc. can be referred to. A method for producing a monodisperse tabular silver halide emulsion is described in JP-A-61-6.
No. 643 can be referred to.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, an aqueous silver nitrate solution is added to an aqueous gelatin solution having a pBr of 2 or less, or an aqueous silver nitrate solution and an aqueous halide solution are simultaneously added. To generate twin seed particles and then grow them by a double jet method. The size of the tabular silver halide grains can be controlled by the temperature during grain formation, the rate of addition of the silver salt and the aqueous halide solution, and the like.

The average silver iodide content and average silver chloride content of the silver halide emulsion (hereinafter referred to as parent grain emulsion) according to the present invention are determined by the composition of the aqueous halide solution to be added, ie, bromide, iodide and chloride. It can be controlled by changing the ratio of objects. During the production of a silver halide emulsion, a silver halide solvent such as ammonia, thioether or thiourea can be used, if necessary.

The emulsion may be subjected to a water washing method such as a noodle water washing method or a flocculation sedimentation method to remove soluble salts (desalting treatment step). As a preferred washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B No. 35-16086,
Alternatively, a method using G3, G8, etc., as an aggregating polymer agent described in JP-A-63-158644 is a particularly preferred desalting method.

The silver halide grains of the present invention may have dislocations. The dislocation is described, for example, in J. Mol. F. Hamilto
n, Photo. Sci. Eng. , 57 (1967)
And T. Shiozawa, J .; Soc. Photo. S
ci. Japan, 35, 213 (1972) and can be observed by a direct method using a low-temperature transmission electron microscope. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains 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, since the electron beam becomes harder to penetrate as the thickness of the particles is larger, it is better to use a high-pressure electron microscope (200 kV or more for particles having a thickness of 0.25 μm) to observe more clearly. Can be.

The tabular silver halide grains undergo cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), and rhodium salts (including complex salts) during the process of forming and / or growing the grains. ) And an iron salt (including a complex salt) to add a metal ion to allow the metal element to be contained inside the particle and / or on the particle surface.

The conditions of the chemical ripening step in the present invention, for example, pH, pAg, temperature, time and the like are not particularly limited, and can be performed under conditions generally used in the art.

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, a reduction sensitization method using a reducing substance, gold or the like, a noble metal sensitization method using a noble metal, or the like can be used alone or in combination. Among them, 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 includes a wide variety of selenium compounds, and useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (such as allyl isoselenocyanate). ), Selenoureas (N, N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoropropylselenourea, N, N, N'- Trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, selenoketones (selenoacetone, selenoacetophenone, etc.), selenoamides (selenoacetamide) , N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (2-sele Propionate, methyl 3-selenobutylate), selenophosphates (tri -p-
And selenides (such as triphenylphosphine selenide, diethyl selenide and diethyl diselenide). Particularly preferred selenium sensitizers are selenoureas, selenamides, selenoketones, selenides.

The amount of the selenium sensitizer used depends on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally 10 ^-8 to 10 ^-4 per mol of silver halide.
Use about moles. Depending on the properties of the selenium compound to be used, the method of addition may be a method of adding it alone or in a mixed solvent of water or an organic solvent such as methanol or ethanol, or a method of adding it by premixing with a gelatin solution. However, a method disclosed in JP-A-4-140739, that is, a method of adding the compound in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer may also be used. The temperature for chemical ripening using a selenium sensitizer is preferably in the range of 40 to 90 ° C, more preferably 45 to 80 ° C. Also, pH
Is preferably in the range of 4 to 9, and pAg is preferably in the range of 6 to 9.5.

With respect to tellurium sensitizers and sensitization methods, a wide variety of tellurium sensitizers are used, and examples of useful tellurium sensitizers are telluroureas (N, N-dimethyltellurourea,
Tetramethyltellurourea, N-carboxyethyl-N,
N'-dimethyltellurourea, N, N'-dimethyl-N '
Phenyltellurourea), phosphine tellurides (tributylphosphine telluride, tricyclohexylphosphine telluride, tri-i-propylphosphine telluride, butyl-di-i-propylphosphine telluride, dibutylphenylphosphine telluride, etc.), Examples include telluramides (telluroacetamide, N, N-dimethyltellurobenzamide, etc.), telluroketones, telluroesters, isotellocyanates, and the like. The technology for using the tellurium sensitizer is based on the technology for using the selenium sensitizer.

When the photosensitive material is subjected to development processing, it is processed by an automatic developing machine, and the steps from development to drying are carried out by 15 to 120.
It is preferably completed within seconds. That is, the time from when the tip of the photosensitive material starts to be immersed in the developing solution to when the tip comes out of the drying zone through a processing step (so-called Dry)
(Dry to dry time) is preferably 15 to 120 seconds, more preferably 15 to 90 seconds.

The development time is preferably from 3 to 40 seconds, more preferably from 6 to 20 seconds. The development temperature is preferably 2
The temperature is 5 to 50C, preferably 30 to 40C. The fixing temperature is preferably about 20-40 ° C, more preferably 29 ° C.
~ 37 ° C and the fixing time is preferably 3-30 seconds,
More preferably, it is 4 to 20 seconds.

In the drying step, hot air of usually 35 to 100 ° C., preferably 40 to 80 ° C. may be blown, or a drying zone provided with a heating means by far infrared rays may be provided in the automatic developing machine.

An automatic developing machine equipped with a mechanism for applying water or a rinsing solution of an acidic solution having no fixing ability to the photosensitive material during each of the developing, fixing and washing steps (Japanese Patent Application Laid-Open No.
-264953) may be used. Further, a device capable of adjusting a developing solution or a fixing solution may be incorporated.

In the processing method of the present invention, the developer and the fixer
The replenishment rate is 180ml / m each ^TwoProcessed by
And more preferably 8 to 160 ml / m^Two
And 10 to 100 ml / m^TwoEspecially preferred to be processed in
New

In the developer used in the processing method according to the first aspect of the present invention, reductones are used as a developer. Examples of the reductone include an enediol type, an enaminol type, an enediamine type, a thiol enol type and an enamine thiol type, and are preferably compounds represented by the above general formula (A).

In the general formula (A), R ₁ and R ₂ are each a hydroxyl group, an amino group (ethyl,
An alkyl group such as butyl and hydroxyethyl), an acylamino group (acetylamino, benzoylamino, etc.), an alkylsulfonylamino group (methanesulfonylamino, butanesulfonylamino, etc.), an arylsulfonylamino group (benzenesulfonylamino) , P-toluenesulfonylamino and the like), an alkoxycarbonylamino group (such as methoxycarbonylamino), a mercapto group and an alkylthio group (such as methylthio and ethylthio), and R ₁ and R ₂ are preferably a hydroxyl group,
Examples include an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

P and Q are each a hydroxyl group, a carboxyl group, an alkoxy group (methoxy, ethoxy, butoxy, etc.), a hydroxyalkyl group (hydroxymethyl, hydroxyethyl, etc.), a carboxyalkyl group (carboxymethyl, carboxyethyl, etc.), Sulfo group (including salt), sulfoalkyl group (sulfoethyl, sulfopropyl, etc.), amino group (including alkyl substitution), aminoalkyl group (aminoethyl, aminopropyl, etc.), alkyl group (methyl, ethyl, propyl, butyl) , Pentyl, etc.)
Or an aryl group (phenyl, p-tolyl, naphthyl, etc.)
Or a non-metallic atomic group bonded to each other to form a 5- to 8-membered ring together with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y. These 5-8
The membered rings may form a saturated or unsaturated fused ring.

Examples of the 5- to 8-membered ring include dihydrofuranone, dihydropyrone, pyranone, cyclopentenone,
Pyrolinone, pyrazolinone, pyridone, azacyclohexenone, uracil, cycloheptenone, cyclohexanone, azepine, cyclooctenone ring and the like are preferred, and a 5- to 6-membered ring is preferred. Among them, preferred examples of the 5- or 6-membered ring include dihydrofuranone, cyclopentenone, cyclohexanone ring, pyrazolinone, azacyclohexenone, and uracil ring.

When Y represents ＮＲNR ₃ , R ₃ is a hydrogen atom,
It represents a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group, and specific examples of each substituent include the above R ₁ , R ₂ , P
And Q, the same groups as those described above.

Hereinafter, specific examples of the compound represented by formula (A) will be shown, but the present invention is not limited thereto.

[0069]

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[0070]

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[0071]

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The salts of reductones include, for example, lithium, sodium, potassium, ammonium and the like.

Among these, preferred is an exemplary compound A-1 of ascorbic acid or erythorbic acid (stereoisomer).

The amount of these reductones to be added to the developing solution is not particularly limited, but is practically in the range of 0.1 to 100 g, preferably 1 to 80 g, more preferably 5 to 80 g per liter of the processing solution. Is desirable.

The reductones may contain only one kind or two or more kinds. Examples of the developing agent used in the processing method according to claims 2 and 4 of the present invention include reductones of the general formula (A), phenidone, hydroquinone, and any other commonly used photographic processing agents. May be.

Further, in addition to sulfite, an organic reducing agent can be used as a preservative. In addition, bisulfite adducts of chelating agents and hardeners can be used. It is also preferable to add a silver sludge inhibitor.
It is also preferable to add a cyclodextrin compound.
Compounds described in -124853 are particularly preferred. An amine compound can be added to the developer, and for example, a compound described in US Pat. No. 4,269,929 is particularly preferable.

A buffer may be used as the developer used in the development processing of the present invention. Examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, and phosphoric acid. Dipotassium, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (5 -Sodium sulfosalicylate), 5-
Potassium sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. However, the developer used in the processing methods of claims 2 and 4 of the present invention does not substantially contain a boric acid compound.

Examples of the development accelerator include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, and other 1-phenyl-3-pyrazolidones. Hydrazines, mesoionic compounds, ionic compounds, imidazoles and the like can be added as necessary.

As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
-Nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-
Nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be mentioned.
-Phenyl-5-mercaptotetrazole and the like.

Further, in the developer composition, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, cyclodextrin compound and the like can be used as an organic solvent for increasing the solubility of the developing agent. Further, various additives such as a stain inhibitor, an anti-sludge agent and a layering effect promoter can be used.

The processing method according to claims 2 and 4 of the present invention is characterized in that the developer in the processing step contains substantially no boric acid or a salt thereof. Here, "substantially not containing boric acid" means that the boric acid concentration is not more than 0.04 mol / liter, preferably not containing at all.

The term “boric acid” or “salt thereof” used in the present invention refers to
Physically H_ThreeBO_Three(Boric acid), HBO _Two(Metaboric acid), N
aBO_Two(Sodium metaborate), KBO_Two(Ca boric acid
), Na_TwoB_FourO₇(Sodium tetraborate / borax),
KB_FiveO₈(Potassium pentaborate) and the like.

When developing the silver halide photographic light-sensitive material of the present invention, a compound known as a fixing agent can be added to the fixing agent used. Fixing agents, chelating agents, pH buffers, hardeners, preservatives, and the like can be added. These are described in, for example, JP-A-4-242246 (page 4) and JP-A-5-136.
No. 32 (pages 2 to 4) can be used. Other known fixing accelerators can also be used.

Prior to the treatment, it is preferable to add a starter, and it is also preferable to add the solidified starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkali metal such as potassium bromide, an organic inhibitor, and a development accelerator are used.

The silver halide emulsion used in the light-sensitive material according to the present invention may be subjected to physical ripening or chemical ripening before and after the process.
Various photographic additives (chemical sensitizers, sensitizing dyes, desensitizing dyes, dyes, development accelerators, fog inhibitors / stabilizers, brighteners, hardeners, surfactants, antistatic agents, plasticizers Agents, slip agents, matting agents, binders, supports, etc.). Known additives include, for example, RD17643
(December 1978), page 23, section III to page 28, section XVII,
RD18716 (November 1979), 648-651
RD308119 (December 1989), 996
Those described in Sections III to 1012, Section XXI can be used.

As a support which can be used for the light-sensitive material according to the present invention, for example, the above-mentioned RD17643-28
And those described on page 1009 of RD 308119.

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

[0088]

Embodiments of the present invention will be described below. However, needless to say, the present invention is not limited to the embodiments described below. Unless otherwise specified, “%” in the examples indicates “% by mass”.

Example 1 (Preparation of tabular silver halide emulsion) A seed emulsion comprising silver iodobromide was prepared using the following solutions. [A ₁ ] Ossein gelatin treated with hydrogen peroxide 40 g Potassium bromide 75.1 g Add water 4000 ml [B ₁ ] Silver nitrate 600 g Add water 803 ml [C ₁ ] Ossein gelatin treated with hydrogen peroxide 16.1 g Potassium bromide 393.7 g Potassium iodide 35.1 g Water was added and 803 ml [D ₁ ] ammonia water (28%) 235 ml Using an apparatus disclosed in JP-A-62-160128,
Supply nozzle to the bottom of the mixing agitation Pera is, solution B for _1,
Solution C _1, was placed so as each becomes six.

The solution B ₁ and the solution C ₁ were added to the solution A ₁ stirred at a high speed of 430 rpm at a temperature of 40 ° C. by a controlled double jet method at a flow rate of 62.8 ml / min.
Was added. The flow rate was gradually increased from 4 minutes and 46 seconds after the start of the addition, and the final flow rate was 105 ml / min. Total addition time was 10 minutes and 45 seconds. With the potassium bromide solution (3.5 mol / L), pBr during addition was 1.
It was kept at 3.

After completion of the addition, the temperature of the mixed solution was raised to 2 for 10 minutes.
0 ℃ linearly down to, and the stirring rotation speed to 460 rpm, a solution D ₁ was added in 20 seconds, was Ostwald ripening for 5 minutes. The bromine ion concentration during aging is 0.02
5 mol / L, ammonia concentration 0.63 mol / L,
pH was 11.7.

Thereafter, acetic acid was added to neutralize the mixture immediately until the pH reached 5.6 to stop ripening, and to remove excess salts, an aqueous solution of Demol N (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate were used. Seed emulsion E after desalting and washing
m-1 was obtained.

Observation of Em-1 with an electron microscope revealed that it was a spherical particle having an average particle size of 0.28 μm and a variation coefficient of the particle size of 21%.

Subsequently, the seed emulsion Em-1 and 3 shown below were used.
Using the seed solutions, a silver halide emulsion mainly comprising tabular twin grains according to the present invention was prepared.

The obtained seed emulsion was used in an amount of 0.027 mol per mol of silver halide of the growing emulsion EM-2, and a copolymer (EO) of polypropylene oxide (PO) and polyethylene oxide (EO) was used as an antifoaming agent. / PO = 0.
(33, molecular weight = 1400) in 62 ° C. aqueous gelatin solution. Subsequently, 3.5 mol /
L of an aqueous solution of silver nitrate and an aqueous solution of 3.4 mol / L of potassium bromide by a control double jet method so that the addition rate at the end of addition is 2.3 times that at the start of addition.
Added over 7 minutes. In addition, temperature 62 degreeC, pH = 5.
8. It was kept throughout at pAg = 8.9. Further, desalting was carried out in the same manner as for the seed emulsion.

The resulting emulsion had an average particle size of 1.30 μm,
It was a tabular silver halide emulsion having an average thickness of 0.32 μm and an average aspect ratio of 4.1. This emulsion was designated as EM-1.

In the above, a growing emulsion was prepared in the same manner except that the pAg was set to 7.9, and the average grain size was set to 0.1.
A tabular silver halide emulsion having a thickness of 93 μm, an average thickness of 0.62 μm and an average aspect ratio of 1.5 was obtained.
And

(Preparation of silver iodide fine grains) 5000 m of a 5.2% gelatin solution containing 0.008 mol of potassium iodide
1,500 ml of an aqueous solution containing 1.06 mol of silver nitrate and potassium iodide were added at a constant flow rate over 35 minutes. The temperature during preparation of the fine particles was kept at 40 ° C. When the obtained silver iodide fine particles were confirmed by an electron micrograph at a magnification of 60,000, the average particle size was 0.05 μm, and β-AgI and γ
-AgI mixture.

(Chemical sensitization of emulsion)
While stirring and holding at 2 ° C., the sensitizing dyes I-6, I-7, I-16, I-31, II-1, and II- according to the present invention described above.
As shown in Table 1, 3, II-13 was added as a methanol solution so as to be 0.18 mmol per mol of EM-1 silver, and 10 minutes later, a chemical sensitizer was added per mol of silver. Potassium thiocyanate 95mg, chloroauric acid 2.5mg, sodium thiosulfate 2.0mg, adenine 15mg, triphenylphosphine selenide 0.2m
g was added in each case. Thirty minutes later, the silver iodide fine grain emulsion was added in an amount equivalent to 1.37 × 10 ⁻³ mol, and after a certain time, 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene (stabilizer) and 1
-Phenyl-5-mercaptotetrazole (antifoggant) was added for stabilization, and each was optimally chemically sensitized.
The obtained emulsions were designated as EM-1-2 to EM-1-8.

Further, the same chemical sensitization was carried out using EM-2 under the same conditions, and the obtained emulsions were subjected to EM2-2 to EM-2-
And 8.

Except that no sensitizing dye was added, those obtained by chemical sensitization under the same conditions were used for EM-1-1 and E-1-1.
M-2-1.

(Preparation of Coated Samples) Emulsions EM-1-1 to EM-1-8 and EM-2-1 to EM-
2-8 was added to the additives described below to prepare an emulsion layer coating solution. At the same time, a protective layer coating solution described below was also prepared. The coating amount of silver weight of 2.5 g / m ² per side, the amount with gelatin on the support at a rate per minute 80m using two slide hopper type coater so that the 1.85 g / m ² Both sides were simultaneously coated and dried in 2 minutes and 20 seconds to obtain coated samples 1-1 to 1-16, respectively. As a support, the concentration of glycidyl methacrylate / methyl acrylate / butyl methacrylate (50/10/40%) copolymer was 10%.
% Of a 175 μm X-ray film-based polyethylene terephthalate (PET) film base which was blue-colored to a concentration of 0.15, using an aqueous dispersion obtained by diluting to a concentration of 0.1%.

The additives used in the emulsion are as follows. The amount of addition is shown in an amount per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-butyl-catechol 82 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 25 g nitrophenyl-triphenylphosphonium chloride 50 mg resorcin-4-ammonium ammonium sulfonate 2.0 g 2-mercaptobenzimidazole-5-sodium sodium sulfonate 1.5 mg compound A 7.2 mg compound B 150 mg compound C 80 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N ( CH ₂ COOH) ₂ 1 g 1-phenyl-5-mercaptotetrazole 15 mg Diethylene glycol 7 g Dextran (average molecular weight 60,000) 600 mg Sodium polyacrylate (average molecular weight 36,000) 2.5 g

[0105]

Embedded image

Next, the following was prepared as a coating solution for the protective layer.
Additives are shown in amounts per liter of coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-decylsulfosuccinate 0.3 g Polymethyl methacrylate (a matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (area average particles) 0.5 g Ludox AM (colloidal silica manufactured by DuPont) 30 g (CH ₂ = CHSO ₂ CH ₂ CONHCH ₂ ) ₂ (hardener) 1.0 g Compound D (surfactant) 0 g Compound E (surfactant) 0.4 g Compound F (preservative) 0.1 g

[0108]

Embedded image

Next, the processing agents used for developing the coated sample will be described. (Preparation of a developing agent containing reductones) A developing tablet and a fixing tablet were prepared according to the following operations (A) to (D).

(A) Preparation of Tablet A for Developing Agent As a developing agent, sodium erythosorbate 13,000 was used.
g in a commercially available bantam mill until the average particle size is 10 μm. Sodium sulfite 4,880
g, 1-phenyl-3-pyrazolidone (phenidone) 9
75 g, pentasodium diethylenetriaminepentaacetate (D
1,635 g of TPA · 5Na) and 440 g of boric acid are added, mixed in a mill for 30 minutes, and granulated by adding 30 ml of water at room temperature for about 10 minutes in a commercial stirring granulator. Is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the water content of the granulated product.

The granules thus prepared were uniformly mixed with 2,172 g of D-mannitol for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH (relative humidity). Thereafter, the obtained mixture was mixed with a tableting machine modified from Tough Presto Collect 1527HU manufactured by Kikusui Seisakusho for 1 hour.
Perform compression tableting with the filling amount per tablet at 10.3 g,
2,500 developing tablet A preparations were prepared.

(B) Preparation of tablet B for development 19,500 g of potassium carbonate, 8.15 g of 1-phenyl-5-mercaptotetrazole, 3,250 g of sodium hydrogen carbonate, glutaraldehyde sulfite adduct 650
g and 1,354 g of D-mannitol are pulverized and granulated in the same manner as in the operation (A). The amount of water to be added is 30.0 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material.

The mixture thus obtained was charged in a tableting machine similar to the one used in the operation (A) in a filling amount per tablet of 9.
The mixture was compressed to 90 g and compression tableting was performed to prepare 2,500 tablets B for development.

(C) Preparation of Fixing Tablet C Preparation: 18,560 g of ammonium thiosulfate, 1,392 g of sodium sulfite, 580 g of sodium hydroxide, and 2.32 g of disodium ethylenediaminetetraacetate were pulverized and granulated in the same manner as in the operation (A). I do. The addition amount of water is 500 ml,
After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules.

The mixture thus obtained was subjected to compression tableting using the above tableting machine at a filling amount per tablet of 8.214 g to prepare 2,500 fixing tablet C preparations.

(D) Preparation of Fixing Tablet D Preparation 186 g of boric acid, aluminum sulfate 18-hydrate 6,500
g, glacial acetic acid 1,860 g, and 925 g of 50% sulfuric acid are pulverized and granulated in the same manner as in the operation (A). The amount of water added is 100m
After the granulation, the mixture is dried at 50 ° C. for 30 minutes to almost completely remove the moisture of the granulated product.

The mixture thus obtained was subjected to compression tableting with the above tableting machine at a filling amount of 4.459 g per tablet to prepare 2,500 tablets D for fixing.

(Preparation of Developing Solution)
Developing solution 16.5 having the following composition using 7 and 254 B agents
One liter was prepared. A starter 330 having the following composition was added to 16.5 liters of the obtained pH 10.70 developer.
Then, the pH was adjusted to 10.45 to obtain a development start solution. Developing solution composition (amount per liter) Potassium carbonate 120.0 g Sodium erythorbate 40.0 g DTPA / 5Na 5.0 g 1-phenyl-5-mercaptotetrazole 0.05 g Sodium hydrogen carbonate 20.0 g Phenidone 3.0 g Sulfurous acid Sodium 15.0 g D-mannitol 15.0 g Glutaraldehyde sulfite adduct 4.0 g Boric acid 1.35 g (Preparation of developer starter) Water was added to 210 g of glacial acetic acid and 530 g of potassium bromide to make the total volume 1 liter.

(Preparation of Fixing Initiation Solution) Fixing Tablet C
Using 237 agents and 149 D agents, 11 liters of a fixing solution having the following composition was prepared and used as a fixing start solution. The pH of the resulting fixing start solution was 4.80. Fixing start solution composition (amount per liter) Ammonium thiosulfate 160.0 g Sodium sulfite 12.0 g Boric acid 1.0 g Sodium hydroxide 5.0 g Glacial acetic acid 10.0 g Aluminum sulfate / 18-hydrate 35.0 g 50% sulfuric acid 5. 0 g Ethylenediaminetetraacetic acid disodium dihydrate 0.02 g (Preparation of replenisher) For both the developer and the fixer, the replenisher contains the above-mentioned developing tablets and fixing tablets, and the respective packaging bags in the refill tablet inlet. Is opened and set. The tablets are put into each built-in chemical mixer, and at the same time, a required amount of hot water at 25 to 30 ° C. is injected. And used as a replenisher for fixing.

(Preparation of a developer containing hydroquinone and no reductone) Part-A (amount per liter of replenisher) Potassium hydroxide 37.5 g Potassium sulfite (50% solution) 170 g Diethylenetetraminepentaacetic acid 10 g Sodium bicarbonate 15 g 5-methylbenzotriazole 0.12 g 5-nitrobenzimidazole 0.04 g 1-phenyl-5-mercaptotetrazole 0.25 g 4-hydroxymethyl-4-methyl-1-phenylpyrazolidone 8.5 g Hydroquinone 30 g Boric acid 5.0 g Sodium octanesulfonate 1.0 g Add water to make up to 500 ml Part-B (amount per liter of replenisher) Glacial acetic acid 10 g 5-Nitroindazole 0.05 g N-acetyl-DL-penicillation Added 0.1g water finish 50ml starter glacial acetic acid 120g Potassium bromide _{225g HO (CH 2) 2 S} (CH 2) 2 S (CH 2) 2 OH 1.0g CH 3 N [(CH _{2) 3} NHCONHCH ₂ CH ₂ SC ₂ H ₅ ] ₂ 1.0 g 5-methylbenzotriazole 1.5 g Add water to finish to 1.0 liter. Developing working solution is prepared by adding Part A, P
artB was added at the same time, and water was added while stirring and dissolving.
Make up to 1 liter and adjust the pH to 10.53 with glacial acetic acid. This is used as a development replenisher.

To 1 liter of the developing replenisher, 20 ml / liter of the above starter was added, and the pH was adjusted to 10.3.
Adjust to 30 and use as working solution.

(Evaluation of Samples) Using the obtained coated samples, experiments (101 to 130) were performed as described below to evaluate the silver tone and the long-term running stability (fog increase width).

<< Silver Tone >> The coated sample was placed on two intensifying screens (KO
-250), X-ray irradiation and exposure were performed at a tube voltage of 80 kVp, adjusting the tube current and irradiation time so that the density after the development processing was 1.1 ± 0.05. Using a modified machine equipped with an automatic developing machine SRX-503 (manufactured by Konica Corporation) equipped with a chemical mixer for tablet dissolution, using any of the above developing solutions and the fixing replenisher, the processing temperature was 35 ° C. for development, 33 ° C. for fixing, and 20 minutes for washing with water.
Each sample was processed at a temperature of 50 ° C. and a drying temperature of 50 ° C., and the processing time was set to be dry to dry for 45 seconds.

When a developer containing no erythorbic acid is used, the developer is prepared in a polyethylene tank outside the automatic developing machine according to the above-mentioned formulation, and the developing solution inside the automatic developing machine is replenished. A supply hose was connected to the replenishing pump of No. 1 and used.

The silver tone of the treated sample was visually evaluated according to the following evaluation criteria. A: Cool black tone B: Slightly yellowish color is felt C: Yellowish color is felt and gives discomfort << Long-term running stability >> Each coated sample is exposed to a new solution without exposure and is similar to the silver color tone evaluation. Processing was performed. Next, for each of the exposed samples in the same manner as the silver tone evaluation, a running solution was prepared by treating each of the samples for 70 pieces in a day at 70 pieces for 2 months to prepare a running solution. Processed.

For each sample, a sample treated with the new solution,
The fog of the sample treated with the running solution for two months is measured,
The difference between the two was evaluated as the fog increase. The smaller the fog rise, the better the long-term running stability.

Table 1 shows the results.

[0128]

[Table 1]

It can be seen that the sample treated by the method of the present invention has a small rise in fog even after the treatment after running for two months.

Example 2 Coated samples 2-1 to 2-16 were prepared in the same manner as coated samples 1-1 to 1-16 of Example 1.

In the preparation of the developing solution, two types of the developing solution containing no erythorbic acid, one containing boric acid in the same amount as in Example 1 and one containing no boric acid, were used.
Experiments (201 to 230) were performed in the same manner as in Example 1 from the preparation of the fixing replenisher to the evaluation of the sample.

Table 2 shows the results.

[0133]

[Table 2]

According to the processing method of the present invention, it can be seen that the silver tone is good and the fog rise during long-term running is extremely small.

[0135]

According to the present invention, first, a silver halide photographic light-sensitive material which does not cause deterioration of silver tone or rise in fog even when a developer using reductones as a developing agent is used for a long period of time. The processing method could be provided. Secondly, a silver halide photographic light-sensitive material and a processing method therefor can be provided which do not cause deterioration of silver tone or rise in fog even when used for a long period of time, even though the developing solution is free of boric acid.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 5/30 G03C 5/30

Claims (4)

[Claims] 1. A support having a silver halide emulsion layer containing tabular silver halide grains on at least one side of a support,
A silver halide photographic material in which the tabular silver halide grains are spectrally sensitized by at least one of sensitizing dyes represented by the following general formulas (I) and (II), A method for processing a silver halide photographic light-sensitive material, comprising processing with a developer containing at least one of the compounds represented by A). Embedded image [Wherein, Z ¹ , Z ² and Z ³ each represent a non-metal atom group forming oxazole, benzoxazole, naphthoxazole, thiazole, benzothiazole or naphthothiazole, and R ¹ , R ² and R ³ each represent , An alkyl group or a substituted alkyl group, R ⁴ represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, X ⁻ represents an acid anion, and n represents 0 or 1. [Chemical formula 2] [Wherein, R ₁ and R ₂ each represent a hydroxyl group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group, or an alkylthio group. P and Q are each a hydroxyl group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group,
A sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or two vinyl carbon atoms bonded to each other and substituted by R ₁ and R ₂ and a carbon substituted by Y Represents a group of non-metallic atoms that form a 5- to 8-membered ring with atoms. Y represents ＯO or ＮＲNR ₃ , and R ₃
Represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group,
Represents a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group. ] 2. A support having a silver halide emulsion layer containing tabular silver halide grains on at least one side of a support,
The tabular silver halide grains are spectrally sensitized with at least one of the sensitizing dyes represented by formulas (I) and (II) to substantially provide boric acid Or a method for processing a silver halide photographic light-sensitive material, wherein the processing is performed with a developer not containing a salt thereof. 3. The tabular silver halide grains have an average aspect ratio of 2.0 to 20.0 and an average thickness of 0.02.
2. A method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the thickness is 1 to 1.0 [mu] m. 4. The tabular silver halide grains have an average aspect ratio of 2.0 to 20.0 and an average thickness of 0.0
3. The method for processing a silver halide photographic material according to claim 2, wherein the thickness is 1 to 1.0 [mu] m.