JPH06175263A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material high in sensitivity and superior in storage stability of a sample with the lapse of time and improved in fluctuation of sensitivity against humidity change at the time of exposure by incorporating a specified silver halide emulsion and a specified cyclic compound in a silver halide emulsion layer. CONSTITUTION:The silver halide emulsion layer contains the spectrally sensitized silver halide emulsion containing >=90mol% silver chloride and the >=9-membered cyclic compound composed of hetero atoms and the moiety of the compound represented by formula in which Q is an atomic group necessary to form a 5- or 6-membered hetero ring optionally condensed with a benzene ring; and M is H, alkali metal, or ammonium. It is preferred that this cyclic compound has a >=4C aliphatic ring and/or <=4 aromatic rings and >=2 ether bonds.

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, and more specifically, it has high sensitivity and is excellent in sensitivity fluctuation due to storage of raw samples with time, and has improved sensitivity fluctuation due to humidity change during exposure. The present invention relates to a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, in order to finish a large amount of prints in a short delivery time, it has been desired to improve the rapid processing performance of a photosensitive material for color photographic paper. As a silver halide emulsion used as one of the methods, it is known to use silver chloride or a silver chlorobromide emulsion having a high silver chloride content to accelerate the process. However, it has been known that silver chloride or a silver chlorobromide emulsion having a high silver chloride content has a drawback of low sensitivity.

Supersensitization method (Supe
rsensitization) is known to be useful. Regarding supersensitization, Photographic Science and Engenee
ring. Volume 13, P. 13-17 (1969), Volume 18, P. 418-
430 (1974), T.W. H. James The Theory of th
e Photographic Process 4th Edition, Macmillan Publishers, 1
977, P. It is known that high sensitivity can be obtained by selecting an appropriate sensitizing dye and a supersensitizer (Supersensitizer).

Conventionally, as supersensitizers, many compounds such as stilbene, azaindene, mercaptoheterocycle, thiourea or a condensate of phenol and hexamethylenetetramine have been known. For example, US Pat.
875,058, 3,340,064, 3,457,078, 3,458,3
No. 18, No. 3,615,632, No. 3,695,888, No. 4,011,083
And JP-A-61-203447. However, when these silver halide emulsions were supersensitized by these conventional techniques, the sensitivity was not sufficiently increased, and there was a problem that the photographic sensitivity varied greatly due to storage of raw samples.

The stability of a photographic light-sensitive material during storage is extremely important from the viewpoint of preventing deterioration of the quality of finished prints, and these techniques are not practically preferable.

Japanese Unexamined Patent Publication (Kokai) No. 2-100048 discloses that a silver halide light-sensitive material contains crown ethers, cyclodextrins and the like as coagulation-disrupting compounds for magenta dyes. However, this technique is for improving the stability of the magenta dye, and does not give any suggestion about the supersensitizing effect of these compounds.

JP-A-4-25833 describes that a tetrazole derivative having a cyclic structure as a chelating agent in the molecule supersensitizes a silver bromide emulsion. However, no supersensitizing effect on silver chloride or silver chloride-rich silver chlorobromide is described. In addition, the results of studies conducted by the present inventors show that the use of a tetrazole derivative having a cyclic structure as a chelating agent for silver chloride-rich silver chlorobromide as a supersensitizer has a small sensitizing effect, and the humidity during exposure is high. It was found that the change in sensitivity was large with respect to the change.

[0008]

In contrast to the problems described above, the object of the present invention is to provide a high sensitivity and excellent storability of a sample over time, and to improve the sensitivity fluctuation with respect to humidity change during exposure. The object is to provide a silver halide photographic light-sensitive material.

[0009]

The above object of the present invention is to provide a silver halide photographic light-sensitive material in which at least one photosensitive emulsion layer containing a silver halide emulsion is provided on a support. Mainly contains silver chloride 90 mol%
It has the above-described spectrally sensitized silver halide emulsion, and contains at least one compound represented by the general formula [S] (Formula 1) and a 9-membered or more cyclic compound containing a hetero atom. And a silver halide photographic light-sensitive material.

The above-mentioned cyclic compound has an aliphatic ring and / or an aromatic and ether bond, the aliphatic ring of the cyclic compound is 4 or less, and the cyclic compound is 2 or more aromatic. It is a preferred embodiment that the compound has a ring and an ether bond, and that the cyclic compound is represented by the general formula [I] (Formula 2), and the range of spectral sensitization is the maximum wavelength.
A thickness of 600 nm or more is also a preferred embodiment.

The details of the present invention will be described below.

First, the compound represented by the general formula [S] will be described.

In the general formula [S], the 5-membered heterocycle represented by Q is, for example, an imidazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, a selenazole ring, a benzimidazole ring, a naphthimidazole ring, a benzothiazole ring. , A naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, a benzoxazole ring, and the like, and the 6-membered heterocycle represented by Q is
Pyridine ring, pyrimidine ring, quinoline ring and the like,
These 5- or 6-membered heterocycles also include those having a substituent.

In the general formula [S], examples of the alkali metal atom represented by M include sodium atom and potassium atom.

The mercapto compound represented by the general formula [S] is preferably a mercapto compound represented by each of the following [S-1], [S-2], [S-3] and [S-4].

[0016]

[Chemical 3]

[Wherein R ₁ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen atom, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or an amino group, and Z represents —NH—, — Represents O- or -S-, M
Is the same as M in the general formula [S]. ]

[0018]

[Chemical 4]

In the formula, Ar represents a group represented by the following (formula 5),

[0020]

[Chemical 5]

R ₂ represents an alkyl group, an alkoxy group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, an amino group, an acylamino group, a carbamoyl group or a sulfonamide group. n represents an integer of 0 to 2. M has the same meaning as M in formula [S].

In the general formulas [S-1] and [S-2], examples of the alkyl group represented by R ₁ and R ₂ include methyl group, ethyl group and butyl group, and examples of the alkoxy group include methoxy group. , Ethoxy group and the like, and examples of the salt of carboxyl group or sulfo group include sodium salt, ammonium salt and the like.

In the general formula [S-1], examples of the aryl group represented by R ₁ include phenyl group and naphthyl group, and examples of the halogen atom include chlorine atom, bromine atom and the like.

In the general formula [S-2], examples of the acylamino group represented by R ₂ include methylcarbonylamino group and benzoylamino group, and examples of the carbamoyl group include ethylcarbamoyl group and phenylcarbamoyl group. Examples of the sulfonamide group include a methylsulfoamide group and a phenylsulfoamide group.

The above-mentioned alkyl group, alkoxy group, aryl group, amino group, acylamino group, carbamoyl group, sulfonamide group and the like also include those further having a substituent.

[0026]

[Chemical 6]

In the formula, Z represents --NR _3- , an oxygen atom or a sulfur atom. R ₃ is a hydrogen atom, an alkyl group, an aryl group,
Alkenyl group, cycloalkyl group, -SR ₃₁ , -NR
_{32 (R 33) -, -} NHCOR 34, -NHSO 2 R represents ₃₅ or a heterocyclic group, R ₃₁ is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, -COR _34, or -SO ₂ R ₃₅ represents R ₃₅ , R ₃₂ and R ₃₃ represent a hydrogen atom, an alkyl group, or an aryl group, and R ₃₄ and R ₃₅ represent an alkyl group or an aryl group. M has the same meaning as M in formula [S].

R ₃ , R ₃₁ , R in the general formula [S-3]
Examples of the alkyl group represented by ₃₂ , R ₃₃ , R ₃₄ and R ₃₅ include a methyl group, a benzyl group, an ethyl group and a propyl group, and an aryl group includes a phenyl group and a naphthyl group.

Examples of the alkenyl group represented by R ₃ and R ₃₁ include a propenyl group and the like, and examples of the cycloalkyl group include a cyclohexyl group and the like. Examples of the heterocyclic group represented by R ₃ include furyl group and pyridinyl group.

The above R ₃ , R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ and R
An alkyl group and an aryl group represented by ₃₅ , R ₃ and R ₃₁
The alkenyl group and cycloalkyl group represented by and the heterocyclic group represented by R ₃ also include those having a substituent.

[0031]

[Chemical 7]

In the formula, R ₃ and M are each represented by the general formula [S-
3] represents a group having the same meaning as R ₃ and M in 3]. R ₃₁ and R ₃₂ each represent a group having the same meaning as R ₃₁ and R ₃₂ in formula [S-3].

Specific examples of the compound represented by the general formula [S] are shown below, but the invention is not limited thereto.

[0034]

[Chemical 8]

[0035]

[Chemical 9]

[0036]

[Chemical 10]

[0037]

[Chemical 11]

[0038]

[Chemical 12]

[0039]

[Chemical 13]

The compound represented by the general formula [S] is, for example, JP-B-40-28496, JP-A-50-89034, Journal of Chemical Society (J. Chem. Soc.) 49, 1.
748 (1927), 4237 (1952), Journal of Organic Chemistry (J.Org.Chem.) 39, 2469 (1
965), U.S. Pat. No. 2,824,001, Journal of Chemical Society, 1723 (1951), JP-A-56-111846.
U.S. Patent No. 1,275,701, U.S. Patent No. 3,266,897, No. 2,
The compounds described in No. 403,927 and the like are included, and the synthetic method can also be performed according to the methods described in these documents.

The compound represented by the general formula [S] according to the present invention (hereinafter referred to as the compound [S]) can be contained in the silver halide emulsion layer according to the present invention in water or in any mixture with water. It may be added after being dissolved in a possible organic solvent (eg, methanol, ethanol, etc.). The compound [S] may be used alone, or may be used in combination with another compound represented by the general formula [S], or a stabilizer other than the compound represented by the general formula [S] or an antifoggant. May be.

The compound [S] is added before the formation of silver halide grains, during the formation of silver halide grains, after the formation of silver halide grains and before the start of chemical ripening, during the chemical ripening and during the chemical ripening. At the end, it may be any time from the end of chemical ripening to the coating. Preferably during chemical aging,
It is added at the end of chemical ripening, or after the end of chemical ripening and before coating. The addition may be carried out all at once or may be added in a plurality of times.

The place of addition may be directly added to the silver halide emulsion or the silver halide emulsion coating solution, or may be added to the coating solution for the adjacent non-photosensitive hydrophilic colloid layer and the diffusion at the time of multilayer coating. Therefore, it may be contained in the silver halide emulsion layer according to the present invention.

The addition amount is not particularly limited, but is usually 1 × 10 ^-6 mol to 1 × 10 ^-1 mol, preferably 1 × 10 ^-5 mol to 1 × 10 ^-2 mol per mol of silver halide. It is added in the range of.

Next, the supersensitizer of the present invention will be described.

The supersensitizer of the present invention contains a hetero atom 9
It is a cyclic compound having a member ring or more. The cyclic compound is preferably one having an aliphatic ring and / or an aromatic ring and an ether bond from the viewpoint that the effect of the present invention is great, and the aliphatic ring forming the cyclic compound is preferably 4 or less, and the aromatic ring is The macrocyclic compound contained therein is more preferable, and the macrocyclic compound represented by the general formula [1] (Formula 2) is further preferable.

Representative compounds are crown ethers, which were synthesized by Pedersen in 1967 and reported their unique properties, and have been synthesized in large numbers. These compounds are C.I. J. Pedersen, Journal of American c
hemical Society vol.86 (2495), 7017 to 7036 (1967),
G. W. Gokel, S. H, Korzeniowski, “Macrocyclicpol
yethr synthesis ”, Springer-Verlag. (1982), Oda,
Shono, Tabushi ed. "Chemistry of Crown Ether" Kagaku Dojin (19
78), Tabushi et al. “Host-Guest” Kyoritsu Publishing (1979), Sasaki, Koga “Organic Synthetic Chemistry” Vol 45 (6), 571-582 (1)
987) etc. in detail.

Specific examples of the cyclic compound used in the present invention are shown below, but the present invention is not limited thereto.

[0049]

[Chemical 14]

[0050]

[Chemical 15]

[0051]

[Chemical 16]

[0052]

[Chemical 17]

[0053]

[Chemical 18]

[0054]

[Chemical 19]

[0055]

[Chemical 20]

The cyclic compound of the present invention may be added to a hydrophilic colloid containing silver halide grains after it is dissolved in water or a hydrophilic organic solvent such as methanol, ethanol or fluorinated alcohol and then added. It may be added at any time before the emulsion is coated, but it is preferably added before the completion of the chemical sensitization. The addition amount of the macrocyclic compound of the present invention varies depending on the kind of the compound, but is usually 1 × 10 ⁻⁶ to 1 × 10 ⁶ per mol of silver halide.
It is in the range of ^-1 mol, preferably 5 x 10 ^-6 to 1 x 10 ^-2 mol.

The supersensitizer of the present invention is preferable for the red-sensitive sensitizing dye because of its large effect of the present invention. Of the red-sensitive sensitizing dyes, the cyanine dyes represented by the general formulas [2] and [3] are particularly useful.

[0058]

[Chemical 21]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent an alkyl group, an alkenyl group or an aryl group.
L ₁ , L ₂ , L ₃ , L ₄ and L ₅ each represent a methyl group. Z ₁ , Z ₂ , Z ₃ and Z ₄ are 5 or 6 respectively.
Represents an atom or group of atoms necessary to complete a heterocyclic nucleus of a member. Z ₅ represents the number of carbon hydrogen atoms required to form a 6-membered ring. m ₁ , m ₂ , m ₃ and m ₄ are 0 or 1 respectively
Represents n represents 0 or 1. X ⁻ represents an acid anion. Y ₁ and Y ₂ each represent 0 or 1, and when the compound forms an intramolecular salt, Y ₁ and Y ₂ each represent 0.

In the sensitizing dye used in the present invention, the alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ of the general formula [2] or [3] may be branched. More preferably, it has 10 or less carbon atoms and may have a substituent. Examples of the substituent include sulfo, aryl, carboxy, amine (primary, secondary, tertiary), alkoxy, aryloxy, hydroxy, alkoxycarbonyl, acyloxy, acyl, aminocarbonyl, and cyan groups, and a halogen atom. be able to. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
Sulfoethyl group, sulfopropyl group, sulfobutyl group,
Benzyl group, phenethyl group, carboxyethyl group, carboxymethyl group, dimethylaminopropyl group, methoxyethyl group, phenoxypropyl group, methylsulfonylethyl group, pt-butylphenoxyethyl group, cyclohexyl group, octyl group, decyl group, carbamoylethyl Base,
Sulfophenethyl group, sulfobenzyl group, 2-hydroxy
-3-sulfopropyl group, ethoxycarbonylethyl group,
2,3-disulfopropoxypropyl group, sulfopropoxyethoxyethyl group, trifluoroethyl group, carboxybenzyl group, cyanopropyl group, p-carboxyphenethyl group, ethoxycarbanylmethyl group, bivaloylpropyl group, propionylethyl group, Anisyl group, acetoxyethyl group, benzoyloxypropyl group, chloroethyl group, morpholinoethyl group, acetylaminoethyl group, N-
Examples thereof include an ethylaminocarbonylpropyl group and a cyanoethyl group.

The alkenyl group is preferably an alkenyl group having 10 or less carbon atoms, and examples thereof include an allyl group, a 2-butenyl group and a 2-propynyl group.

The aryl group is, for example, a phenyl group, a carboxyphenyl group or a sulfonyl group.

L ₁ , L ₂ , L of the general formula [2] or [3]
_3, methine groups represented by L ₄ and L ₅ may have a substituent, if having a substituent represented by the formula (-CR ₅ =), as the group represented by the R ₅ Is a linear or branched alkyl group having about 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, carboxyl group, benzyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, etc.) , And aryl groups (eg, phenyl group, tolyl group, etc.) and the like.

[0064] X in the general formula [2] and [3] ^- anion represented by, for example, chloride, bromide, iodide, perchlorate ion, fluoride Moto硼periodate ions, p-
Toluene sulfonate ion, ethyl sulfonate ion,
Examples thereof include methyl sulfonate ion and nitrate ion.

Further, among the sensitizing dyes represented by the above general formula [2] or [3], particularly useful sensitizing dyes can be represented by the following general formulas [4] and [5].

[0066]

[Chemical formula 22]

In the formula, Y ¹ , Y ² , Y ³ and Y ⁴ each represent an oxygen atom, a sulfur atom or a selenium atom.

A ¹ , A ² , A ³ , A ⁴ , B ¹ , B ² , B ³ , B ⁴ , C ¹ ,
C ² , C ³ , C ⁴ , D ¹ , D ² , D ³ and D ⁴ each represent a hydrogen atom, a halogen atom, an alkyl atom, an alkoxy group, a phenyl group, a cyano group, a nitro group or an alkoxycarbonyl group, A ¹ and B ¹ , B ¹ and C ¹ , C ¹ and D ¹ , A ² and B ² , B ² and
C ² , C ² and D ² , A ³ and B ² , B ³ and C ³ , C ³ and D ³ , A ⁴ and B ⁴ , B ⁴ and C ^4.
At least one of the combination of C ⁴ and D ⁴ may combine with each other to form a benzene ring. R ⁵ and R ⁶ each represent a lower alkyl group. R ¹ , R ² , R ³ , R ⁴ , L ¹ , L ² ,
L ³ , L ⁴ , L ⁵ , X ⁻ , n ¹ , Y ¹ and Y ² are respectively R ₁ , R ₂ , R ₃ , R ₄ , L ₁ in the general formula [2] or [3],
It is synonymous with L ₂ , L ₃ , L ₄ , L ₅ , X ⁻ , n ¹ , Y ₁ and Y ₂ .

A ¹ , A ² , A ^{3 of} the general formula [4] or [5],
The alkyl group represented by A ⁴ , B ¹ , B ² , B ³ , B ⁴ , C ¹ , C ² , C ³ , C ⁴ , D ¹ , D ² , D ³ and D ⁴ has 1 carbon atom. ~
About 5 linear or branched lower alkyl groups (eg, methyl group, ethyl group, propyl group, butyl group, trifluoromethyl group, etc.) and alkoxy groups have 1 carbon atom
~ About 5 linear or branched alkoxy groups (eg, methoxy group, ethoxy group, etc.), halogen atoms such as fluorine, chlorine, bromine or iodine atoms, and phenyl groups such as phenyl without substituents. Examples of the alkoxycarbonyl group such as a group, a hydroxyphenyl group and a carboxyphenyl group include a methoxycarbonyl group and an ethoxycarbonyl group. In addition, n ¹ represents 0 or 1, but is preferably 1.

Next, specific examples of the red-sensitive sensitizing dye of the present invention will be described, but the present invention is not limited thereto.

[0071]

[Chemical formula 23]

[0072]

[Chemical formula 24]

[0073]

[Chemical 25]

The above-mentioned red-sensitizing sensitizing dye is described in, for example, F.M.Harmer, (The Chemistry of Heterocylic Comp.
ounds) Volume 18, (The Cyanine Dyes and Related Comp
ounds) (A.Weissherger ed.Interscience, New Yo
rk 1964) and can be easily synthesized.

The addition amount of the above-mentioned red-sensitive sensitizing dye is not particularly limited, but it is preferable to use 2 × 10 ⁻⁸ mol to 1 × 10 ⁻² mol per mol of silver halide.

Any known blue-sensitive sensitizing dye and green-sensitive sensitizing dye may be used. As the blue-sensitive sensitizing dye, BS described in Japanese Patent Application No. 2-51124, pages 108 to 109 may be used.
-1 to 8 can be preferably used. Examples of the green-sensitizing sensitizing dye include GS-
1-5 are preferably used.

In the silver halide photographic light-sensitive material of the present invention, the silver halide grain emulsion of the present invention contains silver chlorobromide grains or chloride containing substantially no silver iodide and containing 90 mol% or more of silver chloride. It is silver. When substantially free of silver iodide, the silver iodide content is 0.5 mol% or less, preferably
It is 0.1 mol% or less, and more preferably, it is not contained at all. The silver chloride content is preferably 95 mol% or more, more preferably 98 mol% or more, and further preferably 99 mol% or more.

When the silver halide grains of the present invention are silver chlorobromide containing silver bromide, core / shell grains having a different composition within the silver halide grains or a silver bromide localized phase are formed on the grain surface or Although the grains may be contained inside, silver halide grains having a uniform composition from the inside to the surface are preferable.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1 to 2 μm. Is preferred.

The particle size distribution of these particles is
(Standard deviation of particle size distribution divided by average particle size) 20% or less, preferably 15% or less, so-called monodisperse particles are preferable. At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion has a regular crystal form such as a cube, a tetradecahedron or an octahedron, or an irregular crystal form such as a sphere or a plate. Alternatively, a material having a composite form of these can be used.

It may also be a mixture of those having various crystal forms. In the present invention, among these, particles containing 50% or more, preferably 70% or more, and more preferably 90% or more of particles having the above-mentioned regular crystal form are good.

In addition to these, an emulsion having tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more as a projected area of more than 50% of all grains can be preferably used. .

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced in the process of emulsion grain formation or physical ripening. Examples of compounds used include salts of cadmium, zinc, lead, copper, thallium, etc., or salts or complex salts of Group VIII elements iron, ruthenium, rhodium, palladium, osmium, iridium, platinum and the like. it can.
In particular, the above Group VIII elements can be preferably used.
The addition amount of these compounds varies widely depending on the purpose, but is preferably 10 ^-10 to 10 ^-3 mol with respect to the silver halide.

As the apparatus and method for preparing the silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but the one obtained by the simultaneous mixing method. Is preferred. Further, pAg described in JP-A-54-48521 as one form of the simultaneous mixing method
The controlled double jet method can also be used.

Further, a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in the reaction mother liquor described in JP-A-57-92523 and 57-92524.
An apparatus for continuously changing the concentration of water-soluble silver salt and water-soluble halide salt solutions described in German Published Patent No. 2921164, and a reaction mother liquor outside the reactor described in Japanese Patent Publication No. 56-501776. It is also possible to use a device for forming grains while keeping the distance between silver halide grains constant by taking out and concentrating by ultrafiltration.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added and used during the formation of silver halide grains or after the completion of grain formation.

The silver halide emulsion according to the present invention can be used in combination with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and the sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like.

As the gold sensitizer applied to the silver halide emulsion according to the present invention, various gold complexes other than gold chloride silver, gold sulfide, gold thiosulfate and the like can be added. Examples of the pendant compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole.

The amount of the gold compound used depends on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc.
Not uniform but usually 1x per mole of silver halide
It is 10 ^-8 mol.

The silver halide emulsion according to the present invention has the purpose of preventing fog occurring during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuation during storage, and preventing fog occurring during development. Known antifoggants and stabilizers can be used. Examples of compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A No. 2-146036, page 7, lower column, and specific examples thereof include , (IIa-1) to (IIa-8) and (IIb) described on page 8 of the publication.
-1) to (IIb-7) compounds, 1- (3-methoxyphenyl) -5-mercaptotetrazole and the like can be mentioned. These compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, the end of the chemical sensitization step, and a coating solution preparation step depending on the purpose.

In the silver halide photographic light-sensitive material of the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. As the coupler used in the silver halide photographic light-sensitive material according to the present invention, any coupler capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. A compound can be used, but as a typical example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, and a wavelength range of 600 to 600 nm. The one known as a cyan coupler having a spectral absorption maximum wavelength at 750 nm is typical.

A yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is represented by the general formula (Y-
The couplers represented by I) can be mentioned. Specific compounds include those described as YC-1 to YC-9 on pages 9 to 11 of the same specification. Among them, YC-8 and YC-9 described on page 11 of the same specification are preferable because they can reproduce a preferable yellow color.

As the magenta coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention, a general formula (M-
Examples thereof include couplers represented by I) and (M-II). Specific compounds are described in MC-1 on pages 13 to 16 of the specification.
To those described as MC-11 can be mentioned. Among them, MC-8 described on pages 15 to 16 of the same specification.
~ MC-11 is preferable because it has excellent reproduction of colors from blue to purple and red, and also has excellent detail descriptive power.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
The general formula (CI) described in Japanese Patent Application No. 2-234208, page 17,
The coupler represented by (C-II) may be mentioned.
Specific compounds are described in CC-1 to CC-9 on pages 18 to 21 of the specification.
Can be mentioned. When the oil-in-water emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material according to the present invention, it is usually added to a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher, if necessary. And a low-boiling point and / or water-soluble organic solvent are also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. As the high boiling organic solvent that can be used to dissolve and disperse the coupler,
Phthalates such as dioctyl phthalate and phosphates such as tricresyl phosphate are preferably used.

Further, instead of the method using a high boiling point organic solvent, the coupler and the water-insoluble and organic solvent-soluble polymer compound are dissolved in a low boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. It is also possible to employ a method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder. The water-insoluble organic solvent-soluble polymer used at this time is poly (Nt-
Butyl acrylamide) and the like.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described on page 33 of Japanese Patent Application No. 2-234208 and the compound (A'-1) described on page 35 of the specification. And other compounds can be used. Besides, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

For the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

In the present invention, a binder hardener is used. As a hardener, vinyl sulfone type hardener,
Chlorotriazine type hardeners are preferably used. As the vinyl sulfone type hardener, compounds described in JP-A-61-249054, page 25, upper right, line 13 to page 27, upper right, second line can be preferably used. Furthermore, the compound H-12 described on page 26 of the above specification is more preferable. As a chlorotriazine type hardener, JP-A-61-245153, page 3, lower left 1
The compounds described in the 4th line from the lower right of the 3rd page to the 3rd lower line of the lower right of the 3rd page to the lower left of the 5th page are preferably used. Further, the compound represented by XII-1 described on page 4 of the above specification is more preferable. These hardeners are preferably used in combination with different compounds and may be added to any layer.
The hardener is preferably used in an amount of 0.1 to 10% by weight based on the binder.

In the present invention, it is preferable to add an antifungal agent to either layer. As the antifungal agent, preferred compounds are compounds represented by the general formula described in Japanese Patent Application No. 1-298092, page 9. Specific examples of compounds include
Examples of compounds described on pages 69 to 70 of the above specification. 9 to 22 can be mentioned. Of these, particularly preferred compounds are No.
It is a compound represented by 9.

As the reflective support according to the present invention, white pigment-containing polyethylene-coated paper, baryta paper, vinyl chloride sheet, white pigment-containing polypropylene, polyethylene terephthalate support and the like can be used.

Of these, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used in the reflective support according to the present invention, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc and clay. The white pigment is preferably barium sulfate or titanium oxide. The amount of the white pigment contained in the waterproof resin layer on the surface of the reflective support according to the present invention is preferably 10% by weight or more as the content in the waterproof resin layer, and further 13% by weight. The above content is preferable, and 15% by weight or more is more preferable. The dispersity of the white pigment in the water resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method,
The dispersion degree of the white pigment is 0 as the coefficient of variation described in the above publication.
It is preferably 20 or less, more preferably 0.15 or less, and further preferably 0.10 or less.

The silver halide photographic light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or undercoat layer (adhesiveness of the surface of the support, Applied through one or more undercoat layers for improving antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.

The color developing agent used in the color developing solution in the present invention includes aminophenol-based and p-phenylenediamine-based derivatives which are widely used in various color photographic processes.

To the color developing solution applied to the processing of the light-sensitive material of the present invention, known developer component compounds can be added in addition to the above-mentioned primary aromatic amine color developing agent.

The pH value of the color developing solution is usually 9 or more, preferably about 10-13.

The color developing temperature is usually 15 ° C or higher, and generally 20 ° C to 50 ° C. For quick processing
It is preferably carried out at 30 ° C or higher.

The development processing time is generally 10 seconds to 4 seconds.
In terms of minutes, it is preferable to perform the treatment in the range of 10 seconds to 1 minute for the purpose of rapid processing, and in the range of 10 to 30 seconds when further rapid processing is required. The effect of the present invention is more effectively exhibited when such rapid processing is performed.

When the light-sensitive material of the present invention is subjected to a running process while continuously replenishing the color developing replenisher, the replenishing amount of the color developing solution is preferably 20 to 150 ml per 1 m ² of the light-sensitive material, The amount is more preferably 20 to 120 ml, further preferably 20 to 100 ml. The effects of the present invention are more effectively exhibited when such a low replenishment running process is performed. The light-sensitive material of the present invention is subjected to bleach-fixing processing after color development.

After the bleach-fixing treatment, a washing treatment or a stabilizing treatment, or a combined treatment of both treatments is usually carried out.

[0115]

EXAMPLES Examples of the present invention are shown below, but the present invention is not limited thereto.

Example 1 An aqueous solution containing 2.91 g of sodium chloride and 29.8 mg of bromine bromide in 1000 ml of a 2% gelatin aqueous solution kept at 40 ° C. (Liquid A)
And an aqueous solution (solution B) containing 8.5 g of silver nitrate, pAg 6.5, pH
Simultaneously added over 30 minutes while controlling to 3.0, sodium chloride 55.3 g, bromide bromide 565 mg, hexachloroiridate potassium 0.024 mg and hexacyanoferrate potassium 8.4
An aqueous solution containing 4 mg (solution C) and an aqueous solution containing 161 g of silver nitrate (solution D) were added simultaneously over 120 minutes while controlling the pH to 7.3 and pH 5.5.

At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
Desalination was carried out using a 10% aqueous solution of magnesium sulfate and a 30% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size of 0.
40 μm, coefficient of variation (standard deviation of particle size / average particle size) 0.07,
A monodisperse cubic emulsion having a silver chloride content of 99.9 mol% was obtained. The above emulsion was optimally chemically sensitized with sodium thiosulfate and chloroauric acid. Further, the sensitizing dye, supersensitizer and inhibitor shown in Table 1 were added to each of 4 × 10 ⁻⁵ , 2 × 10 ⁻³ and 6 × 10 ⁻⁴ mol per mol of silver halide for spectral sensitization. This gave Em-1 to Em-12.

Next, the cyan couplers CC-1 and CC-2 were dissolved in a mixed solution of dioctyl phthalate (DOP) and ethyl acetate together with the stain inhibitor HQ-1 and the dye image stabilizer ST-1 to give an alkanol B ( It was emulsified and dispersed in an 8% gelatin aqueous solution containing DuPont). This emulsified dispersion was mixed with each of Em-1 to Em-10 of the emulsion to prepare a coating solution, which was coated on a polyethylene-coated paper support to prepare a sample.
101-110 were produced. Gelatin was applied as a protective layer, and the protective layer contained 2,4-dichloro-6-hydroxy-S-triazine sodium (H-1) as a hardener.

The coating contents are shown in Table 3.

Addition amount (g / m ² ) Protective layer Gelatin 1.0 Red sensitive layer Silver chlorobromide emulsion (Em-1 to Em-10) Silver 0.3 Cyan coupler (CC-1) 0.3 Cyan coupler (CC-2) 0.1 Dye image stabilizer (ST-1) 0.2 Anti-staining agent (HQ-1) 0.01 DOP 0.2 Gelatin 1.0 Support Polyethylene laminated paper

[0122]

[Table 1]

[0123]

[Chemical formula 26]

[0124]

[Chemical 27]

The samples thus obtained were evaluated by the following methods.

(Evaluation of Relative Sensitivity) Each sample was subjected to gradation exposure for sensitometry for 0.5 seconds through a red filter, and then subjected to the following development processing. The concentration of the obtained sample was measured using an optical densitometer (PDA-65 type manufactured by Konica Corporation), and the sensitivity was compared between the samples to obtain the relative sensitivity.

(Evaluation of storability) One day after application of each sample, 3 days under the environment of 25 ° C. and 60% (relative humidity).
After storage for a period of one month, exposure and treatment were performed in the same manner as above, and the sensitivities of both were compared.

For sensitivity comparison, the sensitivity of the sample one day after coating was 100%.
The sensitivity of the sample after storage for 3 months was represented by relative sensitivity.

(Evaluation of sensitivity fluctuation due to humidity change during exposure) The ambient temperature during exposure was kept constant at 25 ° C.
The sensitivity was compared by changing it to 15% and 80%, and the sensitivity fluctuation was tested by the change of ambient humidity during exposure. For sensitivity comparison, the sensitivity when the humidity was 15% was 100, and the sensitivity when the humidity was 80% was expressed as relative sensitivity.

[0130] step Temperature Time color development 35.0 ± 0.3 ° C. 45 seconds blix 35.0 ± 0.5 ° C. 45 seconds Stabilization 30 ~ 34 ° C. 90 seconds Drying 60 ~ 80 ° C. 60 seconds color developing solution Pure water 800ml Triethanolamine 10g N, N-diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite 0.3g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0g Ethylenediaminetetraacetic acid 1.0g Catechol-3,5-diphosphonate disodium 1.0 g N-Ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 4.5g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0g Potassium carbonate 27g Add water Adjust the total volume to 1 liter and adjust the pH to 10.10.

Bleach-fixing solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to bring the total volume to 1 liter, and add potassium carbonate or Glacial acetic acid p
Adjust to H = 5.7.

Stabilizing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 1.0 g 1-Hydroxyethylidene 1,1-diphosphonic acid 2.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% Aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.5 g Water is added to make the total volume 1 l, and pH is adjusted with sulfuric acid or potassium hydroxide.
Adjust to 7.0.

The results thus obtained are shown in Table 2.

[0134]

[Table 2]

From the results shown in Table 2, the remarkable effects of the present invention can be seen. That is, samples (101, 10) which do not use the supersensitizer of the present invention.
In the case of 2), the sensitivity of storability is greatly reduced, and the sensitivity changes greatly with changes in humidity during exposure. This sensitivity variation is not improved (104) with the inhibitors of this invention. Although the sample (103) using the supersensitizer of the present invention, which does not use an inhibitor, has improved storage stability, the sensitivity fluctuation with respect to humidity change is conversely deteriorated. However, it can be seen that the samples (105 to 112) using the supersensitizer of the present invention and the inhibitor of the present invention have high sensitivity, excellent storage stability, and little sensitivity fluctuation with humidity.

Example 2 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side where the emulsion layer was coated, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed in a content of 15% by weight was laminated to prepare a reflective support. Each layer having the following constitution was coated on this reflective support to prepare a multilayer silver halide photographic light-sensitive material, Sample 301. The coating liquid was prepared as follows.

26.7 g of yellow coupler (Y-1), 0.67 g of additive (HQ-1) and high boiling point organic solvent (DNP)
To 6.67 g, add 60 ml of ethyl acetate and dissolve.
A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of 10% gelatin aqueous solution containing 9.5 ml of surfactant (SU-1) using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (EM-B1),
A first layer coating solution was prepared. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, (H-2) was added to the second and fourth layers and (H-2) was added to the seventh layer as a hardener. As a coating aid, a surfactant (SU-
2) and (SU-3) were added.

The layer structure is as shown in the table below.

[0139]

[Chemical 28]

[0140]

[Table 3]

[0141]

[Table 4]

[0142]

[Chemical 29]

[0143]

[Chemical 30]

[0144]

[Chemical 31]

[0145]

[Chemical 32]

[0146]

[Chemical 33]

[0147]

[Chemical 34]

(Method for preparing EM-B) 2 kept at 40 ° C.
% Aqueous solution of gelatin containing 2.90 g of sodium chloride and 59.5 mg of bromide (solution A) and solution containing 8.5 g of silver nitrate (solution B) at pAg 6.5 and pH 3.0 of 30%
Simultaneously added over a period of 5 minutes, sodium chloride 55.0 g, bromide bromide 1.13 g, and hexachloroiridium (IV) potassium salt
0.005 mg and potassium hexacyanoferrate (II) trihydrate 3 m
An aqueous solution containing g (Liquid C) and an aqueous solution containing 161 g of silver nitrate (Liquid D) were simultaneously added while controlling the pH to 7.3 and the pH to 5.5.

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
Desalination was carried out using a 10% aqueous solution of magnesium sulfate and a 30% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size of 0.
70 μm, coefficient of variation (standard deviation of particle size / average particle size) 0.09,
A monodisperse cubic emulsion having a silver chloride content of 99 mol% was obtained.

For the above emulsion, sodium thiosulfate,
Optimal sensitization was carried out at 65 ° C. using chloroauric acid, STAB-2, STAB-3 and sensitizing dyes (BS-1, BS-2) to obtain a blue-sensitive silver halide emulsion EM-B.

(Method for preparing EM-G) 2 kept at 40 ° C.
% Aqueous solution of gelatin containing 2.91 g of sodium chloride and 29.8 mg of bromine bromide (solution A) and solution containing 8.5 g of silver nitrate (solution B) at pAg 6.5 and pH 3.0 30
Simultaneously added over a period of 5 minutes, sodium chloride 55.3g, bromide bromide 565mg, potassium hexachloroiridate 0.024
mg and potassium hexacyanoferrate 8.44 mg aqueous solution (C solution) and silver nitrate 161 g aqueous solution (D solution) pAg7.
3. Simultaneously added over 120 minutes while controlling the pH to 5.5.

After the addition is complete, Kao Atlas Co., Ltd. Demol N
Desalination was carried out using a 10% aqueous solution of magnesium sulfate and a 30% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size of 0.
40 μm, coefficient of variation (standard deviation of particle size / average particle size) 0.07,
A monodisperse cubic emulsion having a silver chloride content of 99.9 mol% was obtained. The above emulsion was optimally sensitized at 65 ° C. with sodium thiosulfate, chloroauric acid, the following compound (STAB-1) and sensitizing dye (GS-1) to produce a green-sensitive silver halide emulsion E.
MG was obtained.

[0153]

[Chemical 35]

Based on the samples thus obtained, emulsions of the red-sensitive layer were replaced as shown in Table 6 to prepare photographic materials, and these samples were designated as 201 to 212.

The samples thus obtained were evaluated for sensitivity, storability and sensitivity fluctuations with respect to changes in humidity during exposure in the same manner as in Example 1. The results for the red sensitive layer are shown in Table 8.
The development processing was performed in the following steps.

(Processing step) Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C 27 seconds 81 ml / m ² Bleach-fixing 35.0 ± 0.5 ° C 27 seconds 54 ml / m ² stable 30-34 ° C 90 seconds 150 ml / m ² Dry The composition of the development processing solution is shown below.

(Color developer tank liquid) Pure water 800 ml Diethylene glycol 10 g Potassium bromide 0.01 g Potassium chloride 3.5 g Potassium sulfite 0.25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline Sulfate 6.5g N, N-diethylhydroxylamine 3.5g Ethylhydroxylamine disulfonate 3.5g Triethanolamine 10.0g Diethylenetriaminepentaacetic acid sodium salt 2.0g Optical brightener (4,4'-diaminostilbenesulfonic acid derivative) 2.0g 30 g of potassium carbonate Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.10.

(Color developer replenisher) Pure water 800 ml Diethylene glycol 10 g Potassium sulfite 0.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 10.5 g N, N-diethyl Hydroxylamine 6.0 g Ethyl disulfonate Hydroxylamine 6.0 g Triethanolamine 10.0 g Diethylenetriamine pentaacetic acid sodium salt 2.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 2.5 g Potassium carbonate 30 g Adjust the pH to 10.60 with 1 liter.

Bleach-fixing Bleach-fixing replenisher tank solution diethylenetriaminepentaacetic acid ferric ammonium dihydrate 100g 50g diethylenetriaminepentaacetic acid 3g 3g ammonium thiosulfate (70% aqueous solution) 200ml 100ml 5-amino-1,3,4-thiadiazole-2 -Thiol 2.0 g 1.0 g Ammonium sulfite (40% aqueous solution) 50 ml 25 ml PH 6.5 7.0 Add water to make the total volume 1 liter, and adjust the pH with aqueous ammonia or glacial acetic acid.

(Stable tank solution and replenisher) Orthophenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightening Agent (Tinopearl SFP) 2.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8g PVP (Polyvinylpyrrolidone) 1.0g Ammonia water (25% ammonium hydroxide aqueous solution) 2.5g Ethylenediaminetetraacetic acid 1.0g Ammonium sulfite (40% aqueous solution) ) Add 10 ml water to make the total volume 1 liter, and adjust to pH = 7.5 with sulfuric acid or aqueous ammonia.

Stabilization was supplemented by a three-stage multi-stage countercurrent system.

A running treatment was carried out using the color paper and the treatment liquid thus prepared. In the running process, an automatic processor was filled with the above-mentioned color developing solution, bleach-fixing tank solution and stability tank solution, and the above-mentioned color replenishing solution, bleach-fixing replenishing solution and stable replenishing solution were added every 3 minutes while processing the color paper sample. This was done while replenishing the liquid.

The results obtained are shown in Table 5.

[0164]

[Table 5]

From the results shown in Table 5, the combination of the supersensitizer and the inhibitor of the present invention has high sensitivity, excellent storability of the sample, and small fluctuation in sensitivity to humidity change during exposure. The remarkable effect of the present invention can be seen also in the silver halide photographic light-sensitive material.

Among the supersensitizers of the present invention, a cyclic compound having an aromatic ring has a large sensitizing effect, and a cyclic compound having two aromatic rings has a large sensitizing effect and is preferable.

[0167]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having high sensitivity, excellent storability of a sample with time, and small sensitivity fluctuation with respect to humidity fluctuation during exposure.

Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one light-sensitive emulsion layer containing a silver halide emulsion on a support, wherein the silver halide emulsion layer mainly contains silver chloride in an amount of 90 mol% or more. Halogenated having a sensitized silver halide emulsion and containing at least one compound represented by the following general formula [S] and a 9 or more-membered cyclic compound containing a hetero atom. Silver photographic light-sensitive material. [Chemical 1] [In the formula, Q represents a group of atoms necessary for forming a 5-membered or 6-membered heterocycle or a 5-membered or 6-membered heterocycle bonded to a benzene ring, and M represents a hydrogen atom, an alkali metal atom, or Represents an ammonium group. ] 2. The silver halide photographic light-sensitive material according to claim 1, wherein the cyclic compound has an aliphatic ring and / or an aromatic bond and an ether bond. 3. The silver halide photographic light-sensitive material according to claim 2, wherein the cyclic compound has 4 or less aliphatic rings. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the cyclic compound has two or more aromatic rings and an ether bond. 5. The silver halide photographic light-sensitive material according to claim 1, wherein the cyclic compound is represented by the following general formula [I]. [Chemical 2] [In the formula, R _{1 to} R ₄ are each a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, an alkenyloxy group, an acylamino group, a halogen atom, an alkylthio group, an arylthio group, an alkoxycarbonyl group. Represents an acyloxy group, an acyl group or a sulfonamide group. When two groups of R _{1 to} R ₄ are linked to each other,
A 6-membered ring may be formed. X represents a divalent group containing an oxygen atom or a nitrogen atom. ] 6. The spectral sensitization range has a maximum wavelength of 600 nm.
It is above, The silver halide photographic light-sensitive material of any one of Claims 1-5 characterized by the above-mentioned.