JPH08328191A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material which has high sensitivity and less fogging, and prevents photographic characteristics from changing due to a long-time storage by containing a specific compound in a silver halide emulsion layer or other hydraulic collide layer. CONSTITUTION: At least a layer of silver halide emulsion layers contains photographic sensitive silver halide grains sensitized by selenium or tellurium. At least one kind selected from among compounds expressed by formula I or formula II is contained in the silver halide emulsion layer or other hydrophilic collide layer in relation of water permeability therewith. In the formula, (M) expresses hydrogen atom, a metal atom, or a quaternary ammonium; (Q) which connects to carbon atom and nitrogen atom expresses a nonmetal atom group necessary for forming a monocyclic compound or a condensed heterocyclic compound together with them; (L) expresses a divalent group; (n) expresses an integer of 0-2, and each of R<1> -R<4> expresses hydrogen atom, a cation, or a substituent respectively.

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 particularly to a silver halide photographic light-sensitive material which has high sensitivity, has less fog, and is free from fluctuations in photographic characteristics due to storage over time.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material is superior to other light-sensitive materials in terms of high sensitivity, high resolution and economy, but since it is an image forming system utilizing a chemical reaction, There is a problem that the photographic performance tends to fluctuate during storage over time. Although it is impossible to completely eliminate the temporal change in photographic performance, many researchers have been making studies to reduce it.

As a method for preventing fluctuations in photographic performance, particularly fog, which may occur during storage with time or during development, for example, 1-phenyl-5-mercaptotetrazole, benzotriazole, benzimidazole, or indazoles are used. It is known to add a heterocyclic compound such as the above to a light-sensitive material or a processing liquid, and US Pat. Nos. 3,295,976 and 3,376,310 are known.
No. 3, No. 3,615, 616, No. 3,071, 46
No. 5, No. 3,420,664, No. 2,403,9
No. 27, No. 3,157,509, No. 3,082,
No. 088, No. 3,137,578, No. 3,14
No. 8,066, No. 3,511,663, No. 3,1
06,467, 3,420,670, 1,
763,990, 2,271,229, British Patents 919,061, 768,438 and 2
71,475, 1,344,548, German Patents 617,712, 708,424 and 6
No. 35,769, No. 2,205,539, Belgian Patent No. 671,402, Japanese Patent Laid-Open No. 50-37436, and the like. Particularly in recent years, research on 1-phenyl-5-mercaptotetrazole derivatives has been vigorously carried out, and Japanese Patent Publications No. 61-23542 and 61-47.
415, 63-65137, and JP-A-59-710.
No. 47, Japanese Patent Publication No. 25494/1990 and the like have been proposed. However, even with these compounds, there remain problems that the effect of preventing fluctuations in photographic performance during storage with time is not sufficient, or that sensitivity is lowered.

In recent years, the sensitization of photographic light-sensitive materials has been remarkable, and the introduction of tabular silver halide grains and the introduction of selenium sensitization, tellurium sensitization, or reduction sensitization has become a new sensitization technique. Being tried. However, since all of these techniques tend to increase the sensitivity of the light-sensitive material and unnecessarily increase the fog, the development of a technique that effectively reduces the fog while maintaining the sensitivity and further enhances the storage stability over time. Was longed for.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material having high sensitivity, less fog, and prevented from changing photographic characteristics due to storage over time.

[0006]

The above object of the present invention has been achieved by the following constitution.

(1) In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is selenium-sensitized or tellurium-sensitized. And a hydrophilic colloid layer containing a photosensitive silver halide grain and having a water-permeable relationship with the silver halide emulsion layer, represented by the following general formula [I] or general formula [II]. A silver halide photographic light-sensitive material comprising at least one selected from the compounds described below.

[0008]

Embedded image

[In the formula, M is a hydrogen atom, a metal atom, or 4
It represents a primary ammonium group. Q represents a group of non-metal atoms necessary for bonding to a carbon atom and a nitrogen atom and forming a monocycle or a condensed heterocycle with them. L represents a divalent group, and n represents an integer of 0-2. R ¹ , R ² , R ³ and R
⁴ represents a hydrogen atom, a cation, or a substituent,
R ¹ and R ² , or R ³ and R ⁴ may be the same or different,
Also, they may be bonded to each other to form a ring. (2) In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, at least one silver halide emulsion layer is reduction-sensitized to obtain a photosensitive silver halide. The silver halide emulsion layer or other hydrophilic colloid layer having water permeability to the silver halide emulsion layer, which contains grains, is selected from the compounds represented by the above formula [I] or [II]. A silver halide photographic light-sensitive material comprising at least one kind.

(3) In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is a photosensitive halogen having an aspect ratio of 2 or more. Contains silver halide grains,
In the silver halide emulsion layer or another hydrophilic colloid layer having a water-permeable relationship with the silver halide emulsion layer, at least one selected from the compounds represented by the general formula [I] or the general formula [II].
A silver halide photographic light-sensitive material comprising a seed.

The present invention will be specifically described below.

The compounds represented by the general formulas [I] and [II] of the present invention will be described.

In the general formulas [I] and [II],
As the metal atom represented by M, Li, Na, K, Mg,
Ca, Zn, Ag, etc. are mentioned. Examples of the quaternary ammonium group include NH ₄ , N (CH ₃ ) ₄ and N (C
₄ H ₉ ) ₄ , N (CH ₃ ) ₃ C ₁₂ H ₂₅ , N (CH ₃ ) ₃ C ₁₆ H
₃₃ , N (CH ₃ ) ₃ CH ₂ C ₆ H _{5 and the} like.

Preferred heterocycles formed by Q include imidazole ring, pyrazole ring, triazole ring, tetrazole ring, oxazole ring, thiazole ring,
Examples thereof include a selenazole ring, a tellurazole ring, an oxadiazole ring, a thiadiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and a benzimidazole ring, a benzoxazole ring, and a benzothiazole ring in which an aromatic ring is condensed. Another preferable example is a tetrazaindene ring.

A preferred divalent group represented by L is
Examples thereof include an alkylene group, an arylene group, a heteroarylene group, an ether group, a thioether group, an imino group, an ester group, an amide group, and a sulfonyl group, and these may be combined to form one divalent group. .

The cations represented by R ¹ , R ² , R ³ and R ⁴ include Na ⁺ , K ⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and N.
Represents inorganic cations such as H ₄ ⁺ , organic cations such as triethylammonium ion and pyridinium ion. If the valences do not match, a cation equivalent to one valence (for example, calcium 1/2 ion in the case of calcium ion) ) Represents.

When R ¹ , R ² , R ³ and R ⁴ represent a substituent, the number of carbon atoms contained therein is preferably 10 or less. Specific examples of the substituents are as described below.

R ¹ and R ² , or R ³ and R ⁴ may be bonded to each other to form a 1,2-ethylene group, a 1,3-propylene group or the like.

In the compound of the general formula [I], R ¹ ,
It is preferable that either one of R ² is a hydrogen atom,
In the compound of general formula [II], it is preferable that either R ³ or R ⁴ is a hydrogen atom.

The organic heterocycle formed by Q and the divalent group represented by L may have a substituent, but when the substituent has a carbon atom, it has 10 or less carbon atoms. It is preferable. Of these substituents and R ¹ , R ² ,
Examples of the substituent represented by R ³ and R ⁴ include those shown below.

(Examples of Substituents) Hydrogen atom, nitro group, nitroso group, cyano group, carboxy group, sulfo group, mercapto group, hydroxy group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) substituted Optionally substituted alkyl group or aralkyl group (eg, methyl group, trifluoromethyl group, benzyl group, chloromethyl group, dimethylaminomethyl group, ethoxycarbonylmethyl group, aminomethyl group, acetylmethyl group, ethyl group, carboxyethyl group , Allyl group, n-
Propyl group, t-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, n-undecyl group etc. Alkenyl group which may be substituted (eg, Vinyl group,
2-chlorovinyl group, 1-methylvinyl group, 2-cyanovinyl group, cyclohexen-1-yl group, etc.) Alkynyl group which may be substituted (eg ethynyl group, 1-propynyl group, 2-ethoxycarbonylethynyl group, etc.) ) An optionally substituted aryl group (for example, a phenyl group,
Naphthyl group, 3-hydroxyphenyl group, 3-chlorophenyl group, 4-acetylaminophenyl group, 2-methanesulfonyl-4-nitrophenyl group, 3-nitrophenyl group, 4-methoxyphenyl group, 4-methylsulfonylphenyl group Group, 2,4-dimethylphenyl group and the like) optionally substituted heterocyclic group (for example, 1-imidazolyl group, 2-furyl group, 2-pyridyl group, 5-nitro-2
-Pyridyl group, 3-pyridyl group, 3,5-dicyano-2
-Pyridyl group, 5-tetrazolyl group, 5-phenyl-1
-Tetrazolyl group, 2-benzothiazolyl group, 2-benzimidazolyl group, 2-benzoxazolyl group, 2-
Oxazolin-2-yl group, morpholino group, etc. Acyl group which may be substituted (eg acetyl group, propionyl group, iso-butyroyl group, 2,2-dimethylpropionyl group, benzoyl group, 3,4-dichlorobenzoyl group) , 3-acetylamino-4-methoxybenzoyl group, 4-methylbenzoyl group, etc.) Sulfonyl group which may be substituted (for example, methylsulfonyl group, ethylsulfonyl group, chloromethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, n
-Octylsulfonyl group, phenylsulfonyl group, 4-
Toluenesulfonyl group etc.) Amino group which may be substituted (for example, amino group, methylamino group, dimethylamino group, ethylamino group, ethyl-3-carboxypropylamino group, ethyl-2-sulfoethylamino group, phenylamino) Group, methylphenylamino group, methyloctylamino group, etc.) optionally substituted alkoxy group (eg, methoxy group, ethoxy group, n-propyloxy group, cyclohexylmethoxy group, etc.) optionally substituted aryloxy group or Heteroaryloxy groups (eg phenoxy group, naphthyloxy group, 4-acetylaminophenoxy group, pyrimidine-2
-Yloxy group, etc., optionally substituted alkylthio group (for example, methylthio group, ethylthio group, n-butylthio group, n-octylthio group, t-octylthio group, ethoxycarbonylmethylthio group, benzylthio group, 2-hydroxyethylthio group) Etc.) An optionally substituted arylthio group or heteroarylthio group (eg, phenylthio group, 4-chlorophenylthio group, 2-n-butoxy-5-t-octylphenylthio group, 4-nitrophenylthio group, 2- Nitrophenylthio group, 4-acetylaminophenylthio group, 1-phenyl-5-tetrazolylthio group, 5-methylsulfonylbenzothiazol-2-yl group, etc.) An optionally substituted ammonio group (for example, ammonio group, Trimethylammonio group, phenyldimethylammonio , Dimethylbenzylammonio group, etc.) optionally substituted carbamoyl group (eg, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, bis- (2-methoxyethyl) carbamoyl group, cyclohexylcarbamoyl group, etc.) optionally substituted Good sulfamoyl group (eg, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, bis- (2-methoxyethyl) sulfamoyl group, di-n-butylsulfamoyl group, etc.) optionally substituted acylamino group (For example, acetylamino group, 2-carboxybenzoylamino group, 3-nitrobenzoylamino group, 3-diethylaminopropanoylamino group, acryloylamino group, etc.) Acyloxy group which may be substituted (for example, acetoxy group, benzoyl group) Shi group, a 2-Butenoiruokishi group,
2-Methylpropanoyloxy group etc.) Sulfonylamino group which may be substituted (for example, methanesulfonylamino group, phenylsulfonylamino group,
2-Methoxy-5-n-methylphenylsulfonylamino group, etc. Alkoxycarbonylamino group which may be substituted (for example, methoxycarbonylamino group, 2-methoxyethoxycarbonylamino group, iso-butoxycarbonylamino group, benzyloxycarbonyl group) Amino group, t-
Butoxycarbonylamino group, 2-cyanoethoxycarbonylamino group, etc.) optionally substituted aryloxycarbonylamino group (eg, phenoxycarbonylamino group, 2,4-nitrophenoxycarbonylamino group, etc.) optionally substituted alkoxy Carbonyloxy group (eg, methoxycarbonyloxy group, t-butoxycarbonyloxy group, 2-phenylsulfonylethoxycarbonyloxy group, benzylcarbonyloxy group, etc.) Aryloxycarbonyloxy group which may be substituted (eg, phenoxycarbonyloxy group, 3-Cyanophenoxycarbonyloxy group, 4-acetoxycarbonyloxy group, 4-t-butoxycarbonylaminophenoxycarbonyloxy group, etc.) optionally substituted aminocarbonyl Amino group (eg, methylaminocarbonylamino group, morpholinocarbonylamino group, N-ethyl-N-phenylaminocarbonylamino group, 4-methylsulfonylaminocarbonylamino group, etc.) optionally substituted aminocarbonyloxy group (eg, dimethyl Aminocarbonyloxy group, pyrrolidinocarbonyloxy group, 4-dipropylaminocarbonyloxy group, etc.) optionally substituted aminosulfonylamino group (for example, diethylaminosulfonylamino group, di-n-butylaminosulfonylamino group, phenylamino) Sulfonylamino group, etc.) Sulfonyloxy group which may be substituted (for example, phenylsulfonyloxy group, methylsulfonyloxy group,
Chloromethylsulfonyloxy group, 4-chlorophenylsulfonyloxy group, etc.) Alkoxy or aryloxycarbonyl group which may be substituted (for example, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, 2-memethoxyethoxycarbonyl group, etc.) Specific examples of the compound represented by the general formula [I] or the general formula [II] are shown in, but the present invention is not limited thereto.

[0022]

Embedded image

[0023]

[Chemical 4]

[0024]

Embedded image

[0025]

[Chemical 6]

[0026]

[Chemical 7]

[0027]

Embedded image

[0028]

[Chemical 9]

The compounds represented by the general formula [I] or the general formula [II] are generally disclosed in US Pat. Nos. 2,585,388 and 3,295,976, JP-A-3-145638, by the present applicant. It can be synthesized by the method described in Japanese Patent Specification (Japanese Patent Application No. 7-81931) filed on Mar. 14, 1995.

Specific examples of the synthetic method are shown below.

(Synthesis of Compound a-1) (Synthesis Example of Exemplified Compound a-1) 0.72 g (5 mmol) of 3-aminophenylboronic acid was mixed with sodium hydroxide (0.10 g).
It is dissolved in an aqueous solution of 2 g (5 mmol) and 3 ml of water and cooled with ice. 0.38 ml of thiophosgene when the liquid temperature is below 5 ℃
Add (5 mmol) and stir. After 10 minutes, the precipitated yellow substance is taken out. The yellow substance taken out is added to an aqueous solution of 1.3 g (20 mmol) of sodium azide in 5 ml of water, and the mixture is refluxed for 5 hours. After cooling, concentrated hydrochloric acid was added to the filtrate from which insoluble substances were filtered off, and a white precipitate was formed when the solution was acidified.
0.53 g of-(5-mercaptotetrazol-1-yl) phenylboronic acid was obtained. Recrystallization was performed with an ethanol / water mixed solvent to obtain 0.14 g of colorless needle crystals. Melting point (m
p)> 270 ° C., negative ion FAB-MS (matrix:
Glycerin) m / e 193 (M + Gly-2H ₂ O) Other compounds can be synthesized in the same manner as above.

The compound represented by formula (I) or formula (II) is a selenium-sensitized or tellurium-sensitized photosensitive silver halide grain, or a reduction-sensitized photosensitive silver halide grain, Alternatively, it may be contained in a silver halide emulsion layer containing a photosensitive silver halide grain having an aspect ratio of 2 or more, or another hydrophilic colloid layer having a water permeability relationship with the silver halide emulsion layer. Here, the term "water-permeable" means that water can be transmitted through each other in an alkaline atmosphere during development processing. For example, other silver halide emulsion layers in direct or indirect contact with the silver halide emulsion layer, or an intermediate layer, an anti-color mixing layer, an antihalation layer, a filter layer, a surface protective layer, etc. are included, but on the opposite side of the support. It does not include the back layer and the like. The compound represented by the general formula [I] or the general formula [II] is preferably contained in the silver halide emulsion layer or its adjacent layer, and the addition amount thereof is preferably 2 × 1.
0 ^{−5 to} 0.2 g / m ² , more preferably 1 × 10 ⁻⁴ to
0.1 g / m ² , particularly preferably 2 × 10 ^{−4 to} 0.05
g / m ² .

The compound represented by the general formula [I] or [II] may be added to the silver halide photographic emulsion in the usual manner. For example, methanol, ethanol, methyl cellosolve, acetone,
It can be dissolved in water or a mixed solvent thereof and added as a solution. Alternatively, it may be added as a dispersion liquid prepared by solid dispersion, emulsion dispersion, ultrasonic dispersion, oil protect dispersion, or the like.

The compound represented by the general formula [I] or the general formula [II] may be added at any stage from the step of producing a photographic emulsion or after the production of a photographic emulsion and immediately before the coating step. The preferred addition time in the present invention is from the end of silver halide grain formation to the end of the coating solution adjusting step.

The amount of the compound represented by the general formula [I] or [II] added to the silver halide photographic emulsion is preferably 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide. , And more preferably 5 × 10 ⁻⁶ to 1 × 10 ⁻² mol.

The silver halide emulsion used in the photographic light-sensitive material of the present invention is characterized by being sensitized with a selenium compound or a tellurium compound.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. Specific examples of selenium sensitizers and their use techniques are disclosed in the following patent specifications. That is, US Pat. Nos. 1,574,944 and 1,602,592,
1,623,499, 3,297,446, 3,297,447, 3,320,069, 3,408,196, 3,408,197, 3 , 442, 653, 3,420, 670, 3,591, 385, Japanese Patent Publications No. 52-34491, No. 52-34492, No. 53-295, and No. 57-22.
090, JP-A-59-180536 and JP-A-59-18.
No. 5330, No. 59-181337, No. 59-187.
No. 338, No. 59-192241, No. 60-1500
No. 46, No. 60-151637, No. 61-24673
No. 8, JP-A-3-42221, JP-A-3-24537, JP-A-3-111838, JP-A-3-116132, and JP-A 3-1.
48648, 3-237450, 4-1683.
No. 8, No. 4-25832, No. 4-25832, No. 4
-32831, 4-96059, 4-1092
No. 40, No. 4-140738, No. 4-147250
No. 4, No. 4-149437, No. 4-184331, No. 4-190225, No. 4-191729, No. 4-1.
95035, 4-271341, 4-34446.
No. 36, No. 5-11385, No. 5-40324, No. 5-224332, No. 5-224333, No. 6-4.
0324, 6-43576, 6-75328.
No. 6, No. 6-110149, No. 6-175258, No. 6-175259, No. 6-180478, and No. 6-2.
08184, 6-208186, 6-2651
No. 18, No. 6-281642, etc., and the selenium sensitizers and the techniques for using them can be used.

The technique for selenium sensitization is HESpen.
cer et al., Journal of Photographic Science, Vol. 31,
It is also disclosed in scientific literature such as pages 158 to 169 (1983).

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate), selenoureas (eg, N,
N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-
Heptafluoropropylcarbonyl selenourea, N,
N, N′-trimethyl-N′-4-nitrophenylcarbonylselenourea etc.), selenoketones (eg selenoacetone, selenoacetophenone etc.), selenoamides (eg selenoacetamide, N, N-dimethylselenobenzamide etc.) , Selenophosphates (for example, tri-p-triselenophosphate, etc.), selenides (diethyl selenide, diethyl diselenide,
And triphenylphosphine selenide). Particularly preferred selenium sensitizers are selenoureas, selenophosphates and selenides.

The selenium compound (selenium sensitizer) preferably used in the chemical ripening of the silver halide emulsion of the present invention is as follows.
A specific example of

[0041]

[Chemical 10]

[0042]

[Chemical 11]

[0043]

[Chemical 12]

[0044]

[Chemical 13]

[0045]

Embedded image

[0046]

[Chemical 15]

With respect to the tellurium sensitizer and the sensitizing method used in the chemical sensitization of the present invention, US Pat.
3,499, 3,320,069, 3,77
No. 2,031, No. 3,531,289, No. 3,65
5,394, British Patent Nos. 235,211 and 1,1.
21,496, 1,295,462, 1,39
6,696, Canadian Patent No. 800,958, JP-A-4-204640, 4-271341, and 4-3.
No. 33043, No. 5-303157, No. 6-2757
No. 3, No. 6-175258, No. 6-175259,
6-180478, 6-208184, 6-
No. 208186, and the like. Mata Journal of C
hemical Society Chemical Comunication, 635 pages (1980), 645 pages (1979), 110 pages.
Page 2 (1979) and Journal of Chemical Societ
The technique described in y Perkin Transaction, page 12191 (1980), etc. can be used.

Examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N, N'-).
Dimethyl tellurourea etc.), phosphine tellurides (eg tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride etc.), telluroamides (eg telluroacetamide, N, N-dimethyl tellurobenzamide etc.), Examples thereof include telluroketones, telluroesters, and isotellurocyanates.

The tellurium compounds (tellurium sensitizers) preferably used for the chemical ripening of the silver halide emulsion of the present invention are described below.
A specific example of

[0050]

Embedded image

[0051]

[Chemical 17]

[0052]

Embedded image

The amount of selenium compound and tellurium compound added is not uniform depending on the compound used, the type of silver halide photographic emulsion, the conditions of chemical ripening, etc., but is usually 1 × 10 ^-8 per mol of silver halide. To 1 × 10 ⁻³ mol, and preferably 5 × 10 ⁻⁸ to 1 × 10 ⁻⁴ mol per mol of silver halide.

The method of addition depends on the properties of the selenium compound and tellurium compound to be used, either by dissolving in water or an organic solvent such as methanol, ethanol or ethyl acetate, alone or in a mixed solvent, or by mixing with a gelatin solution in advance. As disclosed in JP-A-4-140739, it is added during chemical sensitization in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent.

The value of pAg (logarithm of reciprocal of silver ion concentration) at the time of chemical ripening is preferably 6.0 to 10.0, and more preferably 6.5 to 9.5. The pH during chemical ripening is preferably 4 to 9, more preferably 4.
0 to 6.5. The temperature during chemical aging is preferably 40
To 90 ° C, more preferably 45 to 85 ° C.

For chemical ripening of the silver halide emulsion of the present invention, other chemical sensitizers can be used together, and it is particularly preferable to use sulfur sensitizers together.

As the sulfur sensitizer, US Pat.
4,944, 2,410,689, 2,27
8,947, 2,728,668, 3,50
1,313, 3,656,955, West German Application Publication (OLS) 1,422,869, JP-A-55-450.
16, JP-A-56-24937, JP-A-5-16513.
The sulfur sensitizers described in No. 5 and the like can be used. Specific examples thereof include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, and 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, and sulfur simple substance. Are preferred examples. The amount of the sulfur sensitizer added is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc.
It is preferably 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁹ mol per mol of silver halide. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

In the present invention, it is also preferable to use a gold sensitizer together. Specifically, in addition to chloroauric acid, gold thiosulfate, gold thiocyanate, etc., thioureas, rhodanins and other various compounds are also preferable. Gold complexes of The addition amount of the gold sensitizer varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁹ mol per mol of silver halide. It is preferably molar. More preferably 1 × 10 ⁻⁵ mol to 1 × 1
It is ^0-8 mol.

In the present invention, it is preferable to use sulfur sensitization and gold sensitization in combination, and the molar ratio of the selenium sensitizer to the sulfur sensitizer and the gold sensitizer is arbitrary, It is preferable to use a sulfur sensitizer in an equimolar amount or more.

Other chemical sensitizers that can be used in combination are, for example, US Pat. Nos. 2,448,060 and 2,56.
Examples thereof include salts of precious metals such as platinum, palladium and rhodium described in No. 6,245, No. 2,566,263 and the like.

The chemical sensitization of the present invention is carried out in the presence of a thiocyanate (eg, ammonium thiocyanate, potassium thiocyanate, etc.) or a tetra-substituted thiourea (eg, tetramethylthiourea, etc.) which is a silver halide solvent. You can also

In the present invention, general formulas [I] and [II]
It is preferable to use reduction sensitization in combination with the compound (1), which is one of the embodiments of the present invention. By placing the silver halide emulsion in an appropriate reducing atmosphere, the inside of the silver halide grains and / or
Alternatively, reduction sensitizing nuclei can be provided on the grain surface. The reduction sensitization is preferably performed during the growth of silver halide grains described later. As the method of applying during the growth, not only the method of performing reduction sensitization while the silver halide grains are growing, but also the method of performing reduction sensitization with the growth of silver halide grains being interrupted and then performing the reduction sensitization It also includes a method of growing the perceived silver halide grains, and specifically, it is carried out by adding a reducing agent and / or a water-soluble silver salt to the silver halide emulsion.

Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and their derivatives. Other preferred reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like. The amount of the reducing agent added is preferably changed depending on the type of reduction sensitizer, the grain size of the silver halide grains, the composition and crystal habit, the temperature of the reaction system, pH, environmental conditions such as pAg, and for example, thiourea dioxide. In the case of 0.01 to 2 m per mol of silver halide
A range of g is preferred. In the case of ascorbic acid, the amount is preferably 0.2 to 50 g per mol of silver halide. As conditions for reduction sensitization, the temperature is 40 to 80 ° C. and the time is 1
The range of 0 to 200 minutes, the pH of 5 to 11, and the pAg of 1 to 10 are preferable.

Silver nitrate is preferred as the water-soluble silver salt. By adding a water-soluble silver salt, so-called silver ripening, which is a kind of reduction sensitization technique, is performed. The pAg during silver ripening is suitably 1 to 6, and more preferably 2 to 4. Temperature, time, p
The conditions such as H are preferably in the above range.

Further, the action of the reducing agent added at the desired time of particle formation is controlled by adding hydrogen peroxide (water) and its adduct, oxidizing agents such as peroxo acid salt, ozone, I ₂ , and thiosulfonic acid at the desired time. It is preferable to deactivate the reducing agent by adding it to suppress or stop the reducing agent. The oxidizing agent may be added at any time from the time of silver halide grain formation to the time of adding the gold sensitizer in the chemical sensitization step (or chemical sensitizer when the gold sensitizer is not used).

The silver halide emulsion of the present invention may be of any halogen composition such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide, or silver iodochloride. Shimmy et Physic Photographic by P. Grafficides (Paul Montel, 1967); Photographic Emulsion Chemistry by G. E. Duffin (1966, The Focal Press); V. El Gerikman et al. Making and Coating Photographic Emulsion (The Focal Pres
S., published in 1964) and the like, JP-A-51-3
No. 9027, No. 55-142329, No. 58-113.
928, 54-48521 and 58-4993.
No. 8, No. 60-138538, etc., The Photographic Society of Japan Showa 5
It can be prepared by the method on page 88 of the 8th Annual Meeting.
That is, any method such as an acid method, a neutral method, an ammonia method, etc. may be used, and a method of reacting a soluble silver salt with a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof, or a method in which grains are mixed with excess silver ion. Any of a method of forming underneath (reverse mixing method), a method of supplying a soluble silver salt and a soluble halogen salt to a fine seed crystal to grow it, and the like may be used.

The silver halide grain size distribution of the silver halide photographic emulsion may be either narrow or wide, but so-called monodispersity with uniform grain size is preferred.

Specifically, (standard deviation of particle size / average particle size) × 100 = 25 when the size of the distribution is defined by the relative standard deviation (variation coefficient) that can be expressed by the width (%) of the particle size distribution. % Or less, more preferably 20% or less.

The average grain size of the silver halide grains used in the present invention is not particularly limited, but the length of one side when converting the volume into a cube is 0.05 to 2.0 μm, preferably 0.1 to 2.0 μm. It is 1.2 μm.

The silver halide grains contained in the silver halide emulsion of the present invention may have a regular shape such as a cube, octahedron or tetrahedron, or may have an irregular shape such as a tabular twin crystal. It may well be a mixture of both, but it is preferable to contain tabular grains.

A twin is a silver halide crystal having one or more twin planes in one grain. The morphology of twins is classified by Klein and Moiser in the article Photographic Correspondents ( (Photographishe Korrespondenz)
99, 99, 100, 57. Twin grains used in the present invention mainly have an even number of parallel twin planes, and these twin planes may or may not be parallel to each other, but particularly preferably 2 twin planes. It has a twin plane.

Another embodiment used in the present invention is that tabular silver halide grains have an average value (average aspect ratio) of the ratio of grain diameter / thickness (aspect ratio) of 2 or more. Is preferably 3 to 10, and more preferably 4 to 8. In these tabular silver halide grains, the outer wall of the crystal may be substantially composed of {111} planes or {100} planes. Further, it may have both a {111} plane and a {100} plane. In this case, 50% or more of the grain surface is the {111} plane, and more preferably 60% to 90%.
% Is the {111} plane, and particularly preferably 70 to 95%
Is the {111} plane. It is preferable that the planes other than the {111} plane are mainly the {100} plane. This surface ratio utilizes the difference in the adsorption dependence between the {111} plane and the {100} plane in the adsorption of the sensitizing dye [T. Tani, J. Imaging Sci.,
29,165 (1985)].

The tabular silver halide grains used in the present invention preferably have a small thickness distribution. Specifically, when the width of the distribution is defined by (standard deviation of thickness / average thickness) × 100 = width of thickness distribution (%), it is preferably 25% or less, more preferably 20%. It is as follows.

Further, it is preferable that the distribution of the halogen content of each grain in the tabular silver halide grain emulsion of the present invention is also small. Specifically, when the width of distribution is defined by (standard deviation of halogen content / average halogen content) × 100 = width of halogen content (%), it is preferably 25% or less, more preferably It is 20% or less.

The tabular silver halide grains are preferably hexagonal. Hexagonal tabular grains (hereinafter sometimes abbreviated as hexagonal tabular grains) are the main planes ({11
The shape of (1} plane) is hexagonal, and the maximum adjacency ratio thereof is 1.0 to 2.0. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. It is also preferable that the hexagonal tabular grains have rounded corners if the maximum adjacent side ratio is 1.0 to 2.0.
It is also preferable that the tabular grains are substantially circular. The length of a side when the corner is rounded is represented by the distance between the straight line portion of the side and the intersection with the line obtained by extending the straight line portion of the adjacent side. It is preferable that 1/2 or more of each side forming the hexagon of the hexagonal tabular grain be substantially linear, and it is more preferable that the ratio of adjacent sides is 1.0 to 1.5.

The rearrangement of halogenated grains is described, for example, in JFHami.
lton, Phot.Sci.Eng., 57 (1967) and T.Shiozawa, J.Soc.P
It can be observed by a direct method using a transmission electron microscope at low temperature described in hot.Sci.Japan, 35, 213 (1972). That is, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion are placed on the mesh for electron microscope observation, and the sample to prevent damage (printout etc.) due to electron beam In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough.
A clearer observation can be obtained by using an electron microscope of 200 KV or more for particles having a thickness of 25 μm.
The position and number of dislocations in each grain can be determined from the photograph of the grain obtained by such a method. The dislocation position of the silver halide grain is preferably in the region of 0.58 L to 1.0 L when the distance from the center of the grain to the outer surface is L, but more preferably 0.80 L. It occurs in the region of 0.98L. The direction of the dislocation line is approximately from the center to the outer surface, but it often meanders. The center of the silver halide grain is the same as the method described in the summary of Inoue et al., Published in the Proceedings of the Photographic Society of Japan, pages 46 to 48, in which silver halide microcrystals are dispersed in a methacrylic resin and solidified to form a microtome. Focusing on the ultrathin section with the maximum cross-sectional area and the section sample having a cross-sectional area of 90% or more than that,
It is the center of the circle when the smallest circumscribed circle is drawn with respect to the cross section. In the present invention, the distance L from the center to the outer surface
Is defined as the distance between the center of the circle and the point that intersects the outer circumference of the particle when a straight line is drawn outward from the center of the circle.

Regarding the number of dislocations in the silver halide grain,
It is desirable that 50% (number) or more of grains containing one or more dislocations are present, and it is more preferable that the ratio (number) of tabular grains having dislocation lines is high.

In the tabular grains, the grain size is the diameter when the projected image of the grain is converted into a circular image having the same area. The projected area of a grain can be calculated from the sum of the grain areas.

Any of them can be obtained by observing, with an electron microscope, a silver halide crystal sample distributed on the sample stage to the extent that grains do not overlap.

The average projected area diameter of the tabular silver halide grains is represented by the circle equivalent diameter of the projected area of the grains, and is preferably 0.30 μm or more, more preferably 0.30 μm.
m-5 μm, more preferably 0.40 μm-2 μm. The particle size can be obtained by enlarging and projecting the particles with an electron microscope at a magnification of 10,000 to 70,000 and measuring the area of the projected image on the print. Further, the average particle diameter (φi) is defined as the number of measured particle diameters is n, and the frequency of particles having the particle diameter φi is ni.
Can be calculated by the following equation.

Average particle size (φi) = (Σnidi) / n (The number of measured particles is indiscriminately 1,000 or more.) The particle thickness is determined by observing the sample obliquely with an electron microscope. Obtainable. The thickness of the tabular grains of the present invention is preferably 0.03 to 1.0 μm, more preferably 0.05 to 0.5 μm.

The ratio (b / a) of the longest distance (a) between two or more parallel twin planes of the silver halide grain and the thickness (b) of the grain is preferably 5 or more. Is preferably 50% (number) or more.

The twin plane distance (a) can be obtained as follows. That is, the section was observed using the transmission electron microscope described above, and 100 tabular silver halide grains having a cross section cut substantially perpendicular to the principal plane were arbitrarily measured.
Select more than one, measure (a) for each particle,
It can be obtained by the averaging. The average value of (a) is preferably 0.008 μm or more, and more preferably 0.010 μm or more and 0.05 μm or less. or,
While (a) is in the above value range, its coefficient of variation is 35
% Or less, but preferably 30% or less.

Further, in consideration of the factors of aspect ratio and grain thickness, the flatness expressed by the following equation: A = ECD / b ²
Is preferably 20 or more. Here, ECD refers to the average projected diameter (μ) of tabular grains, and (b) is the thickness of grains. Here, the average projected diameter represents the number average of diameters of circles having an area equal to the projected area of tabular grains. The silver halide grain used in the present invention may have a core / shell type structure having at least two layer structures having substantially different halogen compositions or a uniform composition in the silver halide grain, but the core / shell type It is preferable to have a structure. In this case, the grain center may have a halogen composition region different from that of the core. In such a case, the halogen composition of the seed grains may be any combination of silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride and the like. For the method for producing a silver halide grain having a core / shell structure, see, for example, West German Patent No. 1,1.
69,290, British Patent Nos. 1,027,146, JP-A-57-15423, and JP-B-51-141.
The method described in No. 7 etc. can be adopted.

The average silver iodide content of the silver halide emulsion according to the present invention is preferably 20 mol% or less, more preferably 0.1 to 10 mol%. In the grains having a layer structure having different halogen compositions, grains having a high silver iodide layer inside the grain and a low silver iodide layer or a silver bromide layer at the outermost surface layer are preferable. At this time, the silver iodide content of the inner layer (core) having the highest silver iodide content is preferably 2.5 mol% or more, more preferably 5 mol% or more. The silver iodide content of 1) is 0 to 10 mol%, preferably 0 to 8 mol%, and the silver iodide content of the core is at least 3 mol% or more than the silver iodide content of the shell. It is preferable. The silver iodide distribution of the core is usually uniform, but it may have a distribution. For example, the concentration may increase from the center toward the outside, or may have a maximum or minimum concentration in the intermediate region.

In the present invention, so-called halogen conversion type (conversion type) particles may be used. Halogen conversion is 0.2 mol% to 2.0 mol% with respect to silver.
Is preferable, and the conversion may be carried out during physical ripening or after completion of physical ripening. As a method for halogen conversion, an aqueous halogen solution or silver halide fine particles having a smaller solubility product with silver than the halogen composition on the grain surface before halogen conversion is usually added. The particle size at this time is preferably 0.2 μm or less, more preferably 0.02 to 0.1 μm.

The silver iodide content and the average silver iodide content of the silver halide grains are measured by the EPMA method (Electron Probe Micro An
alyzer).
According to this method, a sample in which emulsion grains are well dispersed so that they do not come into contact with each other is prepared, and elemental analysis of a portion smaller than X-ray analysis by electron beam excitation by irradiating an electron beam can be performed.
By this method, the halogen composition of each grain can be determined by obtaining the characteristic X-ray intensities of silver and iodide emitted from each grain. E for at least 100 particles
If the silver iodide content is obtained by the PMA method, the average silver iodide content is obtained from the average of them.

Further, the silver halide grains have a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt), in the process of forming the grain and / or in the process of growing.
At least one metal ion selected from rhodium salts (including complex salts) and iron salts (including complex salts) can be added to contain these metal elements inside the particles and / or in the surface layer of the particles.

In the silver halide photographic emulsion of the present invention, unnecessary soluble salts may be removed at the end of the growth of silver halide grains, or may be contained therein. In the case of removing the salts, Research Disclosure (hereinafter abbreviated as RD) No. 17
It can be carried out based on the method described in Item 643, Item II.

In the present invention, two or more kinds of silver halide emulsions, which are separately formed, can be used by arbitrarily mixing them.

Hydrophilic protective colloids used for preparing the silver halide photographic light-sensitive material of the present invention include Product Licensing Index, Vol. 92, P108.
In addition to gelatin used in ordinary silver halide emulsions as described in the section "Vehicles" of the above, gelatin derivatives such as acetylated gelatin and phthalated gelatin, water-soluble cellulose derivatives and other synthetic or natural hydrophilic agents. A polymer is included.

If necessary, various techniques and additives known in the art can be used in the silver halide photographic light-sensitive material of the present invention. For example, auxiliary layers such as a protective layer, a filter layer, an antihalation layer, a crossover light cut layer, and a backing layer can be provided in addition to the light-sensitive silver halide emulsion layer. Sensitizers, noble metal sensitizers, photosensitive dyes, supersensitizers, couplers, high boiling point solvents, antifoggants, stabilizers, development inhibitors, bleaching accelerators,
Fixing accelerator, color mixing inhibitor, formalin scavenger,
Color tones, hardeners, surfactants, thickeners, plasticizers, slip agents, UV absorbers, irradiation prevention dyes, filter light absorption dyes, antibacterial agents, polymer latex, heavy metals, antistatic agents, matting agents Etc. can be contained by various methods.

These additives described above are described in more detail in Research Disclosure, Vol. 176, Item.
/ 17643 (Dec. 1978), vol. 187 Ite
m / 18716 (November 1979) and Vol. 308 I
tem / 308119 (December 1989).

The types of compounds and the places of description shown in these three Research Disclosures are listed below.

Additives RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 IV Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Supports usable in the light-sensitive material of the present invention include, for example, RD-17643, page 28 and RD.
-308119, page 1009, Product Licensing Index, Volume 92, P108, "Supports"
The items described in the section are included.

Suitable supports include cellulose triacetate, cellulose nitrate, polyethylene terephthalate, polyesters such as polyethylene-2,6-naphthalate, polyolefins such as polyethylene, polystyrene, baryta paper, paper laminated with polyethylene, etc.,
Examples thereof include glass and metal.

In order to improve the adhesion of the coating layer, the surface of these supports is subjected to a surface treatment such as corona discharge treatment, ultraviolet irradiation or installation of an undercoating polymer adhesive layer.

The silver halide photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material containing the above-described light-sensitive silver halide emulsion of the present invention, and for example, a black-and-white silver halide photographic light-sensitive material (for example, medical Sensitive materials, printing sensitive materials, microfilm sensitive materials, negative sensitive materials for general photography, etc.), color photographic photosensitive materials (eg, color negative sensitive materials, color reversal sensitive materials, color printing sensitive materials, etc.), diffusion transfer Examples include photosensitive materials and photothermographic materials.

To develop the silver halide photographic light-sensitive material of the present invention, for example, "Process" in Product Licensing Index, Vol. 92, P110,
T. H. James The Theory of the Photographic Process 4th Edition
Photographic Process, fourth Edition) 291-33
Page 4 and the Journal of the American Chemical Soc
, Society, Vol. 73, page 3,100 (1951), which can be effectively used.

[0100]

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

Example 1 << Preparation of Twin Seed Emulsion (T-1) >> JP-A-5-34851
The seed emulsion (T-1) having two parallel twin planes was prepared by the following method with reference to the description of No.

(Solution A) Ocein gelatin 80.0 g Potassium bromide 47.4 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m ± n = 9.77) 10% by weight methanol solution 0.48 ml Add water 8000.0 ml (Solution B) Silver nitrate 1200.0 g Add water 1600.0 ml (Solution C) Ocein gelatin 32.2 g Potassium bromide 790.0 g Potassium iodide 70.34 g Water 1600.0 ml (Liquid D) Ammonia water (28%) 470.0 ml Using the stirring device described in JP-A-62-160128,
The liquid B and the liquid C were added to the liquid A stirred vigorously at 40 ° C. for 7.7 minutes by the double jet method to generate nuclei. During this period, pBr was kept at 1.60.

Then, the temperature was lowered to 20 ° C. over 35 minutes. Furthermore, the D liquid was added in 1 minute, and then the mixture was aged for 5 minutes. KBr concentration during aging is 0.03 mol /
1 and the ammonia concentration was 0.66 mol / l.

After completion of aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. When the seed emulsion grains were observed with an electron microscope, the average grain size was 0.225 μm, and the ratio of double parallel twin planes was 75% in terms of the number of all grains.

<< Preparation of Emulsion (EM-1) >> 5 shown below
An emulsion (Em-1) was prepared using the various solutions.

(Solution A-1) Ocein gelatin 66.5 g Distilled water 3227.0 ml HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m ± n = 9.77) 2.50 ml of 10% by weight methanol solution Seed emulsion (T-1) 98.5 g Finish to 3500 cc with distilled water (solution B-1) 3.5N silver nitrate aqueous solution 4702.0 ml (solution C-1) potassium bromide 2499.0 g Finish with distilled water to 6000 cc (Solution D-1) Fine grain emulsion consisting of 3% by weight of gelatin and silver iodide grains (average grain size 0.05 μm) (*) Preparation method 6 containing 0.06 mol of potassium iodide 6 7.00 mol of silver nitrate in 5000 ml of a 0.0% by weight gelatin solution, 7.
An aqueous solution containing 06 mol of potassium iodide, 2000 m each
1 was added over 10 minutes. The temperature during particle formation is 4
The temperature was controlled at 0 ° C. The finished weight was 12.53 kg.

(Solution E-1) 1.75N Potassium Bromide Aqueous Solution Necessary amount Solution A-1 was added to a reaction vessel and stirred vigorously.
Solution B-1 to solution D-1 were added according to the simultaneous mixing method according to Table 1 to grow a seed crystal to prepare a core / shell type silver halide emulsion.

Here, (1) addition rates of solution B-1, solution C-1 and solution D-1, (2) solution B-1 and solution C
The addition rate of -1 was changed in a function-like manner with respect to time so as to correspond to the critical growth rate of silver halide grains, and in addition to the growing seed emulsion, small grains were generated and polydispersion was achieved by Ostwald ripening. It was properly controlled so that it would not occur.

The temperature of the solution in the reaction vessel was controlled at 75 ° C. and the pAg was controlled at 8.8 over the entire area of crystal growth. Solution E as needed for pAg control
-1 was added. The pH was not controlled but was maintained in the pH range of 5.0 to 6.0 throughout the grain growth. Table 1 also shows the amount of silver added and the silver iodide content of the silver halide phase during the formation with respect to the addition time of the addition solution.

After grain growth, desalting treatment was carried out according to the method described in JP-A-5-72658, 1.19 l of a 20% by weight gelatin aqueous solution was added, and the mixture was dispersed at 50 ° C. for 30 minutes and then at 40 ° C. to pH. Was adjusted to 5.80 and pBr was adjusted to 3.55.

The silver halide grains contained in the obtained silver halide emulsion had an average grain size of 1.34 μm (diameter in terms of projected area circle), an average aspect ratio of 2.6, and a wide grain size distribution of 18.
% Of monodisperse tabular silver halide grains.

[0112]

[Table 1]

<< Preparation of Emulsion (EM-2) >> Emulsion (EM-
In the preparation of 1), pAg in the reaction vessel during grain growth
Was controlled to 9.3, and the addition rates of the solutions B-1, C-1 and D-1 were changed so as to be commensurate with the critical growth rate of silver halide grains. An emulsion (EM-2) was prepared in the same manner.

The silver halide grains contained in the obtained silver halide emulsion had an average grain size of 1.51 μm (diameter in terms of projected area circle), an average aspect ratio of 3.7, and a grain size distribution width of 21.
% Of monodisperse tabular silver halide grains.

<< Preparation of Emulsion (EM-3) >> Emulsion (EM-
In the preparation of 1), pAg in the reaction vessel during grain growth
Was controlled to 9.8, and the addition rates of solutions B-1, C-1 and D-1 were changed so as to be commensurate with the critical growth rate of silver halide grains. An emulsion (EM-3) was prepared in the same manner.

The silver halide grains contained in the obtained silver halide emulsion had an average grain size of 1.60 μm (diameter in terms of projected area circle), an average aspect ratio of 4.4, and a grain size distribution width of 22.
% Of monodisperse tabular silver halide grains.

<< Preparation of Emulsion (EM-4) >> Emulsion (EM-
In the preparation of 3), after the addition of Solution B-1 to Solution D-1 was started, when 6% of the total amount of added silver was added, the pH was adjusted to 8.0 using a 10% aqueous potassium hydroxide solution. Further, after grain growth, desalting treatment was carried out according to the method described in JP-A-5-72658, 1.19 l of 20 wt% gelatin aqueous solution was added, and the mixture was dispersed at 50 ° C. for 15 minutes, and then 50
The pAg was adjusted to 1.5 at 3.5 ° C. with a 3.5N potassium bromide aqueous solution, and the following solution H-0 was added thereto with stirring for 30 seconds, followed by stirring for 20 minutes, and then the pH at 40 ° C. was adjusted to 5.
Emulsion (EM-4) was prepared in exactly the same manner except that 80 and pBr were adjusted to 3.55.

(Solution H-0) 0.212 mol fine grain emulsion consisting of 3% by weight of gelatin and silver bromide grains (average grain size 0.04 μm) The history of pH in the reaction vessel was as follows.

Amount of added silver (%) pH 6.0 8.00 10.0 7.51 25.0 6.40 31.0 6.36 100.0 5.84 << Preparation of emulsion (EM-5) >> Solution B-1 to solution in preparation of emulsion (EM-3) An emulsion (EM-5) was prepared in exactly the same manner except that the following solution K-1 was added when 6% of the total amount of added silver had been added after the addition of D-1.

(Solution K-1) An aqueous solution containing 1 × 10 ^-6 mol of thiourea dioxide corresponding to 1 mol of silver of the emulsion (EM-5).

<< Preparation of Emulsion (EM-6) >> JP-A-60-1
An emulsion (EM-6) having the same halogen composition as the emulsion (EM-1) was prepared according to the method described in No. 38538.

The silver halide grains contained in the obtained emulsion (EM-6) were octahedral grains having an average grain size of 0.9 μm (value converted to the length of one side of a cube having the same volume). The breadth of the distribution was 17%.

Table 2 shows the characteristics of the emulsions (EM-1) to (EM-6).

[0124]

[Table 2]

Example 2 << Emulsion Sensitization >> The emulsion (EM-3) prepared in Example 1 was subjected to sensitizing dye S-1 (9.5 ×) at 55 ° C.
10 ^-5 ) mol / mol Ag), S-2 (9.5 × 10 ^-5 ).
Mol / mol Ag), S-3 (9.5 × 10 ⁻⁵ ) mol / mol Ag), sodium thiosulfate (amount shown in Table 3), selenium tellurium sensitizer (amount shown in Table 3), chloride Auric acid (3.2
(X10 ^-6 mol / mol Ag) and ammonium thiocyanate (8.0 × 10 ^-4 mol / mol Ag) were added, and the mixture was aged for a certain period of time to perform optimum spectral sensitization and chemical sensitization.

Then, the stabilizer ST-1 (600 m
g / mol Ag), a comparative antifoggant AF-1 (amount shown in Table 3) and a compound of the present invention (amount shown in Table 3) were added and the temperature was lowered to stabilize the emulsion.

By the above operation, the sensitized emulsion SEM-3a-
SEM-3n was prepared.

[0128]

[Table 3]

<< Preparation of silver halide photographic light-sensitive material >> One side (surface) of a triacetylcellulose film support is subjected to undercoating, and then the support is sandwiched between the surface opposite to the surface subjected to the undercoating. A layer having the following composition was sequentially formed on the (rear surface) from the support side.

Backside first layer Alumina sol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Industries, Ltd.) 0.8 g Backside second layer diacetylcellulose 100 mg Stearic acid 10 m
g Silica fine particles (average particle size 0.2μm) 50m
g Color photographic light-sensitive materials (Sample Nos. 1 to 14) were prepared by sequentially forming each layer having the composition shown below from the support side on the surface of a triacetyl cellulose film support that had been subjected to undercoating.

First layer: Antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Dye (CC-1) 0.02 g High boiling point solvent (Oil-1) 0.20 g High boiling point solvent ( Oil-2) 0.20 g gelatin 1.6 g Second layer: intermediate layer (IL-1) gelatin 1.3 g Third layer: silver halide photosensitive layer Sensitized emulsion (SEM-3a to 3n, as shown in Table 4) 1.8 g (in terms of silver) Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-1) 0.004 g High boiling point solvent (Oil-2) 0.35 g Gelatin 1.0 g Fourth layer: First protective layer (Pro-1) Fine grain silver iodobromide emulsion (average grain size 0.08 μm) 0.3 g UV absorber (UV-1) 0.07 g UV absorber (UV-2) ) 0.10g Additive 1 (HS-1) 0.2g Additive 2 (H S-2) 0.1 g High boiling point solvent (Oil-1) 0.07 g High boiling point solvent (Oil-3) 0.07 g Gelatin 0.8 g Fifth layer: second protective layer (Pro-2) Additive 3 (HS-3) 0.04g Additive 4 (HS-4) 0.01g Polymethylmethacrylate (average particle size 3μm) 0.02g Methylmethacrylate: ethylmethacrylate: methacrylic acid copolymer (3: 3: 4 weight ratio) (average particle size 3μm) 0.13 g Gelatin 0.5 g In addition, in the above-mentioned coated sample, the activators SA-1 and SA-
2, SA-3, viscosity modifiers, hardening agents H-1, H-2, stabilizers ST-2 (weight average molecular weights of 10,000 and 1,100,000) and preservatives DI-1 Was added.

Oil-1: dioctyl phthalate Oil-2: tricresyl phosphate Oil-3: dibutyl phthalate HS-1: hydantoin HS-2: 4-ureidohydantoin HS-3: sulfosuccinate di (2,2,2) 3,3,4,4,5,5,6,6,7,7
-Dodecylfluoroheptyl) sodium salt SA-1: sodium tri-i-propylnaphthalenesulfonate SA-2: sodium di (2-ethylhexyl) sulfosuccinate SA-3: sodium dodecylbenzenesulfonate H-1: 2,4 -Dichloro-6-hydroxy-S-triazine / sodium H-2: 1,2-bis (α-vinylsulfonylacetamido) ethane

[0133]

[Chemical 19]

[0134]

Embedded image

[0135]

[Chemical 21]

[0136]

[Chemical formula 22]

<< Evaluation of Photographic Performance >> Obtained Sample Nos. 1 to 1
Sample No. 14 was divided into two, A and B. Sample A was subjected to wedge exposure with white light according to a conventional method, and immediately subjected to development processing according to the following processing steps. Further, the sample B was left in an atmosphere of 55 ° C. and a relative humidity of 80% for 7 days, and then subjected to the wedge exposure and the development treatment in the same manner as the sample A. The density of the treated sample was measured using an optical densitometer PDA-65 (manufactured by Konica).

Table 4 shows the experimental results of fog and sensitivity of Samples A and B at the green density of each of Sample Nos. 1 to 14. However, the sensitivity here means that the green density is the fog density +
It is represented by the reciprocal of the exposure amount that gives an optical density of 0.30. It was shown as a relative value when the sensitivity of Sample A of No. 1 was 100. The results are shown in Table 4.

(Treatment process) Treatment process Treatment time Treatment temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ℃ 780ml Bleach 45 seconds 38 ± 2.0 ℃ 150ml Fixation 1 minute 30 seconds 38 ± 2.0 ℃ 830ml Stability 60 Second 38 ± 5.0 ℃ 830ml Drying 1 minute 55 ± 5.0 ℃ − * Replenishment amount is the value per 1 m ² of light-sensitive material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used.

Color developer and color developing replenisher developer Replenisher replenisher Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium hydrogen carbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g Potassium iodide 1.2 mg-hydroxylamine Sulfate 2.5g 3.1g Sodium chloride 0.6g-4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5g 6.3g Diethylenetriaminepentaacetic acid 3.0g 3.0g Potassium hydroxide 1.2g 2.0g Add water to make 1 liter and add potassium hydroxide or 20%
The color developer is adjusted to pH 10.06 and the replenisher is adjusted to pH 10.18 using sulfuric acid.

Bleaching solution and bleach replenishing solution Bleaching solution Replenishing solution Water 700 ml 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g 175 g Ethylenediaminetetraacetic acid 2 g 2 g Sodium nitrate 40 g 50 g Ammonium bromide 150 g 200 g Glacial acetic acid 40 g 56 g Water The pH of the bleaching solution is adjusted to pH 4.4 and the replenishing solution is adjusted to pH 4.0 using ammonia water or glacial acetic acid.

Fixing Solution and Fixing Replenishing Solution Fixing Solution Replenishing Solution Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Ammonia water or glacial acetic acid is used as a fixing solution at pH 6.2.
After adjusting the pH of the replenisher to 6.5, water is added to make 1 liter.

Stabilizer and stable replenisher Water 900 ml Ethylene oxide 10 mol adduct of p-octylphenol 2.0 g Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UC-L-77 ) 0.1g Ammonia water 0.5ml After adding water to make 1 liter, use ammonia water or 50
Adjust to pH 8.5 with% sulfuric acid.

[0145]

[Table 4]

As is clear from the results shown in Table 4, by using the compound of the present invention together with the selenium-sensitized or tellurium-sensitized emulsion, fog can be particularly reduced, high sensitivity can be obtained, and storage is accompanied by storage. It is understood that it is possible to prevent deterioration of photographic performance such as increased fog and decreased sensitivity.

Example 3 << Emulsion Sensitization >> The emulsion (EM-4) prepared in Example 1,
In contrast to (EM-5), the emulsion of Example 2 (EM-
Optimum spectral sensitization and chemical sensitization were carried out in the same manner as 3), and then stabilized and sensitized emulsions SEM-4a to 4j, SEM-
5a-5e were prepared. Sodium thiosulfate, selenium
Table 5 shows the addition amounts of the tellurium sensitizer, the antifoggant AF-1 and the compound of the present invention.

<< Preparation of Silver Halide Photosensitive Material and Evaluation of Photographic Performance >> Sample No. 2 of Example 2 In the preparation of Sample No. 1, except that the sensitized emulsion used for the third layer was changed as shown in Table 6. Sample N
o. 31-45 were created. Then, the photographic performance was evaluated in exactly the same manner as in Example 2. The results are shown in Table 6.

[0149]

[Table 5]

[0150]

[Table 6]

Sample No. shown in the results of Table 6 and Table 4
From the results of 1 and 2, the use of the compound of the present invention, when used together with a reduction-sensitized emulsion, can reduce fog in particular, high sensitivity can be obtained, and photographic properties such as increase in fog and decrease in sensitivity with storage can be obtained. It can be seen that it is effective in preventing deterioration.

Example 4 << Emulsion sensitization >> The emulsion (EM-1) prepared in Example 1,
Optimum spectral sensitization and chemical sensitization were applied to (EM-2) and (EM-6) in the same manner as the emulsion (EM-3) in Example 2, and then stabilized and sensitized emulsion SEM-. 1a ~
1c, SEM-2a-2c, SEM-6a-6e were prepared.

The addition amount of the sensitizing dyes S-1, S-2 and S-3 was changed according to the surface area of the silver halide grains contained in the emulsion. The amounts of sodium thiosulfate, selenium / tellurium sensitizer, antifoggant AF-1 and the compound of the present invention added are shown in Table 7.

[0154]

[Table 7]

<< Preparation of Silver Halide Photosensitive Material and Evaluation of Photographic Performance >> Sample No. 2 of Example 2 In the preparation of Sample No. 1, except that the sensitized emulsion used for the third layer was changed as shown in Table 7, Sample No. Sample N
o. 51-61 were produced. Then, the photographic performance was evaluated in exactly the same manner as in Example 2. Table 8 shows the results.

[0156]

[Table 8]

The sample No. shown in the results of Table 8 and Table 4
From the results of 3 to 5, the use of the compound of the present invention together with tabular grains having a large aspect ratio, in particular, reduces fog and provides high sensitivity, and increases photographic performance such as increase in fog during storage and decrease in photographic performance. It can be seen that it is effective in preventing deterioration of

Example 5 In the same manner as in the preparation of the sensitized emulsion SEM-4f of Example 3, except that the antifoggant AF-1 was not added,
A sensitized emulsion SEM-4K was prepared.

Silver halide photographic light-sensitive material N of Example 3
o. 36, instead of the sensitized emulsion SEM-4f, SE
As shown in Table 9, the compound a- of the present invention was prepared using M-4K.
Sample No. 3 except that 3 was added. Sample No. 36 in exactly the same manner as in No. 36. 71-75 were produced.

[0160]

[Table 9]

Photographic performance of these samples was evaluated in exactly the same manner as in Example 2. The results are shown in Table 10.

[0162]

[Table 10]

From the results shown in Table 10, the effect of the compound of the present invention can be obtained even if it is added to any hydrophilic colloid layer in the photographic light-sensitive material, and it is particularly preferable to add it to the silver halide emulsion layer or its adjacent layer. It turns out to be effective.

[0164]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having high sensitivity, less fog, and prevented from changing photographic characteristics due to storage over time.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein at least one silver halide emulsion layer is selenium-sensitized or tellurium-sensitized. In the hydrophilic silver colloid layer containing the photosensitive silver halide grains and having a water-permeable relationship with the silver halide emulsion layer or the silver halide emulsion layer,
A silver halide photographic light-sensitive material comprising at least one selected from the compounds represented by the following general formula [I] or general formula [II]. Embedded image [In the formula, M represents a hydrogen atom, a metal atom, or a quaternary ammonium group. Q represents a group of non-metal atoms necessary for bonding to a carbon atom and a nitrogen atom and forming a monocycle or a condensed heterocycle with them. L represents a divalent group, n is 0 to
Represents an integer of 2. R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a cation or a substituent, and R ¹ , R ² and R ³
And R ⁴ may be the same or different, and may combine with each other to form a ring. ] 2. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers is reduction-sensitized. The silver halide emulsion layer containing silver particles or another hydrophilic colloid layer having water permeability to the silver halide emulsion layer is added to the above-mentioned general formula [I] or general formula [II].
A silver halide photographic light-sensitive material containing at least one selected from the compounds represented by: 3. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers is a light-sensitive halide having an aspect ratio of 2 or more. The silver halide emulsion layer containing silver particles or another hydrophilic colloid layer having water permeability to the silver halide emulsion layer is selected from compounds represented by the above general formula [I] or general formula [II]. A silver halide photographic light-sensitive material comprising at least one of the following: