JPH0611791A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve stability with the lapse of time and pressure resistance of the photosensitive material by incorporating a specified compound in the constituent layer of the photosensitive material chemically sensitized with a selenium compound. CONSTITUTION:One of the photosensitive silver halide emulsion layer of the photographic sensitive material contains a silver halide emulsion chemically sensitized with the selenium compound and the constituent layers contains at least one of the compounds represented by formulae I-III in which each of R12, R13, R15, and R16, is H, or a group substitutable on the benzene ring; each of R11 and R14 is H or a protective group releasable under alkaline conditions; each of R21 and R26 is same as R12; and each of R<1> and R<2> is hydroxy, hydroxyamino, alkylamino, aryl-amino, or the like.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photographic light-sensitive material using a silver halide emulsion for photography.

[Prior art]

Since photographic light-sensitive materials in recent years are desired to have higher sensitivity and to be processed more rapidly, the silver halide emulsions used therefor can be sensitized and the amount of binder can be reduced to achieve rapid processing. ing. However, increasing the sensitivity to light and reducing the amount of binder (gelatin, high-molecular polymer, etc.) that acts as a protective colloid for silver halide grains exacerbates the pressure blackening and bleaching blackening that occur during the use of photographic materials. It was supposed to be done. Similarly, the occurrence of fogging and the increase / decrease sensation during the passage of time of the photosensitive material are likely to occur.

The selenium sensitization described in the present invention is very well known as a sensitizing technique for silver halide emulsions. Regarding the sensitizing method using this, US Pat.
No. 74944, No. 1602592, No. 162349
No. 9, No. 3297446, No. 3297447,
No. 33200069, No. 3408196, No. 3
No. 408197, No. 3442653, No. 3420
No. 670, No. 3591385, and French Patent No. 26.
No. 93038, No. 2093209, Japanese Patent Publication No. 52-3
No. 4491, No. 52-34492, No. 53-295.
No. 57-22090, JP-A-59-180536.
No. 59-185330, No. 59-181337.
No. 59-187338 and No. 59-192241.
Issue No. 60-150046, Issue No. 60-151637
No. 61-246738, JP-A-3-42221,
Japanese Patent Application Nos. 1-287380, 1-250950, 1-254441, 2-334090 and 2-11
No. 0558, No. 2-130976, No. 2-13918
No. 3, No. 2-229300, and British Patent No. 2558.
No. 46, No. 861984, and HESpencer et al.,
Journal of Photographic Science, Volume 31, 158
~ 169 (1983) and the like.

However, since high sensitivity can be achieved, pressure fog and natural fog tend to occur. It is a well-known technique in the art to add hydroquinone and its derivative into the light-sensitive material layer as a technique for reducing the pressure blackening. These are described in detail, for example, in JP-A-64-72141. Further, as these hydroquinones, those having an adsorption group so that they are easily adsorbed to silver halide, and those having a diffusion resistant group in order to improve diffusion resistance in a light-sensitive material are effective, for example, , Japanese Patent Application No. 2-280457. However, it is not mentioned anywhere that the effect of improving pressure fog of para-hydroquinones is particularly effective when sensitizing selenium. There is no detailed description regarding the relationship with chemical sensitization. Therefore, it cannot be expected that these para-hydroquinones and the like and their derivatives will have a particularly remarkable effect in improving the pressure property of the silver halide emulsion sensitized by selenium or selenium and sulfur sensitization. there were. Further, this emulsion contained 7% of the total projected area of all silver halide grains.
It was totally unexpected that the effect was particularly remarkable when 0% or more was tabular grains having an aspect ratio of 3 or more.

It is described in detail, for example, in JP-A-59-97134 that the triazine compound and its derivative are effective in improving the storability of tabular grains. However, it could not be expected at all that the effect of improving the storability (fog with time, sensitization with time) of this compound was extremely remarkable for a silver halide emulsion chemically sensitized with selenium or a selenium sulfur sensitizer. That is.
The present inventors have found that these triazine compounds and their derivatives have a remarkable improvement effect especially in selenium and silver halide emulsions chemically sensitized with selenium and a sulfur sensitizer. It was also found that the effect was particularly great when the emulsion had tabular grains having an average aspect ratio of 3 or more composed of 70% or more of the total projected area of silver halide grains. Hydroquinone compounds and their derivatives are highly reducible towards silver halides, such as often used as a developing agent. Therefore, it is expected that silver ions will be reduced during storage with time for a high-sensitivity emulsion chemically sensitized with selenium or selenium and a sulfur sensitizer, and fog with time will easily occur. These are TH
This is detailed in James, Logic of the Photographic Process, Fourth Edition. The present inventors have also used general formula (III) to suppress the storage stability (fogging over time) of such selenium and emulsion chemically sensitized with selenium and a sulfur sensitizer and a sensitizing material containing hydroquinone and its derivative. It was newly found that the triazine compound shown is particularly effective.

[0006]

Therefore, the present invention improves the temporal stability and pressure resistance of a light-sensitive material using a high-sensitivity silver halide emulsion chemically sensitized with a selenium compound or a selenium compound and a sulfur compound. That is the purpose.

[0007]

SUMMARY OF THE INVENTION The inventors of the present invention have investigated the pressure property (pressure blackening) and storability (fogging over time) of a light-sensitive material containing a high-sensitivity emulsion chemically sensitized with a selenium compound by the method described below. Sense of change) was improved. (1) In a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, at least 1
Compounds represented by the following general formulas (I), (II) and (III) in a structural layer of a light-sensitive material in which a silver halide emulsion chemically sensitized with a selenium compound is used for the silver halide emulsion of one layer By containing at least one of them, the pressure property and the storability were improved. General formula (I)

[0008]

[Chemical 4]

In the formula (I), R ₁₂ , R ₁₃ , R ₁₅ and R ₁₆
May be the same or different and each is a hydrogen atom or a group capable of substituting for a benzene ring, and R ₁₁ and R ₁₂ are a hydrogen atom or a protecting group capable of being deprotected under alkaline conditions. R ₁₂ to R
₁₆ , OR ₁₁ and OR ₁₄ may together form a ring. General formula (II)

[0010]

[Chemical 5]

In the formula (II), R ₂₂ to R ₂₆ may be the same or different and each is a hydrogen atom or a group capable of substituting on a benzene ring, and R ₂₁ is a hydrogen atom or a protecting group deprotectable under alkaline conditions. is there. R ₂₂ to R ₂₆ and OR ₂₁ may together form a ring. However, in the general formula (II), at least one of R ₂₂ to R ₂₆ has a group that promotes adsorption to silver halide grains, or a substituent having a total carbon number of 6 or more. And at least one is substituted with a hydroxy group or a group deprotectable under allyl potassium conditions. General formula (III)

[0012]

[Chemical 6]

In the formula, R ¹ and R ² may be the same or different from each other and each represents a hydroxy group, a hydroxylamino group,
It represents an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an alkoxy group, a phenoxy group, an alkyl group, an aryl group, an alkylthio group or a phenylthio group. Further, the present inventors have found that the above-mentioned effects are more remarkable when 70% or more of the total projected area of all halogen grains are tabular grains having an aspect ratio of 3 or more.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-13489.
No. 2, JP-A-2-130976, Japanese Patent Application No. 2-22930.
It is preferable to use the compounds described in No. 0 and the like. Specific examples of unstable selenium sensitizers include isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (eg,
2-selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium And so on. The preferred types of labile selenium compounds have been described above, but are not limiting. To those skilled in the art, when it comes to unstable selenium compounds as sensitizers for photographic emulsions, the structure of the compounds is not so important as long as selenium is unstable,
It is generally understood that the organic portion of the selenium sensitizer molecule carries selenium and plays no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used. Examples of the non-labile selenium compound used in the present invention include JP-B-46-4553 and JP-B-53-344.
The compounds described in JP-B No. 92 and JP-B-52-34491 are used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof. Of these selenium compounds, the following general formulas (IV) and (V) are preferable. General formula (IV)

[0015]

[Chemical 7]

In the formula, Z ₁ and Z ₂ may be the same or different and each represents an alkyl group (for example, a methyl group,
Ethyl group, t-butyl group, adamantyl group, t-octyl group), alkenyl group (eg vinyl group, propenyl group), aralkyl group (eg benzyl group, phenethyl group), aryl group (eg phenyl group, penta) Fluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4-octylsulfamoylphenyl group, α-
Naphthyl group), heterocyclic group (for example, pyridyl group, thienyl group, furyl group, imidazolyl group), -NR ₁ (R ₂ ),-
It represents an OR ₃ or -SR _4. R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group.
Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ . However, R ₁ and R ₂ are a hydrogen atom or an acyl group (for example, acetyl group, propanoyl group, benzoyl group, heptafluorobutanoyl group, difluoroacetyl group, 4-nitrobenzoyl group, α-naphthoyl group, 4-trifluoro group). Methylbenzoyl group). In formula (IV), Z ₁ is preferably an alkyl group, an aryl group, or —NR ₁ (R ₂ ).
And Z ₂ represents —NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅
R ₆ and R ₆ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group. In the general formula (IV), more preferably N, N-dialkylselenourea, N, N, N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-
Dialkyl-arylselenoamide, N-alkyl-N
Represents an aryl-arylselenoamide. General formula (V)

[0017]

[Chemical 8]

In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group, -OR ₇ , -NR ₈ (R ₉ ), -SR. ₁₀ , -Se
R ₁₁ , X and a hydrogen atom are represented. R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. , X represents a halogen atom. In the general formula (V), Z ₃ , Z ₄ , Z ₅ , Z ₇ , Z ₈ ,
The aliphatic group represented by Z ₉ , Z ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl group, ethyl group, n-
Propyl group, isopropyl group, t-butyl group, n-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, A propargyl group, a 3-pentynyl group, a benzyl group, a phenethyl group). In the general formula (V), Z ₃ , Z ₄ , Z ₅ ,
The aromatic group represented by Z ₇ , Z ₈ , Z ₉ , Z ₁₀ and R ₁₁ is a monocyclic or condensed ring aryl group (for example, a phenyl group,
Pentafluorophenyl group, 4-chlorophenyl group, 3
-Sulfophenyl group, α-naphthyl group, 4-methylphenyl group). In the general formula (V), Z ₃ , Z ₄ ,
The heterocyclic group represented by Z ₅ , Z ₇ , Z ₈ , Z ₉ , Z ₁₀ and R ₁₁ is a saturated or unsaturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Represents a heterocyclic group (eg, pyridyl group, thienyl group, furyl group, thiazolyl group, imidazolyl group, benzimidazolyl group). In the general formula (V), the cation represented by R ₇ , R ₁₀ and R ₁₁ represents an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Represents In formula (V), preferably Z ₃ , Z ₄ or Z ₅
Represents an aliphatic group, an aromatic group or —OR ₇ , and R ₇ represents an aliphatic group or an aromatic group. In formula (V), more preferably trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate. Specific examples of the compounds represented by formulas (IV) and (V) are shown below, but the invention is not limited thereto.

[0019]

[Chemical 9]

[0020]

[Chemical 10]

[0021]

[Chemical 11]

[0022]

[Chemical 12]

[0023]

[Chemical 13]

[0024]

[Chemical 14]

[0025]

[Chemical 15]

[0026]

[Chemical 16]

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or in Japanese Patent Application Nos. 2-264447 and 2-2.
No. 64448 is added at the time of chemical sensitization. It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one kind, and the selenium sensitizers described above
One or more species can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination. The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the temperature and time of ripening, and the like. It is 1 × 10 ⁻⁸ mol or more per mol. It is more preferably 1 × 10 ⁻⁷ mol or more and 1 × 10 ⁻⁵ mol or less.
The temperature of chemical ripening when a selenium sensitizer is used is preferably 45 ° C. or higher. More preferably 50 ° C or higher and 80 ° C
It is the following. pAg and pH are arbitrary. For example p
The effect of the present invention can be obtained in a wide range of H from 4 to 9. It is more effective to perform selenium sensitization in the presence of a silver halide solvent.

The silver halide solvent which can be used in the present invention is, for example, US Pat. Nos. 3,271,157, 3,531,289, 3,574,628 and JP-A-54-54. (A) Organic thioethers described in 1019, 54-158917 and the like, JP-A-53-824.
No. 08, No. 55-77737, No. 55-2982 and the like (b) thiourea derivatives, JP-A-53-144
(C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, and (d) described in JP-A No. 54-100717.
Examples thereof include imidazoles, (e) sulfite, (f) thiocyanate and the like. Particularly preferred solvents are thiocyanate and tetramethylthiourea. The amount of the solvent used varies depending on the kind, but in the case of thiocyanate, the preferable amount is 1 per mol of silver halide.
It is not less than × 10 ^-4 mol and not more than 1 × 10 ^-2 mol.

The silver halide photographic emulsion of the present invention can achieve higher sensitivity and lower fog by combined use of sulfur sensitization and / or gold sensitization in chemical sensitization. Sulfur sensitization usually involves adding a sulfur sensitizer,
It is carried out by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. For sulfur sensitization, known sulfur sensitizers can be used. For example, thiosulfate, thioureas, allylisothiocyanate, cystine, p-toluenethiosulfonate,
Examples include rhodanine. Other US Patent No. 1,5
74,944, 2,410,689, 2,
278,947, 2,728,668, 3,501,313, 3,656,955, German Patent 1,422,869, Japanese Patent Publication No. 56-
The sulfur sensitizers described in JP-A-24937, JP-A-55-45016 and the like can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and large size of silver halide grains, but it is 1 × 10 ^-7 mol or more and 5 × 10 ^-4 mol per mol of silver halide. The following are preferred.

As the gold sensitizer for the above-mentioned gold sensitization, the oxidation number of gold may be +1 or +3, and a gold compound usually used as a gold sensitizer can be used. Typical examples are chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate ,. Pyridyl trichloro gold etc. are mentioned. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ mol per mol of silver halide. At the time of chemical ripening, it is not necessary to particularly limit the timing and order of addition of a silver halide solvent and a selenium sensitizer or a sulfur sensitizer and / or a gold sensitizer which can be used in combination with a selenium sensitizer. Alternatively, for example, the above compounds can be added at the same time as the initial (preferably) chemical ripening or during the progress of chemical ripening, or at different addition points. In addition, at the time of addition, the above compound may be dissolved in water or an organic solvent capable of mixing with water, for example, a single liquid or a mixed liquid of methanol, ethanol, acetone or the like and added.

The emulsion according to the present invention can be reduction-sensitized if necessary. Methods for reduction sensitization include JP-A-2-191938 and JP-A-2-13685.
No. 2, JP-B-57-33572, ascorbic acid and its derivatives as a reducing agent, thiourea dioxide, stannous chloride, aminoiminomethanesulfinic acid,
Reduction sensitization can be performed using a hydrazine derivative, a borane compound, a silane compound, or a polyamine compound. Further, reduction sensitization can be carried out by keeping the pH of the emulsion at 7 or higher and pAg at 8.3 or lower and ripening. Further, reduction sensitization can be carried out by introducing a single adduct portion of silver ions during grain formation. However, the effect on grain formation and crystal growth is reduced,
From the viewpoint of controlled reduction sensitization, it is preferable to perform reduction sensitization using ascorbic acid and its derivative or thiourea dioxide. The amount of reduction sensitizer used is
Depending on the reducing agent species, it varies from 10 ^-7 mol to 10 ^-2 mol /
A molar Ag amount is preferably used. The reduction sensitization may be performed anywhere during grain formation and at any time after grain formation and before chemical sensitization. The emulsion used in the present invention is described in JP-A-2-191938 and JP-A-2-13938.
The thiosulfonic acid compound described in No. 6852 can be used.

The formula (I) will be described in more detail below. Preferred examples of the substituent represented by R ₁₂ , R ₁₃ , R ₁₅ , and R ₁₆ in the formula (I) include a halogen atom, a hydroxy group, a sulfo group, a carboxyl group, a cyano group, and an alkyl group having 30 or less carbon atoms ( (Straight, branched or cyclic), alkenyl group, alkynyl group, aralkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, carbonamide group, sulfonamide group, ureido group, alkoxycarbol Amino group, aryloxycarbonylamino group, acyloxy group, sulfamoylamino group, sulfonyloxy group, carbamoyl group, sulfamoyl group, acyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group or oxygen / nitrogen / sulfur / phosphorus・ No three members containing at least one of selenium or tellurium It represents a 12 membered heterocyclic group.
These groups may be further substituted with the groups mentioned above. Examples of the protective group represented by R ₁₁ and R ₁₄ in the formula (I) include an acyl group having 25 or less carbon atoms, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbyl group, and JP-A-59-197,037. Same as 59-2
Nos. 01,057, 59-108,776, and U.S. Pat. No. 4,473,537. R ₁₂ to R ₁₃ , R ₁₅ , R ₁₆ and OR ₁₁ , OR ₁₄
And R ₁₂ and O together form a ring.
R ₁₁ , R ₁₂ and R ₁₃ , R ₁₃ and OR ₁₄ , OR ₁₄ and R ₁₅ , R ₁₅
And R ₁₆ or R ₁₆ and OR ₁₁ combine to form a saturated or unsaturated 4- to 8-membered carbon ring or heterocycle. The compound represented by the formula (I) may form a bis form, a tris form, an oligomer or a polymer. The total carbon number of R ₁₂ to R _{16 in} formula (II) is 6 or more, preferably 8 or more. Next, general formula (II) will be described. The protecting group referred to herein for formula (II) is the same as that for R ₁₁ and R _{14 in} formula (I). Also R ₂₂ to R ₂₆ and O
The case where R ₂₁ jointly forms a ring is the same as the case of R ₁₂ to R ₁₆ and OR ₁₁ and OR ₁₄ in the above (I).

The adsorption promoting group to silver halide in the formula (II) can be represented by the following formula. Y- (L) m-Y is an adsorption promoting group to silver halide and L is a divalent linking group. m is 0 or 1. Preferred examples of the adsorption accelerating group for Y represented by Y include a thioamide group, a mercapto group, a group having a disulfide bond and a 5- or 6-membered nitrogen-containing heterocyclic group.

The thioamide adsorption promoting group represented by Y is a divalent group represented by -CS-amino-, which may be a part of the ring structure or an acyclic thioamide group. Good. Useful thioamide adsorption-promoting groups include, for example, US Pat. Nos. 4,030,925 and 4,031,12.
No. 7, No. 4,080,207, No. 4,245,037
No. 4,255,511, 4,266,013
And 4,276,364, and "Research Disclosure" magazine,
Volume 151, No. 15162 (November 1976), and Volume 176, No. 17626 (December 1978).
Can be selected from those disclosed in. Specific examples of the acyclic thioamide group include, for example, thioureido group,
Thiourethane group, dithiocarbamate group, etc.
Further, specific examples of the cyclic thioamide group include, for example, 4-
Thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3,4- Thiadiazoline
Examples include 2-titon, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione and benzothiazoline-2-thione, which may be further substituted. Good.

The mercapto group of Y is a fat-based mercapto group,
Aromatic mercapto group or heterocyclic mercapto group (when the carbon atom to which the -SH group is bonded is adjacent to a nitrogen atom, it is synonymous with a cyclic thioamide group having a tautomer relationship with this, and specific examples of this group Are the same as listed above)
Is mentioned. Examples of the 5-membered to 6-membered nitrogen-containing heterocyclic group represented by Y include 5-membered to 6-membered nitrogen-containing heterocycles consisting of a combination of nitrogen, oxygen, sulfur and carbon. Among these, preferable examples include benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine and the like. These may be further substituted with appropriate substituents. Among those represented by Y, preferred are cyclic thioamide groups (that is, mercapto-substituted nitrogen-containing heterocycles such as 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5
-Mercaptotetrazole group, 2-mercapto-1,
3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.) or nitrogen-containing heterocyclic group (for example,
Benzotriazole group, benzimidazole group, indazole group, etc.). Two or more Y- (L) _m -groups may be substituted and may be the same or different. L
The divalent linking group represented by is an atom or atomic group containing at least one of C, N, S, and O. Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, -NH-,
-N =, - CO -, - SO 2 - ( these groups may also have a substituent) is made of a single or combination of such. For example,

[0036]

[Chemical 17]

[0037]

[Chemical 18]

And the like. Specific examples of the compound represented by formula (I) are shown below.

[0039]

[Chemical 19]

[0040]

[Chemical 20]

Specific examples of the compound of formula (II) are shown below. However, it is not limited to this.

[0042]

[Chemical 21]

[0043]

[Chemical formula 22]

[0044]

[Chemical formula 23]

[0045]

[Chemical formula 24]

[0046]

[Chemical 25]

[0047]

[Chemical formula 26]

[0048]

[Chemical 27]

[0049]

[Chemical 28]

[0050]

[Chemical 29]

[0051]

[Chemical 30]

[0052]

[Chemical 31]

[0053]

[Chemical 32]

[0054]

[Chemical 33]

[0055]

[Chemical 34]

The compound represented by the formula (I) according to the present invention can be synthesized by the methods described in the following patents and the patents cited therein and the methods analogous thereto. That is, U.S. Pat. Nos. 2,701,197, 3,700,453, 3,960,570, 4,232,114, 4,277,553, and 4,443,537. Nos. 4,447,523, 4,476,219, 4,717,651, 4,732,845, and Japanese Patent Publication Nos. 51-12,250.
JP-A-54-29,637, 58-21,249
No. 59-108, 776, 61-48, 456.
No. 61-169,844, 6-309,949.
No. The compounds represented by formulas (I) and (II) of the present invention are preferably contained in the photosensitive emulsion layer in the light-sensitive material.
The amount of the compounds of formulas (I) and (II) added is 1 × 10 ^{−4 to} 1 mol, preferably 1 × 10 ⁻³ to 1 mol, per mol of silver halide.
It is 1 × 10 ^-1 mol.

Next, the general formula (III) will be described in detail. In the formula, R ₁ and R ₂ may be the same or different and each is a hydroxy group, a hydroxylamino group, an amino group, an alkylamino group (preferably a mono- or di-substituted amino group of an alkyl group having 1 to 5 carbon atoms). , An aralkylamino group (preferably having a carbon number of 7 to 11), an arylamino group (preferably an amino group substituted by an aryl group having a carbon number of 6 to 10), an alkoxy group (preferably having a carbon number of 1 to 5)
), A phenoxy group, an alkyl group (preferably having a carbon number of 1 to 5), an aryl group (preferably having a carbon number of 6 to
10), an alkylthio group (preferably having a carbon number of 1 to 1)
5) or a phenylthio group. The alkyl moiety in each of the above groups is a hydroxy group, an alkoxy group (preferably having 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms), an amino group, an alkylamino group (preferably having 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms). It may have a substituent such as an alkyl group (mono- or di-substituted amino group). In each of the groups represented by R ₁ and R ₂ , the aryl or phenyl moiety is a hydroxy group, an amino group or an alkylamino group (preferably having 1 carbon atom).
To 4, especially 1 to 2 mono- or di-substituted amino groups of alkyl groups), alkyl groups (preferably having 1 to 4 carbon atoms, especially 1 to 2 carbon atoms)
Group), an alkoxy group (preferably having 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms), and the like.

Of the compounds represented by the general formula (III), _{one of} R _{1 and} R ₂ represents a hydroxylamino group and the other represents an alkylamino group, and R ₁
It is particularly preferable that R ₂ and R ₂ both represent an alkoxy group or an alkylamino group. The compounds of the general formula (III) preferably used in the present invention are exemplified below.

[0059]

[Chemical 35]

[0060]

[Chemical 36]

[0061]

[Chemical 37]

[0062]

[Chemical 38]

[0063]

[Chemical Formula 39]

[0064]

[Chemical 40]

These compounds are referred to as Journal of the
Organic Chemistry, 27: 4054 (19)
62), Journal of the American Chemical Society, Vol. 73, page 2981 (1951), JP-B-49-10692, and the like. These compounds are used as an aqueous solution, a hydrochloric acid aqueous solution, or a methanol solution in a photographic emulsion or a constituent layer other than the emulsion layer (for example, an overcoat layer, a filter layer, an intermediate layer, etc., but an emulsion layer containing tabular silver halide grains). Adjacent layers are preferred) to make a new aqueous colloid solution. The timing of addition is not particularly limited, but when it is added to a photographic emulsion, it is convenient to add it after chemical ripening and immediately before coating. The amount of these compounds added is usually preferably 0.01 g to 10 g, and particularly preferably 0.05 g to 1 mol per mol of silver.
The range of 1 g is more preferable.

The tabular silver halide grains preferably used in the present invention will be described below. However, it is a preferable idea that can be commonly applied to the selenium-sensitized or selenium- and sulfur-sensitized emulsions contained in the light-sensitive material of the present invention except for the aspect ratio in the following description. The tabular silver halide grain of the present invention preferably has a diameter / thickness ratio of 3 or more, more preferably 5 or more and 100 or less,
It is more preferably 5 or more and 50 or less (particularly preferably 7 or more and 20 or less). Here, the diameter of a silver halide grain means the diameter of a circle having an area equal to the projected area of the grain. In the present invention, the tabular silver halide grains have a diameter of preferably 0.5 to 10 µ, more preferably 0.5 to 5.0 µ, and particularly preferably 1.0 to 4.0 µ. In general, tabular silver halide grains are tabular having two parallel planes, and therefore "thickness" in the present invention means a distance between two parallel planes constituting the tabular silver halide grain. Represented. The halogen composition of the tabular silver halide grains is
Silver bromide and silver iodobromide are preferable, and silver iodobromide having a silver iodide content of 0 to 10 mol% is particularly preferable. Next, a method for producing tabular silver halide grains will be described. The tabular silver halide grains can be produced by appropriately combining methods known in the art. For example, in a relatively high pAg value atmosphere of pBr 1.3 or less, a seed crystal in which tabular grains are present in an amount of 40% or more by weight is formed, and while maintaining the same pBr value, the silver and halogen solutions are added at the same time. Obtained by growing crystals. During this grain growth process, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated. The size of tabular silver halide grains can be adjusted by controlling the temperature, selecting the type and amount of solvent, and controlling the addition rate of silver salt and halide used during grain growth. During the production of the tabular silver halide grains of the present invention, if necessary, a silver halide solvent can be used to control the grain size, grain shape (diameter / thickness ratio, etc.), grain size distribution, grain growth rate. .
The amount of the solvent used is preferably 10 ^{−3 to} 1.0% by weight of the reaction solution, and particularly preferably 10 ⁻² to 10 ⁻¹ % by weight.

For example, as the amount of solvent used increases, the particle size distribution can be made monodisperse and the growth rate can be increased. On the other hand, there is also a tendency that the particle thickness increases with the amount of solvent used. Examples of the silver halide solvent often used include ammonia, thioethers and thioureas. Regarding the thioether, US Pat. Nos. 3,271,157, 3,790,387, and 3,574,628 can be referred to.
When the tabular silver halide grains of the present invention are produced, the addition rate, amount and concentration of the silver salt solution (eg AgNO ₃ aqueous solution) and the halide solution (eg KBr aqueous solution), which are added in order to accelerate the grain growth, are set. A method of increasing the temperature is preferably used. Regarding these methods, for example, British Patent No. 1,335,925 and US Pat. No. 3,672,900.
No. 3, No. 3,650,757, No. 4,242,44
5, JP-A-55-142329 and JP-A-55-1581.
The description in No. 24, etc. can be referred to.

The tabular silver halide grains of the present invention can be chemically sensitized with compounds other than selenium and sulfur, if necessary. As the chemical sensitization method, a so-called gold compound sensitization method (for example, US Pat. No. 2,448,060) is used.
No. 3,320,069) or iridium, platinum,
A sensitizing method using a metal such as rhodium or palladium (for example, US Pat. Nos. 2,448,060 and 2,566,245).
No. 2,566,263).

In the layer containing the tabular silver halide grains of the present invention, the tabular grains are present in an amount of 50% or more, particularly 60% or more by weight based on the total silver halide grains in the layer. Is preferred. The thickness of the layer containing tabular silver halide grains is preferably 0.3 to 5.0 µ, and particularly preferably 0.5 to 3.0 µ. The coating amount of tabular silver halide grains (on one side) is 0.5 to 6 g / m ² , particularly 1 to 4 g.
/ M ² is preferred. Other constitution of the layer containing the tabular silver halide grains of the present invention, for example, a binder, a curing agent, an antifoggant, a stabilizer for silver halide,
There are no particular restrictions on surfactants, spectral sensitizing dyes, dyes, UV absorbers, chemical sensitizers, etc., for example Research
Disclosure 176, 22-28 (December 1978)
You can refer to the description in (Month).

The emulsion layer of the silver halide photographic light-sensitive material of the present invention may contain ordinary silver halide grains in addition to tabular silver halide grains. These are P.Gl
Chimie et Physique Photographique (Paul by afkides
Montel, 1967), by GF Duffin Photographic Em
ulsion Chemistry (The Focal Press, 1966), VL
Making and Coating Photographic E by Zalikman et al
It can be prepared using the method described in mulsion (The FocalPress, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonium method and the like may be used, and as a method for reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. . A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. The silver halide may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloride and the like. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt; a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be present together. Further, if necessary, chemical sensitization can be carried out in the same manner as tabular silver halide grains.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage or during photographic processing or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenztriazoles, mercaptotetrazoles (especially 1
-Phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; azaindenes, such as triazaindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaaza Indenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be added. For example, those described in U.S. Pat. Nos. 3,954,474, 3,982,947 and JP-B-52-28,660 can be used.

There are no particular restrictions on other various additives used in the light-sensitive material of the present invention.
It is possible to use the materials described in the following relevant parts of Japanese Patent No. 68539. Item This section 1. Silver halide emulsion JP-A-2-68539, page 8, lower right column, line 6 from the bottom, or its manufacturing method, page 10 upper right column, line 12 2. Chemical sensitization method Page 10, upper right column, line 13 to left lower column, line 16 3. Antifoggant / stabilization, page 10, lower left column, line 17 to page 11, upper left column, line 7 and agent, page 3 lower left column From line 2 to page 4, lower left column 4. Spectral sensitizing dye, page 4, right lower column, line 4 to page 8, lower right column 5. Surfactants / antistatics, page 11, upper left column, line 14 From page 12 of the same page, upper left column, line 9 Stopping agent 6. Matting agent / slip agent ・ From page 12, upper left column, line 10 to the same, upper right column, line 10 14th Plasticizer, page lower left column, line 10 to right lower column, line 1 7. Hydrophilic colloid, page 12 upper right column, line 11 to lower left column, line 16 8. Hardener, page 12 lower left column Line 17 to page 13, upper right column, line 6 9. Support, page 13 upper right column, lines 7 to 20 10. Dye / mordanting agent, page 13 lower left column, line 1 to page 14, lower left Column, line 9 11. Development method JP-A-2-03037, page 16, upper right column, line 7 to page 19, lower left column, line 15 Japanese Patent Application Laid-Open No. 2-115837, page 3, lower right column, line 5 to page 6, upper right column, line 10 Next, examples will be shown to further describe the present invention.

[0073]

【Example】

Example 1 Preparation of tabular grains 4.5 g potassium bromide and 2 gelatin in 1 liter of water.
0.6 g, 5 of thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH
% Aqueous solution (2.5 cc) and stirred in a container kept at 60 ° C. while stirring, 33 cc of aqueous solution of silver nitrate (3.43 g of silver nitrate), 33 cc of aqueous solution containing 2.97 g of potassium bromide and 0.363 g of potassium iodide are double jet method. For 37 seconds. Next, an aqueous solution of 0.9 g of potassium bromide was added, and then the temperature was raised to 70 ° C., and 53 cc of an aqueous silver nitrate solution (silver nitrate 4.
90 g) was added over 13 minutes. Here, 15 cc of 25% aqueous ammonia solution was added, and after physically aging for 20 minutes at the same temperature, 14 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 133.3 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes by the control double jet method while maintaining the pAg at 8.5. Next, 10 cc of 2N potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, monodisperse tabular grains having a total silver iodide content of 0.26 mol%, an average projected area diameter of 1.10 µm, a thickness of 0.165 µm and a variation coefficient of diameter of 18.5% were obtained. After this, the soluble salts were removed by the sedimentation method. The temperature was raised to 40 ° C again, and 30 g of gelatin and 2.3 of phenoxyethanol were used.
Add 5 g and 0.8 g of sodium polystyrene sulfonate as a thickener, and add pH with caustic soda and silver nitrate solution.
It was adjusted to 5.90 and pAg 8.25. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, 0.043 mg of thiourea dioxide was added and the mixture was held for 22 minutes as it was for reduction sensitization. Then 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene 20 mg
And sensitizing dye

[0074]

[Chemical 41]

500 mg of was added. Further, 0.83 g of calcium chloride was added. Subsequently, 3.3 mg of sodium thiosulfate, 2.6 mg of chloroauric acid and 90 mg of potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. In this way, preparation of tabular grains T-1 was completed. On the other hand, the chemical sensitizer shown in Table 1 was added in place of 3.3 mg of sodium thiosulfate to prepare tabular grains T-2, T-3 and T-4.

[0076]

[Table 1]

Preparation of coating sample T-1 to T- were the same except for the additives shown in Table 2.
Coating samples 1 to 13 were prepared by adding the following chemicals to 1 mol of silver halide of 4 to prepare coating solutions.・ Gelatin (including Gel in emulsion) 65.6 g ・ Trimethylolpropane 9 g ・ Dextran (average molecular weight 39,000) 18.5 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g ・ Hardener 1 , 2-Bis (vinylsulfonylacetamide) ethane Addition amount is adjusted so that the swelling rate is 230%.

[0078]

[Chemical 42]

[0079]

[Table 2]

The surface protective layer was prepared and prepared so that each component had the following coating amount. Contents coating weight Gelatin 0.966 g / m ² · sodium polyacrylate surface protective layer (average molecular weight 400,000) 0.023 - 4-hydroxy-6-methyl-1,3,3a, 7- Tet Razainden 0. 015

[0081]

[Chemical 43]

Polymethylmethacrylate (average particle size 3.7 μm) 0.087 Proxel (adjusted to pH 7.4 with NaOH) 0.0005 Preparation of support (1) Preparation of dye D-1 for undercoat layer Was dyed by a ball mill by the method described in JP-A-63-197943.

[0083]

[Chemical 44]

434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X-200 surfactant (TX-200) were placed in a 2 liter ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO) beads 4
00 ml (2 mm diameter) was added and the contents were crushed for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. Observation of the obtained dye dispersion showed that the particle size of the crushed dye had a wide range of diameters from 0.05 to 1.15 .mu.m, and the average particle size was 0.37 .mu.m. Further, a centrifugation operation was performed to remove dye particles having a size of 0.9 μm or more. Thus, Dye Dispersion D-1 was obtained. (2) Preparation of support Corona discharge treatment was performed on a biaxially stretched 183 μm thick polyethylene terephthalate film, and the first undercoat liquid having the following composition was applied so that the coating amount was 5.1 cc / m ^2. It was applied with a wire bar coater and dried at 175 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the following structure.

[0085]

[Chemical formula 45]

Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 79 cc 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20.5 cc Distillation Water 900.5cc

[0087]

[Chemical formula 46]

On the above-mentioned first undercoat layer on both sides, a second undercoat layer having the following composition was applied to each side so that the coating amount was as described below, and 150 was applied to both sides by a wire bar coater method. Coated and dried at ℃.・ Gelatin 160 mg / m ²・ Dye Dispersion D-1 (26 mg / m ² as a solid dye component)

[0089]

[Chemical 47]

Matting Agent Preparation of Polymethyl Methacrylate 2.5 mg / m ² Photographic Material with Average Particle Diameter 2.5 μm The above emulsion layer and surface protective layer were coated on both sides by a simultaneous extrusion method on the prepared support. The coated silver amount per one side was 1.75 g / m ² . The amount of coated gelatin and the swelling ratio obtained by the freeze-drying method using liquid nitrogen were adjusted by the amount of gelatin added to the emulsion layer and the amount of hardener. Evaluation of photographic performance and pressure resistance Each sample of photographic materials 1 to 13 was exposed for 0.05 seconds from both sides using X Ray Orthoscreen HR-4 manufactured by Fuji Photo Film Co., Ltd. An evaluation was performed. After the exposure, the following processing was performed. Sensitivity is photographic material 207
Was set as 100 and the reciprocal of the ratio of the exposure dose giving a density of 1.0 was used. At this time, a sample subjected to a bending test before exposure was also prepared. [Processing] Automatic developing machine ... The drive motor and gears of SRX501 manufactured by KONICA Co., Ltd. were modified to speed up the transfer speed. <Developer concentrate> Potassium hydroxide 56.6 g Sodium sulfite 200 g Diethylenetriaminepentaacetic acid 6.7 g Potassium carbonate 16.7 g Boric acid 10 g Hydroquinone 83.3 g Diethylene glycol 40 g 4-Hydroxymethyl-4-methyl-1-phenyl-3- Pyrazolidone 22.0 g 5-methylbenzotriazole 2 g

[0091]

[Chemical 48]

Make up to 1 liter with water (adjust to pH 10.60). <Fixing solution concentrate> Ammonium thiosulfate 560 g Sodium sulfite 60 g Ethylenediaminetetraacetic acid / disodium dihydrate 0.10 g Sodium hydroxide 24 g Water is adjusted to 1 liter (pH is adjusted to 5.10 with acetic acid). When the development processing was started, each tank of the automatic processor was filled with the following processing solutions. Developing tank: Starter 1 containing the above developer concentrate 331, water 667 ml, potassium bromide 2 g and acetic acid 1.8 g.
0 ml was added to bring the pH to 10.25. Fixing tank: 200 ml of the above fixing solution concentrate and 800 ml of water Processing speed ... Dry to Dry 35 seconds Development temperature ... 35 ° C. Fixing temperature ... 32 ° C. Drying temperature ... 55 ° C. Replenishment amount ... Developer 22 ml / 10 × 12 inch Fixing solution 30 ml / 10 × 12 inch For oriental bald samples, the degree of pressure blackening was sensory evaluated and the one with the smallest blackening degree was set to 1 and the one showing the maximum blackening was set to 5 It was organized in 5 stages including. Table 3 shows the photographic performance evaluation results and the pressure evaluation results. As is clear from Table 3,
It can be seen that the light-sensitive material of the present invention has a remarkably small degree of pressure blackening despite its high sensitivity.

[0093]

[Table 3]

Example 2 4.5 g of potassium bromide and 2 g of gelatin in 1 liter of water.
0.6 g, 5 of thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH
% Aqueous solution (2.5 cc) and stirred in a container kept at 60 ° C. while stirring, 33 cc of aqueous solution of silver nitrate (3.43 g of silver nitrate), 33 cc of aqueous solution containing 2.97 g of potassium bromide and 0.363 g of potassium iodide are double jet method. For 37 seconds. Next, an aqueous solution of 0.9 g of potassium bromide was added, and then the temperature was raised to 70 ° C., and 53 cc of an aqueous silver nitrate solution (silver nitrate 4.
90 g) was added over 13 minutes. Here, 15 cc of 25% aqueous ammonia solution was added, and after physically aging for 20 minutes at the same temperature, 14 cc of 100% acetic acid solution was added. (The process as it is here is the same as that of T-1.) Subsequently, an aqueous solution of 133.3 g of silver nitrate and a mixed aqueous solution of potassium bromide and potassium iodide were added over 35 minutes by the control double jet method while keeping the pAg of 8.1. did. The potassium iodide consumed here was 0.2 mol% with respect to the total amount of silver in the final grain. Next, 10 cc of 2N potassium thiocyanate solution and AgI fine particles having a diameter of 0.07 μm were added in an amount of 0.20 mol% with respect to the total amount of silver. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, monodisperse tabular grains having a total silver iodide content of 0.46 mol%, an average projected area diameter of 1.15 μm, a thickness of 0.162 μm and a diameter variation coefficient of 20.5% were obtained. After this, the soluble salts were removed by the sedimentation method. The temperature was raised again to 40 ° C., and 30 g of gelatin, 2.35 g of phenoxyethanol and sodium polystyrene sulfonate (0.35 g) as a thickener.
8 g was added, and the pH was adjusted to 5.9 with caustic soda and silver nitrate solution.
0, pAg was adjusted to 8.25. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, 0.043 mg of thiourea dioxide was added and the mixture was held for 22 minutes as it was for reduction sensitization. Next, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 20 mg and T-
500 mg of the sensitizing dye used in Preparation 1 was added. Further, 0.83 g of calcium chloride was added. Subsequently, 3.3 mg of sodium thiosulfate, 2.6 mg of chloroauric acid and 90 mg of potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. Emulsion T-5 was prepared in this manner. Emulsion T-5
Emulsion T-6 was prepared in exactly the same manner, except that the preparation of (1) and the addition of 1.3 mg of sodium thiosulfate and 2.7 mg of selenium compound 21 in place of 3.3 mg of sodium thiosulfate.

Silver iodide 1 having an average grain size of 0.3 μm was obtained by the double jet method while controlling the 60 ° C., pAg = 8.6, and pH = 5.0 so that the silver amount was equal to that of the tabular grains prepared above. A silver iodobromide monodisperse tetradecahedral emulsion containing 0.0 mol% was obtained. The coefficient of variation of this emulsion was 12% in terms of equivalent spherical diameter. This emulsion is desalted in the same manner as the tabular grains,
After the water washing step, the emulsion was chemically sensitized while stirring at 56 ° C. First, 0.020 mg of thiourea dioxide was added and held for 22 minutes for reduction sensitization.
Next, 4-hydroxy-6-methyl-1,3,3a, 7
-Add 10 mg of tetrazaindene and 300 mg of the sensitizing dye used to prepare T-1, and add calcium chloride 0.8.
3 g was added. Then 2.2 mg of selenium compound 21
And chloroauric acid 1.3 mg and potassium thiocyanate 0.6
g was added and after 50 ', cooled to 35 ° C. Emulsion T-7 was prepared in this manner. Emulsion T-8 was prepared in the same manner as above, except that 0.8 mg of sodium thiosulfate and 1.1 mg of compound 21 were added instead of adding selenium compound 21 during chemical sensitization for the preparation of emulsion T-7. Was adjusted. Emulsions T-5, T-6, T- prepared in this way
7 and T-8 were applied in exactly the same manner except that the coated amount of gelatin shown in Table 4 was different from that of the coated sample of Example 1 except that the additives shown in Table 5 were changed. 14-29 was produced.

[0096]

[Table 4]

[0097]

[Table 5]

These samples were tested for photographic sensitivity and pressure blackening in exactly the same way as shown in the examples. These evaluations were performed by the same evaluation method as in Example 1. The results are shown in Table 6, and it is clear that the light-sensitive material of the present invention has high sensitivity and excellent pressure blackening resistance.

[0099]

[Table 6]

Example 3 Coating samples 30 to 13 were prepared in the same manner as coating samples 1 to 13 prepared in Example 1 and coating samples 14 to 30 prepared in Example 2 except that the additives shown in Table 7 were added. 51
Was produced.

[0101]

[Table 7]

The coated sample prepared in this way was coated 5
The results of Table 8 were obtained when the results of the treatment after the day and the results of the treatment after being aged for 12 months in an environment of 30 ° C. and 60% were compared with the sensitization and the treatment conditions of Example 1. Sensitivity was shown with coating sample 1 of Example 1 being 100.

[0103]

[Table 8]

As shown in Table 8, it is clear that the light-sensitive material of the present invention is excellent in storage stability.

Example 4 The coating methods 1 to 29 prepared in Examples 1 and 2 were processed in exactly the same manner as in Example 1 with respect to photographic performance and pressure blackening degree, and processing methods (I) and (II) were shown below. It was processed and evaluated.
The results are exactly the same as in Example 1, and it was found that the light-sensitive material of the present invention had a small degree of pressure blackening in spite of high feeling, and showed excellent performance. At this time, the development was conducted using FPM9000 manufactured by FUJIFILM Corporation, after setting the processing time and changing the processing liquid.

[0106]

[Table 9]

Developer (I) 1-Phenyl-3-pyrazolidone 1.5 g Hydroquinone 30 g 5-Nitroindazole 0.25 g Potassium bromide 3.0 g Anhydrous sodium sulfite 50 g Potassium hydroxide 30 g Boric acid 10 g Glutaraldehyde 5 g Water was added. The total amount is adjusted to 1 liter (pH was adjusted to 10.20) Fixer (I) Ammonium thiosulfate (70 wt / vol%) 200 ml Ethylenediaminetetraacetic acid disodium salt dihydrate 0.02 g Sodium sulfite 15 g Boric acid 10 g Hydroxylated Sodium 6.7 g Glacial acetic acid 15 g Aluminum sulfate 10 g Sulfuric acid (36 N) 3.9 g Water is added to bring the total volume to 1 liter (pH adjusted to 4.25) Developer (II) Potassium hydroxide 29 g Potassium sulfite 44. 2g sodium hydrogen carbonate 7.5g Uric acid 1.0 g Diethylene glycol 12 g Ethylenediaminetetraacetic acid 1.7 g 5-Methylbenzotriazole 0.06 g Hydroquinone 30 g Glacial acetic acid 18 g Triethylene glycol 12 g 5-Nitroindazole 0.25 g 1-Phenyl-3-pyrazolidone 2.8 g Glutaraldehyde (50 wt / wt%) 9.86 g Sodium metabisulfite 12.6 g Potassium bromide 3.7 g Water was added to 1.0 liter.

Example 5 With respect to the coated samples 30 to 51 prepared in Example 3, the change in performance over time with respect to the fresh photographic performance was examined in exactly the same manner as in Example 3. At this time, the processing method is the same as that of the fourth embodiment.
It was carried out in the same manner as in Example 4 according to the processing methods (I) and (II) shown in FIG. The results are almost the same as in Example 3, and it was confirmed that the light-sensitive material of the present invention showed excellent performance both immediately after coating and after aging, and the fluctuation in performance with time was small.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 30, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0069

[Correction method] Change

[Correction content]

In the layer containing tabular silver halide grains of the present invention, the tabular grains are present in an amount of 50% or more, and particularly 60% or more by weight based on the total silver halide grains in the layer. Is preferred. The thickness of the layer containing tabular silver halide grains is 0.3 to 5.0 μm, particularly 0.5 to 3.0 μm.
It is preferably m. The coating amount of the tabular silver halide grains (on one side) is preferably 0.5 to 6 g / m ² , and particularly 1 to 4 g / m ² . Other constitutions of the layer containing the tabular silver halide grains of the present invention, for example, binder, curing agent, antifoggant, silver halide stabilizer, surfactant, spectral sensitizing dye, dye, ultraviolet absorber There is no particular limitation on the chemical sensitizer, etc., for example, Research Disclosure 176 Vol. 2
The description on pages 2-28 (December 1978) can be referred to.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0097

[Correction method] Change

[Correction content]

[0097]

[Table 5]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0099

[Correction method] Change

[Correction content]

[0099]

[Table 6]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0103

[Correction method] Change

[Correction content]

[0103]

[Table 8]

Claims (2)

[Claims] 1. A photosensitive halo of at least one layer on a support.
In a photographic light-sensitive material having a silver genide emulsion layer, the halo
The silver genide emulsion is chemically sensitized with a selenium compound,
In addition, the following general formulas (I), (II) and
Contains at least one of the compounds represented by (III)
A silver halide photographic light-sensitive material characterized by having. General formula (I)R in formula (I)₁₂, R₁₃, R₁₅, R₁₆Are the same but different
Can be replaced with hydrogen atom or benzene ring
R is a base₁₁, R₁₂Under hydrogen atom or alkaline conditions
It is a deprotectable protecting group. R₁₂Through R₁₆, OR₁₁,
OR₁₄May jointly form a ring. General formula (II)R in formula (II)_{twenty two}Through R₂₆Are the same but different
Or a group capable of substituting for a hydrogen atom or a benzene ring.
R_{twenty one}Is a protection that can be deprotected under hydrogen atoms or alkaline conditions
It is a base. R_{twenty two}Through R₂₆, OR_{twenty one}Together form a ring
May be. However, R_{twenty two}Through R ₂₆At least one of
In that group, there is also an adsorption promoting group for silver halide grains.
Substituted by one or the total number of carbon atoms is 6 or more
And is substituted with at least one group
Is a hydroxy group or a group that can be deprotected under alkaline conditions
Has been replaced. General formula (III):R in the formula¹, R²Can be the same or different from each other,
Hydroxy group, hydroxylamino group, amino group,
Rualkylamino group, arylamino group, aralkylamino group
Group, alkoxy group, phenoxy group, alkyl group, aryl
Group, an alkylthio group or a phenylthio group. 2. A total of 70 projected areas of all halogen grains.
2. The silver halide photographic light-sensitive material according to claim 1, wherein% or more is a tabular grain having an aspect ratio of 3 or more.