JPH08220670A - Silver halide photographic sensitive material and development processing method using same - Google Patents

Abstract

PURPOSE: To obtain sensitivity to infrared rays with small fluctuation of sensitivity by spectrally sensitizing a silver halide emulsion into a specified wavelength region with a specified sensitizing dye and incorporating a specified hydrazine compound in the emulsion and specifying the pH value at the surface of a film. CONSTITUTION: This photosensitive material has the photosensitive silver halide emulsion layer containing >=50mol% silver chloride on a support and spectrally sensitized with the sensitizing dye so as to obtain the maximum sensitivity in the longer wavelength region of >=750nm. The film surface of the emulsion layer has a pH of <=6.0 and the emulsion layer and the other hydrophilic colloidal layer contains the hydrazine compound represented by the formula in which R1 is an aliphatic or aromatic group; R2 is an H atom or an alkyl group or the like; G1 is a -CO- group or the like; and both of A1 and A2 is an H atom or one of them is an H atom and the other is an optionally substituted alkylsulfonyl group or the like.

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 spectrally sensitized in the infrared region and a development processing method using the same, and in particular, improvement in storage stability with time and development processing suitability. The present invention relates to a photographic light-sensitive material for plate-making having a super-high contrast characteristic in which the infrared region is spectrally sensitized, and a development processing method using the same.

[0002]

2. Description of the Related Art As one of exposure methods for a photographic light-sensitive material, an original image is scanned, and a silver halide photographic light-sensitive material is exposed on the basis of the image signal to expose a negative image or a positive image corresponding to the image of the original image. There is known an image forming method by a so-called scanner method for forming an image. There are various types of recording apparatuses that use the scanner-type image forming method, and conventionally, glow lamps, xenon lamps, mercury lamps, tungsten lamps, light-emitting diodes, and the like have been used as the recording light sources of these scanner-type recording apparatuses. However, each of these light sources has a practical drawback that the output is weak and the life is short. To compensate for these drawbacks,
There is a scanner that uses a coherent laser light source such as a Ne-He laser, an argon laser, and a He-Cd laser as a light source of a scanner system. Although they can obtain high output, they have drawbacks such as a large device, high cost, and need for a modulator.

On the other hand, a semiconductor laser is small and inexpensive, easy to modulate, has a longer life than the above laser, and emits light in the infrared region. Since the safelight can be used, there is an advantage that handling workability is improved.

Although a light-sensitive material corresponding to a semiconductor laser having such advantages has recently been put on the market, a large space is required as a working environment or a replenisher for use of a large amount of developer in an office. Therefore, there has been a demand for a silver halide photographic light-sensitive material capable of reducing the replenishment amount, or a processing method with less trouble such as silver stain even when the replenishment amount is reduced.

Regarding a photographic light-sensitive material which is sensitive to a semiconductor laser beam, that is, is spectrally sensitized in the infrared region and is composed of silver halide grains containing silver chloride, it is disclosed in JP-A-60-808.
No. 41, No. 62-299838, No. 62-29983.
No. 9, No. 61-70550, No. 63-115159.
No. 63-115160, No. 63-115161
No. 80-8760. For silver bromide or silver iodobromide systems, JP-A-63-49752 and 63-63
-83719 and 63-89838. In order to increase the sensitivity in the infrared region, many sensitizing dyes have been developed in addition to the dyes described in the above patents. These are described, for example, in US Pat. No. 2,095,85.
No. 4, No. 2,095,856, No. 2,955,9
No. 39, No. 3,458,318, No. 3,482,9
No. 78, No. 3,552,974, No. 3,573.
921, 3,582,344, 3,615,6
32, 4,011,083.

Further, in the application of directly printing a positive or negative film from an image setter onto a printing plate (PS plate), the intermediate reversing step is omitted.
A film having ultra-high contrast properties is desired. A system for achieving superhigh contrast with a hydrazine compound in an emulsion spectrally sensitized to the infrared region is known, and JP-A 64-26841,
JP-A-2-35443, -184841, -1
13238. The light-sensitive materials described therein describe a processing method of developing with a developer having a pH of 11.0 or less, but the replenishment amount of the developer is 320 to 450 when processing 1 square meter of the silver halide photographic light-sensitive material.
It is necessary to have about milliliters, and further replenishment amount reduction methods and stable treatment methods are desired. When the replenishment amount is reduced, there is a problem that silver sludge in the developing tank increases and adheres to the photosensitive material. Further, the infrared spectrally sensitized emulsion and the hydrazine system are apt to raise sensitivity or fog (black spots) over time, which is a serious problem.

An example of using chemically sensitized silver chlorobromide in a system using hydrazines is disclosed in JP-A-53-20921,
60-83028, 60-140399, 6
3-46437, 63-103230, JP-A-3
-294844, 3-294845, 4-17
No. 4424 and Japanese Patent Application No. 3-188230. On the other hand, an example in which a silver halide emulsion containing a heavy metal complex such as hydrazine and rhodium or iridium is used in combination is
JP-A-60-83028, 61-47942, 61-47943, 61-29837, and 62-.
201233, 62-235947, 63-1
No. 03232 and the like.

It is known to reduce the change in photographic performance by reducing the change in pH value of the developer,
Stabilizing photographic performance by increasing the buffering capacity of a developing solution is disclosed in Japanese Patent Publication No. 3730/1993. It is known to supply a developing solution as a solid processing agent, and JP-A-61-259921 describes that the stability of the developing solution as a solid processing agent is enhanced. Furthermore, JP-A-5-
No. 265147 discloses a processing method in which a developing solution for processing a hydrazine-containing photosensitive material is supplied as a solid processing agent.

[0009]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a superhigh-contrast silver halide photographic light-sensitive material having sensitivity to infrared light, which has a small sensitivity variation even after a long period of time after coating. That is. The second object of the present invention is to achieve pH 11.
With a stable developer of less than 0, a sufficiently hard negative image can be obtained, the fluctuation of photographic performance is small even if the replenishment amount of the developer is small, and stable performance is always obtained. An object of the present invention is to provide a development processing method for a high-contrast silver halide black and white photographic light-sensitive material.

[0010]

SUMMARY OF THE INVENTION A first object of the present invention is to:
In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the emulsion has a silver chloride content of 50 mol% or more, and the silver halide emulsion is sensitized. It is spectrally sensitized with a dye so as to have a maximum sensitivity in a long wavelength region of 750 nm or more, and a hydrazine compound represented by the following general formula (I) is added to the silver halide emulsion layer and other hydrophilic colloid layers. It was achieved by a silver halide photographic material characterized by containing and having a film surface pH of 6.0 or less.

[0011]

[Chemical 6]

In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group, or a hydrazino group. And G ₁ is a —CO— group,
-SO ₂ group, -SO- group,

[0013]

[Chemical 7]

A --CO--CO-- group, a thiocarbonyl group,
Or an iminomethylene group, A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted Represents an acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

To the second object of the present invention, in the method of developing the silver halide photographic light-sensitive material after imagewise exposure while replenishing the developing solution, the development initiation solution and the development replenishing solution are dihydroxybenzene. The property of containing a system developing agent and an auxiliary developing agent exhibiting super-additivity therewith, and having a pH increase of 0.25 or less when 0.1 mol of sodium hydroxide is added to 1 liter of the solution. Which has a pH of 9.5 to 11.0 and a replenishing amount of the developing solution of 225 ml / m ² or less. Achieved by the method.

The general formula (I) will be described in more detail. In the general formula (I), the aliphatic group represented by R ₁ is preferably an aliphatic group having 1 to 30 carbon atoms, and particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Moreover, this alkyl group may have a substituent. In the general formula (I), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring. Among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group. The aliphatic group or aromatic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group-containing group, a pyridinium group and a hydroxy group. Group, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemicarbazide group, urethane group, group having a hydrazide structure A group having a quaternary ammonium structure, an alkyl or aryl thio group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carboxyl group, a sulfo group, an acyl group, an alkoxy or aryloxy carbonyl group, a carbamoyl group, a sulfamoyl group, Examples include a rogen atom, a cyano group, a phosphoric acid amide group, a diacylamino group, an imide group, a group having an acylurea structure, a group containing a selenium atom or a tellurium atom, a group having a tertiary sulfonium structure or a quaternary sulfonium structure, and the like. As a preferred substituent, a linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 20),
Aralkyl group (preferably 1 to 1 carbon atoms in the alkyl part)
3 monocyclic or bicyclic), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms),
Acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (Preferably having 1 to 3 carbon atoms
0) and so on.

In the general formula (I), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example benzene. It contains a ring. At least one nitrogen as the unsaturated heterocyclic group,
A 5- or 6-membered ring compound containing oxygen and a sulfur atom, for example, an imidazolyl group, a pyrazolyl group, a triazolyl group,
Examples include a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, and a quinolinyl group. A pyridyl group or a pyridinium group is particularly preferable. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic group, the amino group is an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, aryl Amino groups are preferred. R ₂ may be substituted, and as the preferable substituent, those exemplified as the substituent of R ₁ are applicable. Preferred among the groups represented by R ₂ is when G ₁ is a —CO— group,
Hydrogen atom, alkyl group (for example, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (for example, o-hydroxybenzyl group, etc.), Aryl groups (eg phenyl groups, 3,5
-Dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group and the like), and a hydrogen atom and trifluoromethyl group are particularly preferable. Also, G ₁ is -S
In the case of an O ₂ — group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group) or a substituted amino group (eg, , Dimethylamino group, etc.) are preferred. When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group and an amino group are preferable.
As G _{1 in the} general formula (I), —CO— group, —COCO—
Groups are preferred, and -CO- groups are most preferred. Also, R ₂ splits the G ₁ -R ₂ part from the residual molecule, and -G ₁ -R
It may be one that causes a cyclization reaction to form a cyclic structure containing _two atoms, and examples thereof include those described in JP-A-63-29751.

A ₁ and A ₂ are a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group, or the sum of Hammett's substituent constants is-).
Phenylsulfonyl group substituted to be 0.5 or more), acyl group having 20 or less carbon atoms (preferably benzoyl group, or substituted so that the sum of Hammett's substituent constants is -0.5 or more) A benzoyl group, or a linear, branched, or cyclic unsubstituted or substituted aliphatic acyl group (as the substituent, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group Can be mentioned)). A ₁ , A ₂
Is most preferably a hydrogen atom.

The substituents of R ₁ and R _{2 in} the general formula (I) may be further substituted, and preferred examples thereof include those exemplified as the substituents of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent ...
., May be multiply substituted, and preferred examples are also those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (I) may have a ballast group or polymer commonly used in a non-moving photographic additive such as a coupler incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group,
It can be selected from aralkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A No. 1-100530.

R ₁ or R _{2 in} the general formula (I) may be one in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include alkylthio groups, arylthio groups, thiourea groups, heterocyclic thioamide groups, mercaptoheterocyclic groups, and triazole groups, which are disclosed in US Pat.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048.
No. 59-201049, JP-A-61-17073.
No. 3, No. 61-270744, No. 62-948, No. 63-234244, No. 63-234245, No. 6
The groups described in 3-234246 are mentioned.

Particularly preferred hydrazine derivatives in the present invention are those in which R ₁ is a ballast group via a sulfonamide group, an acylamino group or a ureido group, a group which promotes adsorption to the surface of silver halide grains, or a group having a quaternary ammonium structure or It is a phenyl group having an alkylthio group, G is a -CO- group, R ₂ is a hydrogen atom, a substituted alkyl group or a substituted aryl group (the substituent is preferably an electron-withdrawing group or a hydroxymethyl group at the 2-position). ) Is a hydrazine derivative. Any combination of the above R ₁ and R ₂ alternatives is possible and preferred.

Specific examples of the compound represented by formula (I) are shown below. However, the present invention is not limited to the following compounds.

[0024]

Embedded image

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical 12]

[0029]

[Chemical 13]

[0030]

Embedded image

[0031]

[Chemical 15]

[0032]

Embedded image

[0033]

[Chemical 17]

[0034]

Embedded image

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, No. 4,269,929, No. 4,276,364
Nos. 4,278,748, 4,385,108
Issue No. 4,459,347 Issue No. 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016 No. 4,988,604
Issue No. 4,994,365 Issue 5,041,355
No. 5,104,769, British Patent No. 2,011,
391B, European Patent Nos. 217,310 and 301,
799, 356, 898, JP-A-60-1797.
34, 61-170733, 61-27074.
No. 4, No. 62-178246, No. 62-270948.
No. 63, No. 63-29751, No. 63-32538, No. 63-104047, No. 63-121838, No. 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
234246, 63-294552, 63-3
06438, 64-10233 and JP-A-1-90.
No. 439, No. 1-100530, No. 1-105941
No. 1, No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2.
83549, 1-285940, 2-2541.
No. 2, No. 2-77057, No. 2-139538, No. 2
-196234, 2-196235, 2-19
No. 8440, 2-198441, 2-198442.
No. 2-220042, No. 2-221953, No. 2-221954, No. 2-285342, No. 2-2.
85343, 2-289843, 2-3027.
No. 50, No. 2-304550, No. 3-37642,
No. 3-54549, No. 3-125134, No. 3-1
No. 84039, No. 3-240036, No. 3-2400.
No. 37, No. 3-259240, No. 3-280038.
No. 3, No. 3-228536, No. 4-51143, No. 4
-56842, 4-84134, 2-2302
No. 33, No. 4-96053, No. 4-216544,
No. 5-45761, No. 5-45762, No. 5-45
No. 763, No. 5-45764, No. 5-45765,
The thing described in Japanese Patent Application No. 5-94925 can be used.

The addition amount of the hydrazine derivative in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-2 mol per mol of silver halide, particularly 1 × 1.
The preferable addition amount is in the range of 0 ^-5 mol to 2 × 10 ^-2 mol.

The hydrazine derivative of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve. It can be used by dissolving it in Further, by a well-known emulsification dispersion method, it is dissolved by using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the hydrazine derivative powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method. Further, as described in JP-A-2-948, it can be used by being contained in fine polymer particles.

Infrared spectral sensitizing dyes used in the present invention are disclosed in JP-A-60-80841 and JP-A-62-29983.
No. 8 and No. 62-299839 and the general formula (IV
A), (IVb), and the dyes represented by formulas (IIIa) and (IIIb) described in JP-A-2-184841 are preferred. A specific example is shown below.

[0039]

[Chemical 19]

[0040]

Embedded image

[0041]

[Chemical 21]

[0042]

[Chemical formula 22]

[0043]

[Chemical formula 23]

[0044]

[Chemical formula 24]

The above infrared sensitizing dye used in the present invention is 5 × 10 ^-7 mol to 5 × 10 ^-3 mol, preferably 1 × 10 ^-6 mol to 1 × 10 ^-3 mol per mol of silver halide. It is contained in the silver halide photographic emulsion in a molar ratio of from 2.times.10.sup.- ⁶ mol to 5.times.10.sup.- ⁴ mol.

The infrared sensitizing dye used in the present invention can be directly dispersed in an emulsion. Further, these may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. Also, ultrasonic waves can be used for dissolution. As a method for adding the infrared sensitizing dye, as described in US Pat. No. 3,469,987, the dye is dissolved in a volatile organic solvent, and the solution is added to a hydrophilic colloid. A method of dispersing and adding this dispersion into an emulsion, as described in JP-B-46-24185, etc., a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added to the emulsion. Method: A method in which a dye is dissolved in a surfactant as described in U.S. Pat. No. 3,822,135 and the solution is added to an emulsion; red as described in JP-A-51-74624. A method of dissolving with a compound to be shifted and adding the solution to an emulsion; a dye as described in JP-A-50-80826 is dissolved in an acid containing substantially no water, and the solution is added to the emulsion. The method of addition is used In addition, U.S. Pat. Nos. 2,912,343 and 3
The methods described in No. 342,605, No. 2,996,287, No. 3,429,835, etc. are also used.
Further, the general formula (IV
The infrared sensitizing dyes a) and (IVb) may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but of course at any stage during the preparation of the silver halide emulsion. Can also be dispersed.

The sensitizing dye according to the present invention can be used in combination with other sensitizing dyes. For example, U.S. Pat. Nos. 3,703,377, 2,688,545, 3,397,060, 3,615,635,
No. 3,628,964, British Patent Nos. 1,242,5.
No. 88, No. 1,293,862, Japanese Patent Publication No. 43-49
No. 36, No. 44-14030, No. 43-10773
No. 3, U.S. Pat. No. 3,416,927, Japanese Patent Publication No. 43-4
930, U.S. Pat. Nos. 3,615,613 and 3,
The sensitizing dyes described in No. 615,632, No. 3,617,295, No. 3,635,721 and the like can be used.

The photographic light-sensitive material of the present invention has the general formulas (III) and (IV) described in JP-A-60-80841 for the purpose of enhancing the infrared spectral sensitization effect or enhancing the storage stability.
It is preferable to add the compound of (III) and
The compound of (IV) is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion, which can be dispersed directly in the emulsion and can also be dispersed in a suitable solvent such as water. , Methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.) or a mixed solvent containing a plurality of these solvents and added to the emulsion. Other sensitizing dyes can be added in the form of a solution or a dispersion in a colloid according to the method of addition.

For the purpose of improving image quality, it is preferable to add an antihalation dye or an antiirradiation dye to the photographic light-sensitive material of the present invention. Preferred dyes are those represented by the general formula (Va) described in JP-A-60-80841.
It is a dye represented by (Vd). The above general formula (V
Specific examples of the dyes represented by a) to (Vc) include, in addition to those described above, JP-A-62-3250 and 61-17.
No. 4540, No. 62-123454, and Japanese Patent Application No. 60-1
Those described in the specification of No. 74940 can also be used. These dyes may be used alone or in combination of two or more. These dyes are used in the backing layer 74
It is used in such an amount that the transmission optical density at 0 to 840 nm is 0.6 or more. Although the specific amount used varies depending on the type of dye, it is generally 10 ^-3 g / m ^{2 to} 1 g / m ^{2 and} especially 1
0 ^-3 g / m ² preferred amount in the range of to 0.5 g / m ² can be found.

The general formula (II) will be described in detail.

[0051]

[Chemical 25]

In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group or a heterocyclic residue, which may further have a substituent. . m represents an integer, L represents an m-valent organic group which is bonded to a P atom and its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X is linked to L. You may have. Examples of the groups represented by R ₁ , R ₂ and R ₃ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s
an aralkyl group such as a linear or branched alkyl group such as an ec-butyl group, a tert-butyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecyl group or an octadecyl group, a substituted or unsubstituted benzyl group; Cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, aryl groups such as phenyl group, naphthyl group, phenanthryl group; alkenyl groups such as allyl group, vinyl group, 5-hexenyl group; cyclopentenyl group,
Cycloalkenyl groups such as cyclohexenyl group; heterocyclic residues such as pyridyl group, quinolyl group, furyl group, imidazolyl group, thiazolyl group, thiadiazolyl group, benzotriazolyl group, benzothiazolyl group, morpholyl group, pyrimidyl group, pyrrolidyl group Is mentioned. Examples of the substituents substituted on these groups include a fluorine atom, a chlorine atom, a bromine atom, in addition to the groups represented by R ₁ , R ₂ and R ₃ .
Halogen atom such as iodine atom, nitro group, 1, 2, 3
Primary amino group, alkyl or aryl ether group, alkyl or aryl thioether group, carbonamido group, carbamoyl group, sulfonamide group, sulfamoyl group,
Hydroxyl group, sulfoxy group, sulfonyl group, carboxyl group, sulfonic acid group, cyano group or carbonyl group,
Is mentioned. Examples of the group represented by L are R ₁ ,
In addition to the groups synonymous with R ₂ and R ₃ , polymethylene groups such as trimethylene group, tetramethylene group, hexamethylene group, pentamethylene group, octamethylene group and dodecamethylene group, phenylene group, biphenylene group, naphthylene group and the like 2 Polyvalent aliphatic groups such as valent aromatic groups, trimethylenemethyl group, tetramethylenemethyl group, phenylene-1,3,
Examples thereof include polyvalent aromatic groups such as 5-toluyl group and phenylene-1,2,4,5-tetrayl group. Examples of the anion represented by X include halogen ions such as chlorine ion, bromine ion, and iodine ion, acetate ion, oxalate ion, fumarate ion, carboxylate ion such as benzoate ion, p-toluenesulfonate, and methanesulfonate. Examples thereof include sulfonate ion such as butane sulfonate and benzene sulfonate, sulfate ion, perchlorate ion, carbonate ion and nitrate ion. In the general formula (II), R ₁ ,
R ₂ and R ₃ are preferably groups having 20 or less carbon atoms, and aryl groups having 15 or less carbon atoms are particularly preferred. m is preferably 1 or 2, and when m is 1, L is preferably a group having 20 or less carbon atoms, and particularly preferably an alkyl group or aryl group having 15 or less total carbon atoms. When m represents 2, the divalent organic group represented by L is preferably an alkylene group, an arylene group or a divalent group formed by combining these groups, and further, these groups and a -CO- group. , -O
-Group, -NR ₄ -group (provided that R ₄ represents a hydrogen atom or a group having the same meaning as R ₁ , R ₂ and R ₃ and when a plurality of R ₄ are present in the molecule, they may be the same. May be different, and may be bonded to each other), -S
- is a divalent group formed by combining groups - group, -SO- group, -SO _2. When m represents 2, L is particularly preferably a divalent group having a total carbon number of 20 or less, which is bonded to a P atom at that carbon atom. When m represents an integer of 2 or more,
There are a plurality of R ₁ , R ₂ and R _{3 in the} molecule,
The plurality of R ₁ , R ₂ and R ₃ may be the same or different. n is preferably 1 or 2 and m is preferably 1 or 2. X may combine with R ₁ , R ₂ , R ₃ or L to form an inner salt. Many of the compounds represented by the general formula (II) of the present invention are known and commercially available as reagents. As a general synthetic method, there is a method of reacting a phosphinic acid with an alkylating agent such as an alkyl halide or a sulfonate: or a method of exchanging a counter anion of a phosphonium salt by a conventional method. Specific examples of the compound represented by the general formula (II) are shown below. However, the present invention is not limited to the following compounds.

[0053]

[Chemical formula 26]

[0054]

[Chemical 27]

[0055]

[Chemical 28]

[0056]

[Chemical 29]

General formulas (III) and (IV) will be described in more detail.

[0058]

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In the formula, A represents an organic group for completing the heterocycle, and may contain a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom, and the benzene ring may be condensed. . As a preferred example, A can be a 5- or 6-membered ring, and a more preferred example is a pyridine ring. B, 2 divalent group represented by C is an alkylene, arylene, alkenylene, -SO ₂ -, -
SO -, - O -, - S -, - N (R 5) - those constituted alone or in combination are preferred. However, R ₅ represents an alkyl group, an aryl group, or a hydrogen atom. As particularly preferable examples, B and C are alkylene, arylene, and -O.
-, -S- may be used alone or in combination. R ₁ and R ₂ are preferably alkyl groups having 1 to 20 carbon atoms and may be the same or different. A substituent may be substituted on the alkyl group, and as the substituent,
Halogen atom (eg, chlorine atom, bromine atom), substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.), substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl) Group), a substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), sulfo group, carboxy group, hydroxy group, alkoxy group (eg, methoxy group, ethoxy group, etc.), It represents an aryloxy group, an amide group, a sulfamoyl group, a carbamoyl group, a ureido group, an unsubstituted or alkyl-substituted amino group, a cyano group, a nitro group, an alkylthio group and an arylthio group. As a particularly preferred example, R ₁ and R ₂ each represent an alkyl group having 1 to 10 carbon atoms. Examples of preferred substituents include an aryl group, a sulfo group, a carboxy group, and a hydroxy group. R ₃ and R ₄ represent a hydrogen atom or a substituent, and examples of the substituent are selected from the substituents mentioned above as the substituents of the alkyl group of R ₁ and R ₂ . As preferred examples, R ₃ and R ₄ have 0 to 10 carbon atoms, and specific examples thereof include an aryl-substituted alkyl group and a substituted or unsubstituted aryl group. X represents an anion group, but in the case of an inner salt, X
Is not necessary. Examples of X include chlorine ion, bromine ion,
It represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate. Next, specific compounds of the present invention are described, but are not limited thereto. Further, the compound of the present invention can be easily synthesized by a generally well-known method, and the following documents are helpful. (See Quart. Rev., 16, 163 (1
962). )

Specific compounds of the general formulas (III) and (IV) are shown below, but the invention is not limited thereto.

[0061]

[Chemical 31]

[0062]

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The general formula (V) will be described in more detail.

[0064]

[Chemical 33]

The nitrogen-containing heteroaromatic ring represented by Z may contain a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom in addition to the nitrogen atom, and the benzene ring may be condensed. The heteroaromatic ring formed is preferably a 5- or 6-membered ring, more preferably a pyridine ring, a quinoline ring, or an isoquinoline ring. R ₅ is preferably an alkyl group having 1 to 20 carbon atoms, and may be a straight chain, branched chain, or cyclic alkyl group. More preferred is an alkyl group having 1 to 12 carbon atoms, and 1 to 8 carbon atoms
Is most preferred. X ⁻ represents an anion group, but in the case of an intramolecular salt, X ⁻ is not necessary. Examples of X ⁻ include chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate.

The groups represented by Z and R ₅ may be substituted and preferred substituents include a halogen atom (eg chlorine atom, bromine atom), a substituted or unsubstituted aryl group (eg phenyl group, Tolyl group, p-chlorophenyl group, etc.), substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), sulfo group, carboxy group, hydroxy group,
Represents an alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group, unsubstituted or alkyl-substituted amino group, cyano group, nitro group, alkylthio group, arylthio group . Examples of particularly preferable substituents include an aryl group, a sulfo group, a carboxy group, and a hydroxy group. Other examples of the substituent of A include a substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.) and a substituted or unsubstituted aralkyl group (eg, benzyl group, p-methoxyphenethyl group, etc.). preferable. Next, specific compounds of the present invention are described, but are not limited thereto. Further, the compound of the present invention can be easily synthesized by a generally well-known method, and the following documents are helpful. (See Quart. Rev., 16, 163 (196
2). ) Specific compounds of the general formula (V) are shown below, but the present invention is not limited thereto.

[0067]

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[0068]

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The amino compound that functions as a built-in nucleation accelerator will be described in detail. Effective amino compounds are described in US Pat. No. 4,975,354,
(1) contains at least one secondary or tertiary amino group, and (2) at least 3 in their structure.
A group consisting of one repeating ethyleneoxy unit and (3) exhibiting at least one, preferably at least three, most preferably at least four partition coefficients,
It is an amino compound.

The range of amino compounds used as built-in nucleation accelerators includes monoamines, diamines and polyamines. These amines may contain aliphatic amines or aromatic or heterocyclic moieties. The aliphatic, aromatic and heterocyclic groups present in the amine can be substituted or unsubstituted groups. The amino compounds of the present invention are compounds of at least 20 carbon atoms. The amino compound used as a built-in nucleation accelerator is a bis-tertiary amine having a distribution coefficient of at least 3 represented by the following formula.

[0071]

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In the above formula, n is an integer value of 3 to 50, more preferably 10 to 50, and R ₁ , R ₂ , R ₃ and R
₄ is independently an alkyl group having 1 to 8 carbon atoms, or R ₁ and R ₂ together represent an atom necessary for completing a heterocyclic ring, or R ₃ and R ₃ R ₄ represents an atom necessary to complete a heterocyclic ring together.

Another amino compound used as a built-in nucleation accelerator is a bis-secondary amine having a partition coefficient of at least 3 having a structure represented by the following formula.

[0074]

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In the above formula, n is an integer value of 3 to 50, more preferably 10 to 50, and each R is independently a straight chain or branched chain substituted or unsubstituted group having at least 4 carbon atoms. It is a substituted alkyl group. Preferably, the group consisting of at least 3 repeating ethyleneoxy units is directly attached to a tertiary amino nitrogen atom, and most preferably the group consisting of at least 3 repeating ethyleneoxy units is a bis-tertiary amino compound. Is linked to the tertiary amino nitrogen atom of. The most preferred amino compound is a compound represented by the following formula. Pr represents n-propyl.

[0076]

[Chemical 38]

Another amino compound useful as a built-in nucleation accelerator is the amino compound described in US Pat. No. 4,914,003 and is represented by the following formula.

[0078]

[Chemical Formula 39]

In the above formula, R ₂ and R ₃ may be substituted or unsubstituted alkyl groups or may be linked to each other to form a ring, and R ₄ is a substituted or unsubstituted alkyl, aryl or heterocyclic ring. the stands, a represents a divalent linking group, X is _{-CONR 5 -, - O-CONR} 5, -NR 5
CONR ₅ , -NR ₅ COO-, -COO-, -OCO
-, - CO -, - NR 5 CO -, - SO 2 NR 5 -, -
NR ₅ SO ₂ —, —SO ₂ —, —S— or —O— group, R ₅ in these groups represents a hydrogen atom or a lower alkyl group, and n represents 0 or 1, provided that The total number of carbon atoms contained in R ₂ , R ₃ , R ₄ and A is 20 or more.

Further, another amino compound useful as a built-in nucleation accelerator is the amino compound described in US Pat. No. 5,030,547 and is represented by the following formula. Y ₀ [(A ₀ ) _n B] _{m In the} above formula, Y ₀ represents a group that promotes adsorption to silver halide, A ₀ represents a divalent linking group, B represents an amino group, an ammonium group or nitrogen. Represents a heterocyclic group containing, m is 1, 2 or 3, and n is 1 or 2.

General formula (II), general formula (III), general formula (I
The addition amount of V), the compound represented by the general formula (V) and the amino compound useful as a nucleation accelerator is not particularly limited as long as it is added in a necessary amount depending on the characteristics of the photosensitive material. When used in the present invention, the preferable addition amount is 1 ×
10 ^{−5 to} 2 × 10 ⁻² mol / molAg, more preferably 2
It is x10 ^-5 to 1 x 10 ^-2 mol / molAg.

The compounds of the general formula (II), general formula (III), general formula (IV) and general formula (V) of the present invention and the amino compound useful as a nucleation accelerator are suitable water-miscible organic solvents. , For example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. can be used after dissolving. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, it can be used as a fine dispersion by a method known as a solid dispersion method.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is silver chlorobromide or silver iodochlorobromide having a silver chloride content of 50 mol% or more. The silver iodide content is 3 mol% or less, more preferably 0.
It is 5 mol% or less. The shape of the silver halide grains may be any of a cube, a tetradecahedron, an octahedron, an irregular shape and a plate shape, but a cube is preferable. The average grain size of silver halide is 0.
It is preferably 1 μm to 0.7 μm, more preferably 0.
It is 2 μm to 0.5 μm. Regarding particle size distribution,
It is preferable that the coefficient of variation represented by {(standard deviation of particle size) / (average particle size)} × 100 is 15% or less, more preferably 10% or less and the particle size distribution is narrow. The silver halide grains may have a uniform inner layer and a surface layer, or may have different layers. The photographic emulsion used in the present invention is described in P.
Chimie et Physique Photograhique (Paul by Glafkides
Montel, 1967), GF Duffin, Photograp
hic Emulsion Chemistry (The Focal Press, 1966
,) By VL Zelikman et al Making and Coating Phot
ographic Emulsion (The Focal Press, 1964)
And the like.

As the method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in the presence of excess silver ion (so-called reverse mixing method)
Can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferably, it is a tetra-substituted thiourea compound and is disclosed in JP-A-53-824.
08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinethione. In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016 and Japanese Examined Patent Publication No. 48-3689.
0, No. 52-16364, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent No. 4,242,44.
As described in JP-A-55-158124 and JP-A-55-158124, it is preferable to use the method of changing the concentration of the aqueous solution to grow it quickly within a range not exceeding the critical saturation.

A preferable complex for achieving the object of the present invention is a hexacoordinated complex represented by the following general formula. [ML ₆ ] ^m (In the formula, M is a metal selected from rhodium, ruthenium, rhenium and osmium, and L is a bridging ligand.
m = 0, -1, -2, -3. ) Preferred bridging ligands are nitrosyl and thionitrosyl,
Halide ligand (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenocyanate ligand, tellurocyanate ligand, azide coordination Child and aco ligands. When an aco ligand is present, it preferably occupies one or two of the ligands. Particularly preferred examples of M are rhodium and ruthenium.

Specific examples of the transition metal coordination complex are shown below. 1 [Ru (NO) Cl ₅ ] ^-2 2 [Ru (H ₂ O) Cl ₅ ] ^-1 3 [Ru (NO) (H ₂ O) Cl ₄ ] ^-1 4 [Rh (NO) Cl ₅ ] ^{- 2} 5 [Rh (H ₂ O) Cl ₅ ] ^-2 6 [Re (H ₂ O) CN ₅ ] ^-2 7 [Re (NO) ClCN ₄ ] ^-2 8 [Rh (NO) ₂ Cl ₄ ] ^-1 9 _{[Rh (NO) (H 2 O} ) Cl 4 ] ^-1 10 [Ru (NO) CN _5] ^-2 11 [Ru (NO) Cl _5] ^-2 12 [Rh (NS) Cl _5] ^-2 13 [Os (NO) Cl _5] ^-2 14 [Re (H ₂ O) Cl _5] ^-1 15 _{[Os (NS) Cl 4 (TeCN} ) ] ^-2 16 [Ru (NS) l _5] ^-2 17 [ Re (NS) Cl ₄ (SeCN)] ^-2 18 [Os (NS) Cl (SCN) ₄ ] ^-2

The above metal complex can be added to the silver halide during grain preparation. The content of the transition metal in the silver halide grains of the present invention is at least 10 ^-8 to 1 × 10 ^-6 mol, and preferably 10 ^{-7 to} 5 × 10 ^-7 mol per mol of silver halide. .

The silver halide photographic light-sensitive material of the present invention preferably contains an iridium compound in order to achieve high sensitivity and high contrast. Although various compounds can be used as the iridium compound used in the present invention,
For example, hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium and the like can be mentioned. These iridium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or an alkali halide (eg, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide.

The total addition amount of the iridium compound according to the present invention is 1 per mol of the finally formed silver halide.
^{X10 -8 to} 5 X 10 ^-6 mol is suitable, and preferably 5
It is x10 ^-8 to 1 x 10 ^-6 mol. The addition of these compounds can be appropriately carried out during the production of silver halide emulsion grains and before each step of coating the emulsion, but it is particularly preferable to add these compounds at the time of emulsion formation and to incorporate them into the silver halide grains. .

The silver halide grains used in the present invention include
It may contain metal atoms such as iron, cobalt, nickel, palladium, platinum, gold, thallium, copper and lead. The above metal is 1 × 10 ⁻⁹ to 1 × 10 ⁻⁴ per mol of silver halide.
Molar is preferred. Further, in order to contain the above metal, a metal salt in the form of a single salt, a double salt or a complex salt can be added and added at the time of preparation of particles.

The silver halide emulsion of the present invention is preferably chemically sensitized. As the chemical sensitization method, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method and a noble metal sensitization method can be used, and they can be used alone or in combination. When used in combination,
For example, the sulfur sensitizing method and gold sensitizing method, the sulfur sensitizing method, selenium sensitizing method and gold sensitizing method, the sulfur sensitizing method, tellurium sensitizing method and gold sensitizing method are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. As the sulfur sensitizer, known compounds can be used. For example, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines are used. be able to. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The amount of the sulfur sensitizer added varies depending on various conditions such as pH, temperature and size of silver halide grains during chemical ripening, but it is 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ⁻⁵ to 10 ⁻³ mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As unstable selenium compounds, JP-B-44-15748 and 43-13489,
Japanese Patent Application Nos. 2-13097, 2-229300, and 3
The compounds described in No. 121798 and the like can be used. Particularly, the general formula (VIII) in Japanese Patent Application No. 3-121798.
It is preferable to use the compounds represented by and (IX).

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride, which is presumed to serve as a sensitizing nucleus, on the surface or inside of silver halide grains. Regarding the rate of silver telluride formation in a silver halide emulsion, Japanese Patent Application No. 4-
It can be tested by the method described in 146739.
Specifically, U.S. Patent Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496.
No. 1, No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33
No. 3819, No. 3-53693, No. 3-131598.
No. 4-129787, Journal of Chemical Society Chemical Communication (J.Chem.Soc.Chem.Commun.) 635 (1980), ibid
1102 (1979), ibid 645 (1979),
Journal of Chemical Society Perkin Transaction (J.Chem.Soc.Perkin.Trans.)
1, 2191 (1980), edited by S. Patai, The Chemistry of Organic Selenium and Tellurium Campounds
rganic Serenium and Tellunium Compounds), Vol 1
(1986) and Vol. 2 (1987) can be used. In particular, the compounds represented by the general formulas (II) (III) (IV) in Japanese Patent Application No. 4-146739 are preferable.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions, etc., but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide, Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to. It is 85 ° C.

Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium and iridium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide. About 10 ^-7 to 10 ^-2 mol per mol of silver halide is used. Can be used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of formation of silver halide grains or physical ripening. Reduction sensitization can be used in the present invention. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound and the like can be used. The silver halide emulsion of the present invention can be prepared by the method disclosed in European Patent Publication (EP) -293,917.
A thiosulfonic acid compound may be added. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, those having chemical sensitization, Those with different conditions) may be used in combination.

In the present invention, it is preferable to add an acid in order to keep the film surface pH at 6.0 or less. The acid for adjusting the film surface pH used in the present invention may be either an organic acid or an inorganic acid, but acids such as citric acid, phthalic acid, citric acid ester, salicylic acid and phosphoric acid are preferable, and an undercoat layer, an emulsion It may be added to any layer such as a layer and a protective layer. The "film surface pH" in the present invention means that 0.05 cc of water is added on the measuring surface of a photographic light-sensitive material of 1 cm ² and 90%.
It is a value measured using a silver chloride flat type composite electrode after being left for 10 minutes in an atmosphere of RH or more. A specific example of the flat electrode is a pH meter manufactured by Toa Denpa Kogyo Co., Ltd. The film surface pH in the present invention is 6.0 or less, but 4.5 to 5.8 is particularly preferable.

Other various additives to be used in the light-sensitive material of the present invention are not particularly limited in addition to the above, and for example, those described in the following parts can be preferably used. Items Applicable places 1) Hydrazine production JP-A-2-12236, page 2, upper right column, line 19 to nucleating agent, page 7, upper right column, line 3, line 3-174143, page 20, lower right column General formula (II) and compounds II-1 to II-54 from line 1 to page 27, upper right column, line 20. 2) Nucleation accelerators JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 from general formulas (II-m) to (II-p) and compound II- 1 to II-22, compounds described in JP-A-1-179939. 3) Silver halide milk, JP-A-2-97937, page 20, right lower column, line 12; agent and its manufacturing method, page 21, left lower column, line 14; JP-A-2-12236, page 7 upper right column. The selenium sensitization method described in line 19 to line 12, lower left column of the same, and Japanese Patent Application No. 3-189532. 4) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4; JP-A-2-103536, page 16, lower right column, line 3 to page 17, lower left Spectral sensitizing dyes described in column 20, line 20 and JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, and Japanese Patent Application Nos. 3-189532 and 3-41-1064.

5) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to same, lower right column, line 7 and JP-A-2-18542, page 2, left lower column, line 13 Page 4, lower right column, line 18. 6) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5; and JP-A-1-237538 The thiosulfinic acid compound described in the official gazette. 7) Polymer Latte JP-A-2-103536, page 18, lower left column, line 12 to line 20. 8) Chemical compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to compound 19th line, upper left column, first line. 9) Matting agent / slip JP-A-2-103536, page 19, upper left column, line 15 From agent / plasticizer, page 19 upper right column, line 15 10) Hardeners, JP-A-2-103536, page 18, upper right column, lines 5 to 17; 11) Dyes Dyes in the lower right column, lines 1 to 18 of page 17 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and JP-A-3-185773. 12) Binders JP-A-2-18542, page 3, lower right column, lines 1 to 2. 13) Anti-black spot agent Compounds described in U.S. Pat. Examples 1 to 50), the general formulas (R -1), (R-2) and (R-3) described in JP-A 3-174 143, page 3 to page 20, compound examples 1 to 75, Furthermore, the compounds described in Japanese Patent Application Nos. 3-69466 and 15648. 15) Monomethine compound Compounds of general formula (II) described in JP-A-2-287532 (particularly compounds II-1 to II-26). 16) Dihydroxybe Compounds described in JP-A-3-39948, page 11, upper left column to twelfth genus, page lower left column, and EP452772A.

The developer used in the development processing of the light-sensitive material of the present invention may contain additives usually used (eg, developing agent, alkaline agent, pH buffering agent, preservative, chelating agent). . Any known method can be used for the development processing of the present invention, and a known development processing solution can be used. The developing agent used in the developing solution used in the present invention is not particularly limited, but contains dihydroxybenzenes and auxiliary developing agents exhibiting superadditivity therewith. Furthermore, in terms of developing ability, it is 1 with dihydroxybenzenes.
A combination of -phenyl-3-pyrazolidones, a combination of dihydroxybenzenes and p-aminophenols is preferred.

Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone,
Isopropyl hydroquinone, methyl hydroquinone,
There are hydroquinone monosulfonate, etc., but hydroquinone is particularly preferable. Examples of the developing agent for 1-phenyl-3-pyrazolidone or its derivative used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,
4-dimethyl-3-pyrazolidone, 1-phenyl-4-
Methyl-4-hydroxymethyl-3-pyrazolidone and the like. As the p-aminophenol-based developing agent used in the present invention, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-
There are aminophenol, N- (4-hydroxyphenyl) glycine and the like, and among them, N-methyl-p-aminophenol is preferable. The dihydroxybenzene-based developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / liter. Particularly preferably, it is in the range of 0.2 to 0.6 mol / liter. When the combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.0
5 to 0.6 mol / liter, more preferably 0.2 to
0.5 mol / liter, the latter is preferably used in an amount of 0.06 mol / liter or less, more preferably 0.03 mol / liter or less.

Examples of the preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite and formaldehyde sodium bisulfite.
Sulfite is used in an amount of 0.20 mol / liter or more, particularly 0.3 mol / liter or more, but if added in an excessively large amount, it causes silver stain in the developing solution, so the upper limit is 1.2 mol / liter. Is desirable. Particularly preferably, 0.
It is 35 to 0.7 mol / liter. As a preservative for a dihydroxybenzene-based developing agent, a small amount of an ascorbic acid derivative may be used in combination with sulfite. Examples of the ascorbic acid derivative include ascorbic acid, its stereoisomer, erythorbic acid, and alkali metal salts (sodium and potassium salts) thereof, and sodium erysorbate is preferably used from the viewpoint of material cost. The addition amount is preferably in the range of 0.03 to 0.12, and particularly preferably in the range of 0.05 to 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

The developer 1 used in the present invention
The definition will be explained in detail because the pH increase when 0.1 mol of sodium hydroxide is added to liter is 0.25 or less. The developer has a p of the developer when 0.1 mol of sodium hydroxide is added to 1 liter of the developer having a pH of 10.5.
A developer having an H value of 10.75 or less. More preferably, the pH increase is 0.2 or less.

As the alkali agent used for setting the pH, a usual water-soluble inorganic alkali metal salt (eg sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used. As additives used other than the above, development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; alkanolamines such as diethanolamine and triethanolamine, Development accelerators such as imidazole and its derivatives; mercapto compounds, indazole compounds, benzotriazole compounds, benzimidazole compounds as antifoggants or black pep
per) inhibitor may be included. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-
Nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenztriazole, 4-[(2-mercapto-1,3,4-
Thiadiazol-2-yl) thio] butanesulfonate sodium, 5-amino-1,3,4-thiadiazole-
2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. The amount of these antifoggants is usually 0.01 to 10 mmol, and more preferably 0.1 to 2 mmol, per liter of the developing solution.

Further, various organic / inorganic chelating agents can be used in combination in the developer of the present invention. As the inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate or the like can be used. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used. As the organic carboxylic acid, acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, asieleic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid , Itaconic acid, malic acid, citric acid, tartaric acid and the like, but are not limited thereto.

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid. Acetic acid,
Triethylene tetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, etc. JP-A-52-25632, 55-67
No. 747, No. 57-102624, and Japanese Patent Publication No. 53-53
The compounds described in the specification of No. 40900 and the like can be mentioned.

As the organic phosphonic acid, US Pat.
4454, 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (1979)
May issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

Examples of the organic phosphonocarboxylic acid include JP-A Nos. 52-102726, 53-42730, and 54.
-112127, 55-4024, 55-40
No. 25, No. 55-126241, No. 55-65955.
No. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of alkali metal salts or ammonium salts. The addition amount of these chelating agents is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, more preferably 1 ×, per 1 liter of the developing solution.
It is 10 ⁻³ to 1 × 10 ⁻² mol.

Further, as a silver stain preventing agent in a developing solution, JP-A-56-24347, JP-B-56-46585,
The compounds described in JP-B-62-2849 and JP-A-4-362942 can be used. Further, the compound described in JP-A-62-212651 can be used as the development unevenness preventing agent, and the compound described in JP-A-61-267759 can be used as the dissolution aid. Further, if necessary, a color toning agent, a surfactant, an antifoaming agent, a hardener and the like may be contained.

The developer used in the present invention contains a carbonate as a buffer, boric acid described in JP-A-62-186259, sugars (eg saccharose) described in JP-A-60-93433, and oximes. (Eg acetoxime),
Phenols (for example, 5-sulfosalicylic acid), tertiary phosphates (for example, sodium salt, potassium salt) and the like are used, and carbonate and boric acid are preferably used. The pH of the developer is preferably 9.5 to 11.0, and particularly preferably 9.8 to 10.7. The developing temperature and time are interrelated and are determined in relation to the total processing time. Generally, the developing temperature is about 20 ° C to about 50 ° C, preferably 25 to 45 ° C, and the developing time is 5 seconds to 2 seconds. Minutes, preferably 7 seconds to 1 minute 30 seconds. When processing 1 square meter of the silver halide black and white photographic light-sensitive material, the replenisher amount of the developer is 225 ml or less, preferably 180 ml to 60 ml. It is preferable to concentrate the treatment liquid and dilute it at the time of use for the purpose of transportation cost of the treatment liquid, packaging material cost, space saving and the like. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

The fixing agent of the fixing solution in the present invention is not particularly limited, but ammonium thiosulfate, ammonium thiosulfate, sodium thiosulfate and mixtures thereof can be preferably used. The amount of the fixing agent used can be appropriately changed. The concentration in the working solution is generally 0.7 to about 2.0 mol / liter. The fixing treatment agent in the present invention contains a water-soluble aluminum salt which acts as a hardener, and examples thereof include ammonium sulfate, potassium alum, ammonium alum, zinc alum, aluminum nitrate, aluminum chloride, aluminum chlorate and the like. . These are preferably contained in an amount of 0.01 to 0.15 mol / liter as the aluminum ion concentration in the used liquid.

As the aluminum stabilizer in the present invention, 5-sulfosalicylic acid, iminodiacetic acid, sodium gluconate, sodium glucoheptanate, malic acid and tartaric acid are preferable.

Among them, gluconic acid, iminodiacetic acid, 5-
Sulfosalicylic acid, glucoheptanoic acid, their derivatives, or their salts are preferred. Here, the gluconic acid may be an anhydride having a lactone ring. Among the above-mentioned compounds, gluconic acid, iminodiacetic acid and their alkali metal salts or ammonium salts are particularly preferable, and when these compounds dissolve the fixing agent of the present invention in water,
0.005-0.2 mol / liter, preferably 0.0
Used at a concentration of 05-0.1 mol / l. These compounds may be used alone or in combination of two or more. Furthermore, malic acid, tartaric acid, citric acid, succinic acid, oxalic acid, maleic acid, glycolic acid, benzoic acid, salicylic acid, tyron, ascorbic acid, glutaric acid, organic acids such as adipic acid, aspartic acid, glycine, cysteine, etc. The combined use with aminopolycarboxylic acids such as amino acids, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-propanediaminetetraacetic acid and nitrilotriacetic acid, and sugars is also preferable as an embodiment of the present invention.

If desired, the fixer may contain preservatives (eg, sulfite, bisulfite, etc.), pH buffers (eg, acetic acid, sodium carbonate, sodium hydrogencarbonate, phosphoric acid, etc.), and pH adjusters (eg. For example, sodium hydroxide, ammonia, sulfuric acid, etc.), a chelating agent having the ability to soften water, a compound described in JP-A-62-78551, a surfactant, a wetting agent, a fixing accelerator and the like can be contained.
Examples of the surfactant include anionic surfactants such as sulfates and sulfin oxides, polyethylene-based surfactants and amphoteric surfactants described in JP-A-57-6840, and known defoaming agents are used. You can also do it. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of fixing accelerators include alkyl- and allyl-substituted thiosulfonic acids and salts thereof, and Japanese Patent Publications Nos. 45-35754 and 58-122.
Thiourea derivatives described in JP-A Nos. 535 and 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat. No. 4,126,459, JP-A-64-4739, JP-A-1-47939. No. 4739, 1-1
The mercapto compounds described in Nos. 59645 and 3-101728, the mesoionic compound described in No. 4-170539, and ammonium thiocyanate can be included. The fixing solid agent (powder, granule, granule, lump, paste) and tablet of the present invention may be composed of a plurality of layers such that adjacent layers do not have components that react with each other when they contact each other. Alternatively, a single and / or a blend of multiple components that do not react with each other may be coated with a water-soluble coating agent and / or a water-soluble film and packaged.

Any known method can be used for producing the fixing solid agent and the tablet in the present invention. For example, as a packaging method, there is JP-A-61-259921.
The methods described in JP-A-4-16841 and JP-A-4-78848 can be used. Further, as a method of solidification and tableting, there are disclosed in JP-A-4-85533 and JP-A-4-85533.
No. 85534, No. 4-85535, No. 5-13436.
No. 2, No. 5-197090, No. 5-204098,
No. 5-224361, No. 6-138604, No. 6-
The method described in 138605 or the like can be used.

As a method for dissolving and replenishing the treating agent of the present invention, a certain amount is dissolved with a dissolving device having a stirring function,
Method of replenishing, dissolving with a dissolving device having a dissolving portion and a portion for stocking the completed liquid, replenishing from the stock portion, adding a treating agent to the circulating system of the automatic developing machine according to the treatment to dissolve and replenish There are methods such as a method and a method of dissolving and replenishing with an automatic developing machine having a dissolving tank built therein, and any other known method can be used.

The pH of the fixing processing agent of the present invention when dissolved is 4.
It is 0 or more, preferably 4.6 to 5.5. The replenishing amount of the fixing solution is 600 ml / m ² or less with respect to the processing amount of light-sensitive material, preferably ^{500ml / m 2 ~60ml / m 2} .

The light-sensitive material which has been developed and fixed is then washed with water or stabilized. For washing or stabilizing treatment, the amount of washing water is usually ² per 1 m ^{2 of} silver halide light-sensitive material.
It is performed at 0 liters or less, and a replenishment amount (0 liters or less
It can also be carried out by including, that is, washing with water. That is, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated. As a method of reducing the replenishment amount of flush water, a multistage countercurrent method (for example, 2
Stages, 3 stages, etc.) are known. When this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the normal direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially processed. Washed with water. When the washing with water is carried out with a small amount of water, JP-A-63-18
It is more preferable to provide washing tanks for squeeze rollers and crossover rollers described in No. 350 and No. 62-287252. Alternatively, addition of various oxidizing agents and filter filtration may be combined in order to reduce the pollution load which becomes a problem when washing with a small amount of water. Furthermore, a part or all of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with antifungal means according to the method according to the present invention is disclosed in JP-A-60- 23
As described in No. 5133, it can also be used for a processing solution having a fixing ability, which is a processing step before that. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness that tends to occur when washing with a small amount of water and / or to prevent the processing agent component attached to the squeeze roller from being transferred to the processed film. Good. Further, in order to prevent contamination by dyes eluted from the light-sensitive material, JP-A-63-16345
The dye adsorbent described in No. 6 may be installed in the washing tank. In addition, in some cases, stabilization treatment may be performed following the water washing treatment,
As examples thereof, JP-A-2-201357 and JP-A-2-132
No. 435, No. 1-102553, JP-A-46-444.
A bath containing the compound described in No. 46 may be used as the final bath of the light-sensitive material. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, fungicides, alkanolamines and surface active agents. Agents can also be added. Water used in the washing or stabilization process includes tap water, deionized water, halogen, water sterilized with ultraviolet germicidal lamps and various oxidizers (ozone, hydrogen peroxide, chlorate, etc.). It is preferable to use, and washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. Washing or stabilizing bath temperature and time is 0-5
0 ° C. and 5 seconds to 2 minutes are preferable.

The treatment liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store the packaging material having low oxygen permeability described in No. 73147. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The roller-conveying type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971, and is referred to simply as a roller-conveying type processor in this specification. The roller conveyance type processor comprises four steps of developing, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. . Instead of the water washing step, four stable steps may be used.

The solid processing agent used in the present invention is powder,
Tablets, granules, powders, lumps, or pastes are used, and the preferred form is the form or tablet described in JP-A-61-259921. The method for producing tablets is described in, for example, JP-A Nos. 51-61837 and 54-155038.
No. 52-88025, British Patent No. 1,213,808, and the like, and can be produced by a general method. Further, as a granule treating agent, for example, JP-A Nos. 2-109042 and 2-109.
It can be produced by a general method described in Nos. 043, 3-39735 and 3-39739. Further, the powder treating agent can be prepared by a general method as described in, for example, JP-A-54-133332, British Patents 725,892 and 729,862, and German Patent 3,733,861. Can be manufactured.

The high density of the solid processing agent of the present invention is 0.5 to 0.5 from the viewpoint of its solubility and the effect of the object of the present invention.
It is preferably 6.0 g / cm ³ , particularly 1.0 to 5.0.
It is preferably g / cm ³ .

"Two types of particles having at least two types of mutually reactive particulate substances, separated by at least one intervening separation layer of a substance inert to adjacent layers of reactive substances. In the solid processing agent, characterized in that the reactive substance is placed in a vacuum-packable bag as a packaging material, and the bag is evacuated and sealed, the word "inert" means that when the substances are in physical contact with each other. It means that it does not react under normal conditions in the package, or that there is no reaction if there is any reaction. The inert substance, apart from being inert to the two mutually reactive substances, need only be inert in the intended use of the two reactive substances. Furthermore, an inert substance is a substance that is used simultaneously with two reactive substances. For example, since hydroquinone and sodium hydroxide react with each other in the developer in direct contact, they can be stored in the package for a long time by using sodium sulfite or the like as a separation layer between hydroquinone and sodium hydroxide in vacuum packaging. Used as packaging materials for these vacuum packaging materials are bags made from a laminate of inert plastic film, plastic material and metal foil.

[0124]

Example An emulsion was prepared by the following method. Emulsion A: 0.13 M silver nitrate aqueous solution, and (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ corresponding to 1.5 × 10 ^-7 moles and K corresponding to 2 × 10 ^-7 moles per 1 mole of silver. 0.04M including ₃ IrCl ₆
The aqueous solution of halogen salt containing potassium bromide and 0.09M sodium chloride was added to an aqueous gelatin solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinethione by a double jet method at 38 ° C. for 12 minutes while stirring. Nucleation was performed by adding and obtaining silver chlorobromide grains having an average grain size of 0.14 μm and a silver chloride content of 70 mol%. Subsequently, similarly, a 0.87 M silver nitrate aqueous solution, 0.26 M potassium bromide, and a halogen salt aqueous solution containing 0.65 M sodium chloride were added over 20 minutes by the double jet method.

Thereafter, 1 × 10 ⁻³ mol of KI solution was added to each emulsion for conversion, and the emulsion was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added per 1 mol of silver, pH 6.0, pAg 7.5. At a temperature of 65 ° C., sodium benzenethiosulfonate 7 mg and benzenesulfinic acid 2 mg per mol of silver,
Chloroauric acid (8 mg), potassium thiocyanate (200 mg) and sodium thiosulfate (5 mg) were added and chemically sensitized to obtain optimum sensitivity, and then 4-hydroxy-6- as a stabilizer.
Methyl-1,3,3a, 7-tetrazaindene 150mg
Then, 100 mg of proxel was added as a preservative. Then, the temperature was adjusted to 55 ° C., and 100 mg of sodium salt of 5,5′-dichloro-9-ethyl-3,3′-bis (3-sulfopropyl) oxacarbocyanine was added.
To give silver chloride, and stir for 15 minutes to add silver chloride to 69.
A silver chloroiodobromide cubic emulsion A containing 9 mol% and having an average size of 0.25 μm was prepared. Emulsions BF shown in Table 1 were prepared in the same manner. Emulsions C and D had the chemical sensitization changed as follows. Preparation of Emulsion C The conditions for chemical sensitization of Emulsion A were pH 5.9, pAg7.
5, temperature 65 ° C., sodium thiosulfate 2.0 mg, triphosphine selenide 3.0 mg, chloroauric acid 6 mg, benzenethiosulphonic acid soda 4 mg, benzenesulfinic acid soda 1 mg Emulsion C was prepared. Preparation of Emulsion D The conditions for chemical sensitization of Emulsion A were pH 5.9, pAg7.
5, temperature 65 ° C., sodium thiosulfate 2.0 mg, triphosphine telluride 3.0 mg, chloroauric acid 6 mg, benzenethiosulphonic acid soda 4 mg, benzenesulfinic acid soda 1 mg Emulsion D was prepared.

[0126]

[Table 1]

Example 1 Infrared sensitization was carried out by adding an infrared sensitizing dye represented by IR-6 to these emulsions in an amount of 1.5 × 10 ^-3 mol per mol of silver. This emulsion has 3 parts for supersensitization and stabilization.
× 10 ^-3 mol / mol Ag of 4,4'-bis- (4,6-
Dinaphthoxy-pyrimidin-2-ylamino) -stilbene disulfonic acid disodium salt and 4 × 10 ⁻³ mol / mol Ag of 2,5-dimethyl-3-allyl-benzothiazole iodo salt were added. Furthermore, 4 x 10 per mol of silver
^-4 mol of the mercapto compound represented by (a), 4 × 10
^-4 mol of the triazine compound represented by (b) and the hydrazine derivatives I-37 and I-41 of the present invention, 5 × 10 ^-4 mol, 1 × 10 ^-4 mol, per 1 mol of silver, represented by the following structural formula. Nucleation accelerator, 15 wt% polyethyl acrylate for gelatin, 15 wt% latex copolymer for gelatin (n-butyl acrylate / styrene / 2-acetoacetoxyethyl methacrylate / methacrylic acid copolymer = 54/20 / 16/10), 2-bis (vinylsulfonylacetamido) ethane as a hardener 80 mg / m ² , 2,4-dichloro-6-hydroxy-S
-Triazine (40 mg / m ^{2) was} added, and silver (3.0 g / m ² ) was coated on a polyester support having an undercoat layer (0.5 μm) made of a vinylidene chloride copolymer. The gelatin was 1.5 g / m ² .

[0128]

[Chemical 40]

[0129]

Embedded image

On these emulsion layers, gelatin 0.5 g / m ² as a protective layer upper layer, 40 mg / m ^{2 of} amorphous SiO ₂ matting agent having an average particle size of about 3.5 μm, silicone oil 50 mg / m ² , colloidal silica 80 mg / m fluorosurfactant 5 mg / m ² of sodium dodecylbenzenesulfonate 10 represented by ² and the following structural formula as a coating aid (c)
0 mg / m ² , and 0.8 g of gelatin as the lower layer of the protective layer /
Table 3 was prepared by adding m ² , hydroquinone 100 mg / m ² , ethyl acrylate latex 400 mg / m ² and the following dyes.
A sample like the above was prepared. The pH of the film surface was adjusted as shown in Table 3 by adding citric acid to the emulsion layer. The pH value was measured by the method described in the specification.

[0131]

Embedded image

[0132]

[Chemical 43]

The back layer and the back protective layer were coated by the following formulation.

[Back Layer Formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ² Polyvinyl-benzene sulfonate 30 mg / m ²

[0135]

[Chemical 44]

SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² dye Mixture of dye [a], dye [b] and dye [c] dye [a] 50 mg / m ² Dye [b] 100 mg / m ² Dye [c] 50 mg / m ²

[0137]

Embedded image

[Back protective layer] Gelatin 0.8 mg / m ² polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfonic acid Sodium 15 mg / m ² Sodium acetate 40 mg / m ²

With respect to the sample produced by the above method, a replenishing amount was reduced and a running test was carried out to compare with a new liquid performance (photographic characteristic 1). The results are shown in Table 3. As is clear from Table 3, the combination of the present invention shows good results with small changes in sensitivity and gradation even when running with low replenishment.
Moreover, the sensitivity does not increase with time, which is good.

Evaluation was carried out by the following methods. (Photographic property 1) A sample was exposed with a xenon flash of 10 ^-6 sec through an interference filter having a peak at 780 nm and a continuous step wedge, and the following composition was used as a developing solution and a fixing solution having the formulation shown in Table 2 as a developing solution. Development was carried out using an FG-680A automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) at 35 ° C. and 30 ″ development. The evaluation results are shown in Table 2. Here, the sensitivity is 35 ° C. It is shown by the relative value of the reciprocal of the exposure amount that gives a density of 1.5 in 30 seconds development.

[0141]

[Table 2]

Fixing solution Ammonium thiosulfate 119.7 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.03 g Sodium thiosulfate pentahydrate 10.9 g Sodium sulfite 25.0 g NaOH (pure) 12.4 g Glacial acetic acid 29.1 g Tartaric acid 2 .92 g sodium gluconate 1.74 g aluminum sulfate 8.4 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.8 add water 1 liter

[0143]

[Equation 1]

(Photographic property 2: running performance) A running experiment was conducted using the sample prepared above. The running conditions are 40% of each full-size paper size (50.8 x 61.0 cm) with 80% blackening (8 out of 10 are exposed) per day, and it runs for 6 days. We had six runs, one round, a day off. Replenishment amount is 1
70 ml / m ² . Using each developer after running,
Photographic properties 1 and 2 were evaluated under the same conditions as Photographic Properties 2 and 3. [Preservability] Samples are stored at a humidity of 55% RH and a temperature of 40 ° C for 2
After being left for 0 days, sensitometry was performed under the condition of Photographic property 1 to evaluate the change in sensitivity to Photographic property 1.

[0145]

[Table 3]

Example 2 A running test and a silver stain test similar to those in Example 1 were conducted by combining the sample prepared in the same manner as in Example 1 with the developers D3 to D5 shown in Table 2. The results are shown in Table 4. As is apparent from Table 4, the combination of the present invention showed good results. In particular, the combination of D3 and D5 with a small pH change is good.

[0147]

[Table 4]

The silver stain was visually evaluated in 5 grades. The state where no silver stains are generated on the film, the developing tank, or the roller is set as "5", and the silver stain is generated on the entire surface of the film, and a large amount of silver stains is also generated on the developing tank and the roller. " “4” is not generated in the film, but is slightly generated in the developing tank and the roller, but it is a practically acceptable level. "3" or less has a problem in practical use or is unacceptable. Example 3 In the sample of Example 2, the hydrazine derivative was I-
10, the combination of I-29, and I-33, I-24
Even if the combination was changed to the above combination, good results were obtained with the configuration of the present invention. Example 4 In the sample of Example 1, the infrared spectral sensitizing dye was used as an IR.
Even if the -6 was changed to IR-12 or IR-20, the constitution of the present invention showed good results.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 1/09 G03C 1/09 1/20 1/20 1/295 1/295 5/26 520 5 / 26 520 5/29 501 5/29 501 5/30 5/30 5/31 5/31

Claims (10)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the emulsion has a silver chloride content of 50 mol% or more,
Also, the silver halide emulsion is 750 nm with a sensitizing dye.
It is spectrally sensitized to have maximum sensitivity in the above long wavelength region, and further contains a hydrazine compound represented by the following general formula (I) in the silver halide emulsion layer and other hydrophilic colloid layers, The pH of the film surface on the emulsion layer side is 6.
A silver halide photographic material characterized by being 0 or less. Embedded image In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group,
Represents an alkoxy group, an aryloxy group, an amino group, or a hydrazino group, G ₁ represents a —CO— group, a —SO ₂ group,
-SO- group, , -CO-CO- group, thiocarbonyl group, or iminomethylene group, both A ₁ and A ₂ are hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted group. It represents a substituted arylsulfonyl group or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the group defined for R ₂ ,
It may be different from R ₂ . 2. A silver halide photographic light-sensitive material containing at least one compound selected from general formulas (II), (III), (IV) and (V) and an amino compound acting as a nucleation accelerator. The silver halide photographic material according to claim 1, wherein the silver halide photographic material is contained. Embedded image In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group and a heterocyclic residue, which may further have a substituent. m represents an integer of 1 to 4, L represents an m-valent organic group which is bonded to the P atom by its carbon atom, and n is 1
Represents an integer of 3 to 3, X represents an n-valent anion, X
May be linked to L. [Chemical 4] In the formula, A represents an organic group for completing the heterocycle. B and C each represent a divalent group. R ₁ , R
₂ represents an alkyl group or an aryl group,
R ₃ and R ₄ represent a hydrogen atom or a substituent. X is
Represents an anionic group, but is not necessary when forming an intramolecular salt. Embedded image In the formula, Z represents an atomic group necessary for forming a nitrogen-containing heteroaromatic ring, R represents an alkyl group, and X ⁻ represents a counter anion. 3. The silver halide photographic material according to claim 1, wherein the silver halide grains are sensitized with a selenium sensitizer or a tellurium sensitizer. 4. A method of developing the silver halide photographic light-sensitive material according to claim 1 or 2 after imagewise exposure while replenishing a developing solution, wherein the development initiation solution and the development replenishing solution are a dihydroxybenzene-based developing agent and the developing agent. It contains an auxiliary developing agent exhibiting super-additivity, and is 0.
It is a liquid having a property that the pH rise when 1 mol of sodium hydroxide is added is 0.25 or less, the pH of the development starter is 9.5 to 11.0, and the replenishment amount of the developer is A method for developing a silver halide black and white photographic light-sensitive material, characterized in that it is 225 ml / m ² or less. 5. The development processing method according to claim 4, wherein the developer contains a carbonate in an amount of 0.5 mol / liter or more. 6. The development processing method according to claim 4, wherein the developing solution contains a dihydroxybenzene-based developing agent in an amount of 0.23 mol / liter or more. 7. A 1-phenyl-3-pyrazolidone-based compound and / as an auxiliary developing agent exhibiting superadditivity to a developing solution.
7. The development processing method according to claim 4, which further comprises a p-aminophenol compound. 8. The developer contains 0.3 to 1.2 mol / liter of free sulfite ion and an ascorbic acid derivative, and the concentration ratio of the ascorbic acid derivative / dihydroxybenzene type developing agent is 0.03 to 0. The development processing method according to any one of claims 4 to 7, wherein the development processing is performed with a developing solution of No. 12. 9. The development processing method according to claim 4, wherein the developer is prepared by using a solid processing agent. 10. A layer comprising at least two mutually reactive particulate materials, separated by at least one intervening separation layer of a material inert to adjacent layers of reactive material. 10. The development processing method according to claim 9, wherein the solid processing agent is used in which a reactive packaging material is placed and a vacuum-packable bag is used as a packaging material, and the bag is evacuated and sealed.