JP2000275775A - Silver halide photographic sensitive material and processing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material for an image setter capable of raid processing and less liable to cause stain by forming a layer containing a specified compound and specifying the immersion time. SOLUTION: The silver halide photographic sensitive material has a layer containing a compound of the formula and is developed in 5-60 sec immersion time. In the formula, Y1 is O, S, Se, -(CH=CH) or -NR2, Z is an atomic group required to form a condensed ring having >=5 atoms, R1 and R2 are each H or an aliphatic group, L1-L6 are each methine, n, m1 and m2 are each 0 or 1, Q is a group of nonmetallic atoms required to form an acidic ring, in the case of m1=m2=1, at least one of L1-L6 has a specified substituent in the case of m1=1 and m2=0, at least one of L1-L4 has a specified substituent, and in the case of m1=m2=0, at least one L1-L2 as a specified substituent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for processing a black-and-white silver halide photographic light-sensitive material, and more particularly to a method for processing a silver halide photographic light-sensitive material for printing plate making for an image setter.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter, also referred to as a "light-sensitive material") for printing plate making is often processed by an automatic developing machine connected to a laser output device called an image setter. . In many cases, the light-sensitive material output from the image setter is used as an exposure original of a PS plate as a final plate, and it is an important performance that the light-sensitive material is free from contamination. On the other hand, in order to improve the production efficiency of the image setter, it is desired to improve the holding speed (transport speed) of the photosensitive material of the automatic developing machine and to shorten the entire processing time.

[0003]

However, if the conveying speed of the automatic developing machine is increased or the processing time is shortened, the amount of dirt adhering to the photosensitive material increases. In particular, when the water temperature in the washing step is 10 ° C. or lower, the stain may be so deteriorated that the processed photographic material cannot be used. As a technique for preventing the adhesion of dirt to the photosensitive material, a method of adding an oxidizing agent to washing water is known and widely used, but it is not perfect, and dirt is generated regardless of the presence or absence of this means. Turns out there are cases.

Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material for an image setter which can be rapidly processed and is hardly stained, and a processing method therefor.

[0005]

An object of the present invention is to provide a silver halide photographic material having a layer containing a compound represented by the above general formula (1), and a immersion time for the photographic material. This is achieved by performing development processing for 5 to 60 seconds.

The sensitizing dye is disclosed in Japanese Patent No. 25618.
No. 26 discloses a technique relating to a sensitizing dye in which the STERIMOL parameter is defined, but relates to sensitivity and storage stability, and it is completely known that the dye of the present invention has a stain-improving effect with respect to the mother nucleus dye. Had not been.

Hereinafter, the present invention will be described in detail.

In the general formula (1), Z is preferably 5
A six-membered ring, a six-membered ring, and a seven-membered ring.

R ¹ represents a hydrogen atom or an aliphatic group, and may be substituted, particularly preferably an alkyl group substituted with at least one water-soluble group. The water-soluble group include a water-soluble group and its precursors are generally known, for _{example, - (CH 2) n-} COOM, -CH 2
—C ₆ H ₄ —COOM, —CH ₂ —COO—CH ₂ —COO
_{Ri, -CH 2 -COO-CH 2} -CO-M, - (C
_{H 2) n-SO 3 M} , -C 6 H 4 -SO 3 M, - (CH 2) n
-OH, - a _{(CH 2) n-OCO-} Ri ( where, n represents an integer from 1 to 6, M is hydrogen, an ammonium group, an alkali metal atom, an organic amine salt, Ri is preferably an alkyl group. ) And the like.

A preferred group for Q is

[0011]

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[Rl ₁ and Rl ₂ in the formula each include an alkyl group, an aromatic group, a heterocyclic group, a carbonylalkyl group, an alkylthio group, an amide group, an ureido group, a thioureido group, an oxyalkyl group and the like. Can be These may further have a substituent, particularly preferably a water-soluble group. ].

L is Ferloop, Hogenstraten, Tipcar (A. Verloop, W. Hooge)
Nstraten, J.A. Tipker), "Drug Design", Volume 7,
(Edited by EJ Ariens) Academic Press
Published in New York (1976), pp. 180-185, etc. (unit: Å), where B is the sum of STERIMOL parameters B
Represents the smaller value of ₁ + B ₄ and B ₂ + B ₃ (unit is Δ). Here, the STERIMOL parameter will be described in detail. For example, Chemistry Special Issue No. 122, “Structure-Activity Relationship of Drugs-Guidelines for Drug Design and Action Mechanism Research” 1
As described in pp. 39-141, 1979 (Nankodo), the STERIMOL parameter is one of the steric parameters widely used in the field of structure-activity relationship of drugs. STERIMOL parameters L, B ₁ , B ₂ ,
B ₃ and B ₄ is defined as follows.

L: It is assumed that all the substituents are on the benzene nucleus. The L axis is taken in the longitudinal direction of the bond connecting the substituent and the benzene nucleus. In consideration of the bonding distance of each atom constituting the substituent and the van der Waals radius, these projections to the L axis are considered, and the longest value is L.

B ₁ , B ₂ , B ₃ and B ₄ : The shape of the substituent is projected onto a plane perpendicular to the L axis. In the projection, the widths in four directions perpendicular to each other starting from the passing point of the L axis are determined as B ₁ , B ₂ , B ₃ , and B ₄ from the smallest one. That is, B ₁ ≦ B ₂ ≦ B
₃ ≦ B ₄ .

Such a STERIMOL parameter has various advantages, for example, (1) the steric effect constant E ₁
Although the measured values of the substituents are limited,
The IMOL parameter can be obtained by calculation for any substituent. (2) The steric effect of the substituent on the medicinal effect can be divided into the effect of the width of the substituent and the effect of the length of the substituent. Can be recognized more accurately.

Specific examples of the substituent satisfying SP ≦ 544 include a branched alkyl group having 3 or more carbon atoms, a benzyl group, a phenethyl group, and an alkoxycarbonyl group having 4 or more carbon atoms. Is, for example, isopropyl, branched butyl, branched pentyl, branched hexyl, branched octyl, benzyl, phenethyl, t-
There is a butylcarbonyloxy group.

Examples of the compound represented by the general formula (1) are shown below, but are not limited thereto.

[0019]

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[0020]

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[0021]

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[0022]

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In the present invention, it is particularly preferable that the immersion time in the liquid in the developing treatment is 5 to 60 seconds. The silver halide photographic light-sensitive material for plate making is usually processed by an automatic developing machine including at least a developing bath, a fixing bath and a washing (or stabilizing bath). The water washing bath may be composed of a plurality of tanks, or may be a tank for treating while supplementing a liquid containing chemicals such as anti-bacterial agent, oxidizing agent and chelating agent instead of just water. The immersion time in the liquid in the present invention is a time during which the photographic material is immersed in the liquid in each tank, and does not include a time such as wading.

The light-sensitive material of the present invention can be applied to an output device using a laser beam having a wavelength of 600 to 800 nm as a light source. It is particularly preferable to have sensitivity in this wavelength region because the selection of the output device is widened.

The silver halide photographic light-sensitive material of the present invention can have a generally known structure, and particularly preferably contains an organic contrast agent.

In the present invention, the organic contrasting agent may be a hydrazine derivative or a hydrazine derivative described in JP-A-10-10680.
It is preferable to use a tetrazolium compound which is a nitrogen-containing heterocyclic derivative having 6 to 6 members, and it is particularly preferable to use a hydrazine derivative.

Examples of the hydrazine derivative include those represented by the following general formula (H).

[0028]

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In the formula, A represents an aryl group or a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents-
(CO) n-group, sulfonyl group, sulfoxy group, -P
(＝ O) represents a R ⁵² — group or an iminomethylene group, n represents an integer of 1 or 2, both A ₁ and A ₂ are a hydrogen atom or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl R represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino A carbamoyl group or an oxycarbonyl group. R ⁵² represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, and amino group.

Among the compounds represented by the general formula (H), a compound represented by the following general formula (Ha) is more preferred.

[0031]

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In the formula, R ¹¹ represents an aliphatic group (eg, octyl group, decyl group), an aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (eg, pyridyl group, chenyl group, Furyl group),
These groups are preferably further substituted with an appropriate substituent. Furthermore, the R ¹¹ preferably contains at least one ballast group or a silver halide adsorption accelerating group.

As the ballast group, those commonly used in immobile photographic additives such as couplers are preferable, and those having 8 carbon atoms are preferable.
For example, alkyl, alkenyl, alkynyl, alkoxy, phenyl, phenoxy, alkylphenoxy and the like which are relatively inert to the above photographic properties can be mentioned.

Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula (Ha), X represents a group that can be substituted on a phenyl group, m represents an integer of 0 to 4,
Is 2 or more, X may be the same or different.

In the general formula (Ha), A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula (H), and both are preferably hydrogen atoms.

In the general formula (Ha), G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the formula (Ha), R ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, allyl group, heterocyclic group, alkoxy group, hydroxyl group, amino group, carbamoyl group, Represents an oxycarbonyl group. Desirable R ¹² is a substituted alkyl group in which a carbon atom substituted by G is substituted with at least one electron-withdrawing group, a —COOR ¹³ group, and a —CON
(R ¹⁴⁾ (R ¹⁵⁾ group (R ¹³ represents an alkynyl group or a saturated heterocyclic group, R ¹⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ¹⁵ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group). More preferably, it represents a substituted alkyl group substituted by two electron-withdrawing groups, particularly preferably three electron-withdrawing groups. R ¹²
The electron withdrawing group for substituting the carbon atom substituted with G preferably has a σp value of 0.2 or more and a σm value of 0.3 or more, for example, halogen, cyano, nitro, nitrosopolyhaloalkyl, polyhaloaryl, Alkyl or arylcarbonyl group, formyl group, alkyl or aryloxycarbonyl group, alkylcarbonyloxy group,
A carbamoyl group, an alkyl or aryl sulfinyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfonyloxy group, a sulfamoyl group, a phosphino group, a phosphine oxide group, a phosphonate ester group, a phosphonamide group, an arylazo group,
It represents an amidino group, an ammonio group, a sulfonio group, or an electron-deficient heterocyclic group.

R ^{12 in the} formula (Ha) particularly preferably represents a fluorine-substituted alkyl group, a monofluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

Next, specific examples of the compound represented by formula (H) are shown below, but the present invention is not limited thereto.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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Specific examples of other preferred hydrazine compounds are (1) to (252) described in US Pat. No. 5,229,248, columns 4 to 60. These hydrazine compounds can be synthesized by a known method. For example, US Pat.
It can be synthesized by the method as described in column 0.

The amount of addition may be any amount that makes the contrast high (the amount of the contrast enhancement).
Although the optimum amount varies depending on the degree of chemical sensitization and the type of the inhibitor, it is generally 10 ^-6 to 10 per mol of silver halide.
^-1 mol, preferably 10 ^-5 to 10 ^-2 mol. The hydrazine compound is added to at least one layer on the silver halide emulsion layer side, preferably to the silver halide emulsion layer and / or a layer adjacent thereto, more preferably to the emulsion layer. The amount of the hydrazine derivative contained in the photographic component layer closest to the support among the hydrazine derivative-containing photographic component layers is 0% of the total amount of the hydrazine derivative contained in the photographic component layer farther from the support. .2
0.8 molar equivalent. Preferably, it is 0.4 to 0.6 molar equivalent. The hydrazine derivatives used in the present invention may be used alone or in combination of two or more.

When the above-mentioned high contrast agent is used in the light-sensitive material to be processed, it is preferable to use a nucleation accelerator to promote the high contrast.

As the nucleation accelerator, a compound represented by the following general formula [Na] or [Nb] is preferably used.

[0057]

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In the general formula [Na], R ₁₁ , R ₁₂ , R
_{And 13} represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group, or a substituted aryl group, and R ₁₁ , R ₁₂ and R ₁₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable,
A molecular weight of 300 or more is particularly preferred. Preferred adsorbing groups include a heterocyclic ring, a mercapto group, a thioether group, a selenoether group, a thione group, and a thiourea group. Particularly preferred as the general formula [Na] are compounds having at least one thioether group as a halogen adsorbing group in the molecule.

Specific examples of the nucleation accelerator [Na] will be described below.

[0060]

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[0061]

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[0062]

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[0063]

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In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic or heterocyclic group. R ₁₄ represents a hydrogen atom, an alkyl group, an alkynyl group, or an aryl group,
Ar and R ₁₄ may be linked by a linking group to form a ring.
These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Preferred examples of the silver halide-adsorbing group include groups having the same meaning as the silver halide-adsorbing group of the compound represented by formula (H).

Specific examples of the compound represented by the general formula [Nb] include the following.

[0066]

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[0067]

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Specific examples of other preferred nucleation promoting compounds include the compounds (2-1) to (2-20) and 6-2587 described in JP-A-6-258571.
No. 51, (3-1) to (3-6), JP-A-7-27
No. 0957, onium salt compounds described in JP-A-7-104
No. 420, a compound of the formula I, JP-A-2-103536.
No. 19, page 19, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5;
No. 8 thiosulfonic acid compound.

The nucleation accelerator can be used in any photographic constituent layer on the side of the silver halide emulsion layer, but is preferably used in the silver halide emulsion layer or a layer adjacent thereto. The addition amount is the particle size of the silver halide grains,
Although the optimum amount varies depending on the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., it is generally preferably in the range of 10 ^-6 to 10 ^-1 mol, particularly preferably 10 ^-5 to 1 mol per mol of silver halide.
A range of 10 ^-2 mol is preferred.

The halogen composition of silver halide in the silver halide emulsion of the light-sensitive material of the present invention is not particularly limited. However, when processing is carried out with a small amount of replenishment or when rapid processing is carried out,
It is preferable to use a silver halide emulsion having a composition of silver chlorobromide containing 60 mol% or more of silver chloride and silver chloroiodobromide containing 60 mol% or more of silver chloride.

The average grain size of the silver halide is 1.2 μm.
m or less, particularly 0.8 to 0.1 μm
Is preferred. The particle size means a particle diameter when the particles are spherical or particles that can be approximated to spheres. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see C.I. E. FIG. Mees
& T. H. By James: The theory of
the photographic processes
s, 3rd edition, pp. 36-43 (1966 (Mcmill
an company).

The shape of the silver halide grains is not limited.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

In the present invention, the method of reacting the soluble silver salt with the soluble halogen salt may be any of a single-sided mixing method, a double-sided mixing method, and a combination thereof.

The silver halide emulsion contains tabular grains,
It is preferred that 50% or more of the total projected area of all grains in the emulsion layer in which the tabular grains are used are tabular grains having an aspect ratio of 2 or more. In particular, the ratio of tabular grains is 60 to
More favorable results are obtained with an increase to 70% and even to 80%. The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of a tabular grain to the distance between two parallel planes.

Among these tabular grains, tabular grains having a (100) plane having a silver chloride content of 50 mol% or more and having a main plane as a main plane are preferably used, and these are described in US Pat. No. 5,264,337. Nos. 5,314,798, 5,320,958, etc., and intended tabular grains can be easily obtained.

In the tabular grains, silver halides having different compositions can be epitaxially grown or shelled at specific surface portions. In order to control the photosensitive nucleus, a transition line can be provided on the surface or inside of the tabular grains. In order to provide a transition line, fine grains of silver iodide can be present during chemical sensitization or can be formed by adding iodine ions. The preparation of the particles can be appropriately selected from an acid method, a neutral method, an ammonia method and the like. When doping a metal, it is particularly preferable to form particles under acidic conditions of pH 1 to 5.

For controlling the growth of grains during the formation of tabular grains, for example, ammonia, thioether, thiourea compounds, thione compounds and the like can be used as a silver halide solvent.

At the time of physical ripening or chemical ripening, metal salts such as zinc, lead, thallium, iridium, rhodium, ruthenium, osmium, palladium and platinum can coexist. In order to obtain high illuminance characteristics, iridium is preferably doped in a range of 10 ^<-9> to 10 ^{< -3 >} mol per mol of silver halide. In order to obtain a high-contrast emulsion, rhodium, ruthenium, osmium and / or rhenium is preferably doped in a range of 10 ^-9 mol to 10 ^-3 mol per mol of silver halide.

The silver halide emulsion and its preparation method are described in detail in Research Disclosure (RD).
176: 17643, pp. 22-23 (Dec. 1978
Mon)) or in the literature cited.

The silver halide emulsion may be chemically sensitized.
Known methods of chemical sensitization include sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization, and any of these methods may be used alone or in combination.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5
-Mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3,3a, 7). -Tetrazaindenes), pentazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like can be added.

Gelatin is advantageously used as a binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used.

The photographic emulsion may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or acrylic acid, A polymer having a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid or the like as a monomer component can be used.

In the photosensitive photographic emulsion and the non-photosensitive hydrophilic colloid layer according to the present invention, an inorganic or organic hardener can be added as a crosslinking agent for a hydrophilic colloid such as gelatin.

In the light-sensitive material of the present invention, various other additives can be used, and examples thereof include a desensitizer, a plasticizer, a slipping agent, a development accelerator and an oil.

The support used for the photosensitive material is transparent,
It may be either non-permeable but is preferably a permeable plastic support. For plastic supports,
A support made of a polyethylene compound (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), a triacetate compound (eg, triacetate cellulose, etc.), a polystyrene compound, or the like is used.

The thickness of the support is preferably 50 to 2
It is 50 μm, particularly preferably 70 to 200 μm.

Further, it is preferable that the following compounds are contained in the constituent layers of the silver halide photographic light-sensitive material.

(1) Solid-dispersed fine particles of a dye JP-A-7-5629, page (3) [0017] to (1)
6) Compound described on page [0042] (2) Compound having an acid group Compound described in JP-A-62-237445, page 292 (8), lower left column, line 11 to page 309 (25), lower right column, line 3 (3) Acidic polymer JP-A-6-186659, page (10) [0036]
(4) Sensitizing dye JP-A-5-224330, page (3) [0017] to (17)
(13) Compound described on page [0040] JP-A-6-194777 (page 11) [0042]
Compound described in [0094] to page (22) [0015] to page (2) in JP-A-6-242533
(8) Compound described on page [0034] JP-A-6-337492 (3) page [0012]-
(34) Compound described on page [0056] JP-A-6-337494 (4) page [0013]-
(14) Compound described on page [0039] (5) Supersensitizer JP-A-6-347938 (3) page [0011] to
(16) Compound described on page [0066] (6) Tetrazolium compound JP-A-6-208188, page (8) [0059]-
(10) Compound described on page [0067] (7) Pyridinium compound JP-A-7-110556 (5) page [0028]-
(29) Compound described in [0068] (8) Redox compound JP-A-4-245243, pages 235 (7) to 250
(22) Compound described on page (9) SPS support Support described in JP-A-3-54551 The above-mentioned additives and other known additives are described, for example, in (RD) No. 17643 (December 1978),
No. No. 18716 (November 1979) and the same No.
308119 (December 1989).

In the present invention, the processing is preferably carried out by employing an automatic developing machine having at least four processes of development, fixing, washing (or stabilization) and drying.

As the developing solution used in the present invention, known developing agents can be used.
It is preferable to use a developing agent represented by

[0092]

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In the general formula (A), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group. R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and k =
When it is 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

In the compound represented by the general formula (A),
The following general formula [A] wherein R ₁ and R ₂ are bonded to each other to form a ring
-A] is particularly preferred.

[0095]

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In the formula, R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, It represents an amide group or a sulfonamide group, Y ₁ represents O or S, and Y ₂ represents O, S or NR ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

The alkyl group in the formula (A) or the formula [Aa] is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, an alkoxy group is preferably a lower alkoxy group, and an aryl group is preferably a phenyl group or a naphthyl group, and these groups may have a substituent. Preferred examples of the substitutable group include a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, and a sulfonamide group.

Specific examples of the compound represented by formula (A) or [Aa] according to the present invention are shown below.
The present invention is not limited to these.

[0099]

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[0100]

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These compounds are typically ascorbic acid or erythorbic acid and salts thereof or derivatives derived therefrom, and are commercially available or can be easily synthesized by a known synthesis method.

An alkali agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.) are added to the developer. Is preferred.

When the compound represented by the formula (A) is used as a developing agent, it preferably contains a sulfite as a preservative. The addition amount is preferably 0.02 to 0.3 mol / L, particularly preferably 0.1 to 0.2 mol / L.

If necessary, dissolution aids (polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants ,
Antifoaming agents, antifoggants (halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (ethylenediaminetetraacetic acid or Alkali metal salts, nitrilotriacetates, polyphosphates, etc.), development accelerators (US Pat. No. 2,304,025, JP-B-47-455).
No. 41), a hardening agent (glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent.

The pH of the developer is preferably adjusted to 7.5 or more and less than 10.5. More preferably, pH8.
5 or more and 10.2 or less.

As the fixing solution, those having a commonly used composition can be used. Further, a water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum, or an aldehyde compound (glutaraldehyde or a sulfurous acid adduct of glutaraldehyde) can be added.

It is preferable that the concentration of ammonium ion in the fixing solution is 0.1 mol or less per liter of the fixing solution. Particularly preferably, it is in the range of 0 to 0.05 mol. Preferably, the concentration of acetate ions in the fixing solution is less than 0.33 mol / L. More preferably, it is 0.22 mol or less per liter, particularly preferably 0.13 mol or less, whereby the amount of acetic acid gas generated can be greatly reduced. Most preferred are those that are substantially free of acetate ions.

The replenishing amount of the washing water is 1 m ^{2 of} the photosensitive material to be processed.
The volume is preferably 10 to 500 ml, more preferably 50 to 200 ml. Further, it is preferable to carry out a water washing treatment with washing water containing a purifying agent containing an oxidizing agent and a bactericide.

Examples of the oxidizing agent include metal or nonmetal oxides, oxyacids or salts thereof, peroxides, and compounds containing an organic acid system. From the viewpoint of discharging to drainage pipes, the oxyacids include sulfuric acid, nitrous acid, nitric acid,
Hypochlorous acid and the like are preferred, and as the peroxide, aqueous hydrogen peroxide and fentonic acid are particularly preferred. Most preferred is aqueous hydrogen peroxide. The amount of the oxidizing agent added to the washing tank is 槽 of the amount of thiosulfate brought into the photosensitive material.
The molar ratio is preferably in the range of 10 moles to 10 moles, and particularly preferably 1/2 mole to 3 moles.

The bactericide may be any as long as it does not adversely affect the photographic performance. Specific examples include thiazolylbenzimidazole compounds, isothiazolone compounds, chlorophenol compounds, bromophenol compounds, thiocyanic acid and isothiocyanic acid. Compounds, acid azide compounds,
Diazine and triazine compounds, thiourea compounds,
Alkylguanidine compounds, quaternary ammonium salts, organotin and organozinc compounds, cyclohexylphenol compounds, imidazole and benzimidazole compounds,
There are various antibacterial agents and fungicides such as sulfamide compounds, active halogen compounds such as chlorinated sodium isocyanurate, chelating agents, sulfite compounds, and antibiotics represented by penicillin. Other L. E. FIG. Wes
t. “Water Quality Criteri
a "Photo. Sci. and Eng. Vol.
No. No. 6 (1965);
No. 542, No. 58-105145, No. 59-1265
No. 33, No. 55-111942, and No. 57-157
No.244 various anti-bacterial agents; described in "Bactericidal and Fungicide Chemistry" written by Hiroshi Horiguchi and published by Sankyo Publishing Co., Ltd. (Showa 57); Chemicals and the like as described above can be used.

In the present invention, a developing and fixing replenisher prepared from a solid processing agent can be used. The term "solid processing agent" as used herein means a powder processing agent, a tablet, a pill, a granule, etc., which is subjected to a moisture-proof treatment as required.

In view of the demand for reducing the amount of waste liquid, it is preferable that the processing is performed while replenishing a fixed amount in proportion to the area of the photosensitive material. The fixing replenishment amount is 300 ml or less per m ² , preferably 30 to 250 ml per m ² .
The amount of replenishment for development is preferably 250 ml or less per m ² , more preferably 30 to 200 m ² per m ² .
l. Here, the fixing replenishing amount and the developing replenishing amount are the replenishing amounts of the respective solutions when replenishing the same solution as the developing mother liquor and the fixing mother liquor. The total volume of each of the concentrated solution and water when replenishing with a solution prepared by dissolving the solid developing agent and the solid fixing agent in water. And the sum of the volume of the solid processing agent and the volume of water when the solid developing agent and the solid fixing agent are separately replenished with water. When replenished with a solid processing agent, it is preferable to express the total amount of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the replenishing water added separately. The developing replenisher and the fixing replenisher may be the same as the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine, or different liquids or solid processing agents, respectively.

Due to the demand for shortening the development time, when processing is performed using an automatic processor, the total processing time (Dry) from when the leading end of the film is inserted into the automatic processor until it comes out of the drying zone.
to Dry) is preferably 70 seconds or less and 10 seconds or more. The term "total processing time" as used herein includes the total process time required for processing the black-and-white photosensitive material, and specifically includes processing, such as development, fixing, bleaching, washing, stabilization, and drying. Time including all process time, ie Dr
It is the time of y to Dry. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening.
More preferably, the total processing time (Dry to Dry) is 30 to 60 seconds.

In order to remarkably exert the effects of the present invention, a heat transfer material (for example, 60.degree.
~ 130 ° C heat roller etc.) or radiant object above 150 ° C (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc.) Those that transmit heat energy to a radiator such as copper, stainless steel, nickel, or various ceramics to generate heat or emit infrared rays) and have a drying zone are preferably used.

In the present invention, an automatic developing machine having the method and mechanism described below can be preferably used.

(1) Deodorizing device: JP-A-64-37560
No. 544 (2), upper left column to page 545 (3), upper left column (2) Waste liquid treatment method: JP-A-2-64638, 388
(2) Lower left column of page 391 (5) Lower left column of page (3) Rinse bath between developing bath and fixing bath: JP-A-4-31
No. 3749, page 18 [0054] to page (21) [00]
65 "(4) Water replenishment method: JP-A-1-281446 250
(2) Lower left column to lower right column of page (5) Method of detecting outside air temperature and humidity to control drying air of automatic developing machine: JP-A-1-315745, page 496 (2) lower right column to page 501 (7) Lower right column and JP-A-2-10805
No. 1, page 588 (2), lower left column to page 589 (3), lower left column (6) Method for recovering fixing waste silver: JP-A-6-27623, page (4), "0012" to page (7), "0071".

[0117]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 (Preparation of silver halide emulsion A) Aqueous solution of silver nitrate B and Na
A water-soluble halide solution C composed of Cl and KBr is adjusted to pH 3.
The mixture was added at a temperature of 0, 40 ° C. and a constant flow rate in Solution A for 30 minutes by the simultaneous mixing method, and 0.20 μm of AgCl 70 mol%, AgBr 3
0 mol% of cubic crystals were obtained. At this time, the silver potential (EAg) was 160 mV at the start of mixing and 100 mV at the end of mixing. Unnecessary salts were removed by ultrafiltration, and then 15 g of gelatin per mol of silver was added to adjust the pH to 5.7, followed by dispersion at 55 ° C. for 30 minutes. After dispersion, 4 × 10 ⁻⁴ mol of chloramine T was added per mol of silver. The silver potential of the resulting emulsion is 190 mV (40 ° C.)
Met.

A: ossein gelatin 25 g nitric acid (5%) 6.5 ml ion-exchanged water 700 ml Na [RhCl ₅ (H ₂ O)] 0.02 mg B: silver nitrate 170 g nitric acid (5%) 4.5 ml ion-exchanged water 200 ml C: 47.5 g of NaCl 51.3 g of KBr 6 g of ossein gelatin 0.15 mg of Na ₃ [IrCl ₆ ] 200 ml of deionized water 200 ml of 4-hydroxy-6 per mole of silver in the obtained emulsion.
Methyl-1,3,3a, 7-tetrazaindene is added to 1.5
× 10 ⁻³ mol and 8.5 × 10 ⁻⁴ mol of potassium bromide were added to adjust the pH to 5.6 and the EAg to 123 mV. Next, the sulfur dispersed in the form of fine particles was converted into sulfur atoms by 2 × 10
^-5 mol and 1.5 × 10 ^-5 mol of chloroauric acid were added and chemically ripened at a temperature of 50 ° C. for 60 minutes, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrahydrofuran was added. Seindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and 1.5 × 10 ⁻³ mol of potassium iodide. Then, after the temperature was lowered to 40 ° C., 2 × 10 ⁻⁴ mol of sensitizing dyes S-1 and S-2 were added per mol of silver.

Using the obtained emulsion, one side of the undercoated support was adjusted so that the coating weight per m ² was as follows.
From the support side, the following first and second layers were simultaneously coated in multiple layers and cooled and set (emulsion formulation A). Then, the following backing layer was applied on the undercoating layer having the antistatic layer on the opposite side at a coating speed of 200 m / min, and cooled and set at -1 ° C.
A sample was obtained by drying both sides simultaneously.

(Support, Undercoat Layer) After a corona discharge of 30 W / (m ² · min) was applied to both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm), an undercoat layer having the following composition was coated on both sides. And dried at 100 ° C. for 1 minute.

Copolymer of 2-hydroxyethyl methacrylate (25) -butyl acrylate (30) -t-butyl acrylate (25) -styrene (20) (numbers are by weight) 0.5 g / m ² surfactant A 3.6 mg / m ² Hexamethylene-1,6-bis (ethylene urea) 10 mg / m ² (Antistatic layer) A corona discharge of 10 W / (m ² · min) was applied to a polyethylene terephthalate support provided with an undercoat layer. After that, an antistatic layer having the following composition was coated on one side at 70 m / min.
Apply using a roll-fit coating pan and air knife at a speed of 90 ° C., dry at 90 ° C. for 2 minutes,
Heat treated at 90 ° C. for 90 seconds.

Water-soluble conductive polymer B 0.6 g / m ² Hydrophobic polymer particles C 0.4 g / m ² Polyethylene oxide compound (MW 600) 0.1 g / m ² Curing agent E 0.1 g / m ² First layer (Emulsion layer) Gelatin 1.0 g Silver halide emulsion A 3.3 g as silver amount Hydrazine derivative H-34 0.015 g Hydrazine derivative H-39 0.020 g 5-Nitroindazole 0.01 g 2-Mercaptohypoxanthine 0.02 g A suspension polymer of colloidal silica 75% by weight, vinyl acetate 12.5% by weight, and vinyl pivalinate 12.5% by weight 1.4g Dextran (average molecular weight 60,000) 0.2g 4-mercapto-3,5 6-fluorophthalic acid 0.05 g sodium polystyrene sulfonate (average molecular weight 500,000) 0.015 g It was .2.

Second layer (protective layer) Gelatin 0.9 g Dextran (average molecular weight 60,000) 0.2 g Nucleation promoter Na-21 0.15 g Colloidal silica 0.10 g Disinfectant Z 0.005 g Polyoxyethylene lauryl ether Sodium sulfonate 0.001 g Sodium dihexyl sulfosuccinate 0.015 g Silica (average particle size 5 μm) 0.015 g Silica (average particle size 8 μm) 0.15 g Hardener (1) 0.15 g Backing layer Gelatin 1.8 g F- 1 0.01 g F-2 0.03 g F-3 0.10 g Suspension polymer of 75% by weight of colloidal silica, 12.5% by weight of vinyl acetate, and 12.5% by weight of vinyl pivalinate 0.7g Polystyrene sulfone Sodium acid salt 0.010 g Matting agent: monodispersed polymethyl methacrylate having an average particle size of 3 μm G 0.045 g Hardener (2) 0.05 g Backing protective layer Gelatin 1.8 g Matting agent: Monodispersed polymethyl methacrylate having an average particle size of 3 μm 0.045 g Sodium polyoxyethylene lauryl ether sulfonate 0.005 g Dihexyl sulfosuccinic acid Sodium 0.005g Hardener (1) 0.15g

[0125]

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[0126]

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[0127]

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[0128]

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The obtained film sample A was 633 nm, 6
Exposure was possible with a 70 nm laser diode light source. The following processing was performed on this sample A.

(Development start solution: 1 L) Diethylenetriaminepentaacetic acid 1 g Sodium sulfite 30 g Potassium hydrogen carbonate 17 g 1-phenyl-4-methyl-4′-hydroxymethyl-3-pyrazolidone 1.5 g Sodium erythorbate monohydrate 40 g 1-phenyl-5-mercaptotetrazole 0.025 g potassium bromide 4 g 5-methylbenzotriazole 0.21 g 2,5-dihydroxybenzoic acid 5 g 8-mercaptoadenine 0.07 g KOH was used in such an amount that the used solution became pH 9.8. In addition, it was finished to 1L.

(Development replenisher: 2-fold concentrated solution) Diethylenetriaminepentaacetic acid 1 g Sodium sulfite 30 g Potassium carbonate 70 g Potassium hydrogen carbonate 17 g 1-phenyl-4-methyl-4'-hydroxymethyl-3-pyrazolidone 1.5 g 1-phenyl -5-mercaptotetrazole 0.03 g potassium bromide 1 g 5-methylbenzotriazole 0.30 g 2,5-dihydroxybenzoic acid 5 g 8-mercaptoadenine 0.10 g KOH was added in such an amount that the pH of the working solution became 10.15. ,
Finished to 0.5L.

(Fixing start solution: 1 L) Sodium thiosulfate 200 g Sodium sulfite 22 g Na gluconate 5 g Citric acid 3Na.2H ₂ O 12 g Citric acid 12 g Adjusted to pH 5.4 with sulfuric acid so that the pH of the working solution becomes 5.4. , 1
L finished.

(Washing Water) To 1 L of tap water, 8.8 ml of the following purifying agent was added and placed in a washing tank to prepare washing water.

(Preparation of Purifying Agent) Pure water 800 g Salicylic acid 0.1 g 35% by weight hydrogen peroxide water 171 g Pluronic F-68 3.1 g Hoksite F-150 15 g DTPA · 5Na 10 g Finished with pure water to 1 L.

[0135] (Amount of replenishment of processing solution) A developer, a fixing replenisher, a purifying agent, and tap water for dilution of the above-mentioned formulation are respectively supplied to a developing tank, a fixing tank,
The washing tank was replenished directly under the following conditions.

Developer replenishment amount Working solution 65 ml / m ² dilution water 65 ml / m ² Fixer replenishment rate Concentrate 65 ml / m ² dilution water 65 ml / m ² Rinse water replenishment amount Tap water 2.3 L / m ² Purifier 20 ml / m ² after 20 sheets continuously processed at 3-minute intervals as the running method, allowed to stand for 90 minutes, likewise repeated task of continuous treatment of 20 sheets were treated with total Encyclopedia 60 sheets of film samples a. The emulsion was inserted face down into the automatic processor. As the automatic developing machine, one capable of changing the transport speed at 365 to 4380 mm / min was used. Maximum processing width of photosensitive material is 864
mm. The transport speed during development was 1620 mm /
Minutes. The obtained samples were visually evaluated for stains, and the number of stains observed and the level of the most stained were ranked according to the following criteria. The stains were blue-violet stains and white stains.

That is, if the meaning of the dirt rank is 2 or less, there is a problem in practical use, 3 is a level that can be used but the dirt is clearly recognizable, 4 is a level where dirt is present but cannot be noticed unless seen carefully, and 5 is a dirt level. Not a level. The number of stains generated is desirably 10 or less during the processing of 60 sheets, and preferably 5 or less.

The results are shown below.

Experiment No. Type of sensitizing dye Type number of stains Soil rank Remarks 1 Comparative compound D 36 1 Comparison 2 d-2 34 Inventive 3 d-505 Inventive 4 d-605 Inventive 5 d- 9 34 The present invention 6 d-13 14 The present invention 7 d-17 24 The present invention

[0140]

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As is clear from the above, according to the embodiment of the present invention, both the frequency and the degree of the occurrence of dirt are greatly improved.

Example 2 The same experiment as in Example 1 was carried out except that the immersion time in the solution was changed as follows, while changing the number of seconds for development.

Experiment number Type of sensitizing dye Type of immersion time in liquid Number of stains Soil rank 8 d-6 5 9 3 9 d-6 10 1 4 10 d-6 45 0 5 11 d-6 60 3 4 12 d- 6 90 7 3 13 d-15 5 8 3 14 d-15 10 3 4 15 d-15 45 0 5 16 d-15 60 1 4 17 d-15 90 63 As is clear from the above, in the embodiment of the present invention, the liquid is used. The effect is even greater when the intermediate immersion time is 10 to 60 seconds.

Example 3 The same experiment as in Example 1 was carried out, except that the compositions of the developing solution and the fixing solution were changed as follows, and similar results were obtained.

Developer composition (per liter) Diethylenetriaminepentaacetic acid / pentasodium salt 1.0 g Sodium sulfite 42.5 g Potassium sulfite 17.5 g Potassium carbonate 55.0 g Hydroquinone 20.0 g 1-phenyl-5-mercaptotetrazole 0.03 g 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 0.85 g potassium bromide 4.0 g benzotriazole 0.21 g boric acid 8.0 g diethylene glycol 40.0 g 8-mercaptoadenine 0.07 g water and potassium hydroxide To a volume of 1 L, and pH10.
Make 4

Fixer composition (per liter) Ammonium thiosulfate (70% aqueous solution) 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Aluminum sulfate (27 % Aqueous solution) 25 ml The working solution pH was 4.9.

[0147]

As described above, the silver halide photographic light-sensitive material for an image setter of the present invention can be processed quickly and the generation of stains can be suppressed.

Claims (4)

[Claims] 1. A silver halide photographic material comprising a support and a layer containing a compound represented by the following general formula (1). Embedded image Wherein Y ¹ is O, S, Se,-(CH = CH) or-
In NR ² , Z represents an atomic group necessary for forming a fused ring having 5 or more atoms, and R ¹ and R ² each represent a hydrogen atom or an aliphatic group. L ^{1 to} L ⁶ represent a methine group, n,
m ₁ and m ₂ are each independently 0 or 1. Q represents a nonmetallic atom group necessary for forming an acidic ring. Where m ₁ =
When m ₂ = 1, at least one of L ^{1 to} L ⁶ satisfies m ₁ =
1, when m ₂ = 0, at least one of L ^{1 to} L ⁴ is m ₁
= M ₂ = 0, at least one of L ¹ and L ² is SP
It has a substituent such that ≤544. Here SP is S
P = 33.563L−2.661B + 535.4, L represents a STERIMOL parameter (Å), and B represents the smaller value of the sum of the STERIMOL parameters B ₁ + B ₄ and B ₂ + B ₃ ( Å). 2. In the general formula (1), m ₁ = 1 and m ₂ = 0
The silver halide photographic light-sensitive material according to claim 1, wherein 3. The silver halide photographic material according to claim ^1, wherein R ¹ in the formula (1) contains a water-soluble group. 4. A method for processing a silver halide photographic light-sensitive material, comprising developing the silver halide photographic light-sensitive material according to claim 1 for a liquid immersion time of 5 to 60 seconds.