JPH11282121A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance image quality, such as acutance and resolution, and to improve reproducibility of Ming type and Gothic letters and to obtain a wide doe gradation reproduction range by incorporating a compound to exhibit a restraining power by being changed with an oxidation developing agent, and a specified amount of an anionic surfactant. SOLUTION: The silver halide photographic sensitive material having a silver halide emulsion layer contains the anionic surfactant in an amount of 10-100 mg/m<2> and one kind of the compounds to exhibit a restraining power by being changed with an oxidation developing agent, preferably, the compounds represented by the formula in which each of R, R', and R'' is an H atom or a univalent substituent, such as an aromatic, heterocyclic, carboxy, sulfo, nitro, alkyl, alkoxy, cyano group or the like, each optionally substituted, or a halogen atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material for photolithography.

[0002]

2. Description of the Related Art In a photographic light-sensitive material for printing plate making, a halftone image is usually used, so a photographic technique capable of reproducing a super-high contrast image is used. In the past, lith development was the main role, but because of the drawbacks such as long processing time, many restrictions on photosensitive material design, and poor processing stability, for example, US Pat. Techniques utilizing nucleation development, such as a silver halide photographic light-sensitive material containing a hydrazine derivative described in JP-A-269,929, etc., have become mainstream. Further, the printing prepress operation includes a step of faithfully reproducing a halftone image. In order to produce an excellent printed matter, it is necessary that a target halftone dot is faithfully reproduced on a plate-making photosensitive material.

[0003] In recent years, in the field of printing plate making, further improvement in dot quality has been demanded. For example, it is called high-definition printing of 600 lines / inch or more or FM screening constituted by a random pattern of uniform minimum points. In the method, 25
It is necessary to reproduce minute points of μm or less. These include exposure with an image output machine equipped with a laser light source such as an Ar laser, HeNe laser, or semiconductor laser, a so-called plate-making scanner, and return work for exposing a transparent halftone image original with a printer. It is necessary that the target minute halftone dot is faithfully reproduced. In addition, in order to improve the quality such as enlargement (expansion) and reduction (shrinkage) of the halftone photograph in the line drawing shooting process, and to improve the reproducibility of light spots, it is necessary to faithfully reproduce the target minute halftone dot. It is.

However, if various measures are taken to improve the image reproducibility such as the halftone dot reproducibility, there arises a problem that the sensitivity of the photographic material is reduced each time.

For example, compounds which release a photographically useful group through an oxidation-reduction reaction and exhibit a development inhibiting effect corresponding to the image density in a development processing step are known. The technology using these compounds has improved the reproducibility of original manuscripts in the Ming Dynasty and Gozinky characters, copy dots and enlargement work with the diversification and complexity of printed materials in the field of silver halide photographic materials for photoengraving. It is a technology that was adopted because it was strongly desired.

The photoengraving step includes a step of converting a continuous tone original into a halftone image. For this step, a technique capable of reproducing images with ultra-high contrast is desired.
A method using a hydrazine derivative as described in JP-A-6-106244 or the like is used. According to this method, although photographic characteristics with a high contrast and high sensitivity are obtained, the infectious developability is too strong. The gradation was very short, and the reproducibility of the original document was poor, which had a drawback in image quality.

In order to improve the reproducibility, a mechanism for selectively suppressing development of only a large dot portion or a portion where a thin line of a character is missing has been required.

Attempts to satisfy these are described in, for example, JP-A-61-213847 and JP-A-62-2601.
Hydrazine derivatives disclosed in JP-A-53-53, JP-A-4-136839 and the like;
No. 8, JP-A-4-563, JP-A-4-6548, and JP-A-4-6551. A redox compound such as a hydroquinone derivative is added to a silver halide emulsion layer and developed in a silver image-like manner. Methods for releasing inhibitors are known. However, when these compounds are used, a decrease in sensitivity is still unavoidable. Generally, such a decrease in sensitivity is dealt with by increasing the sensitivity of the photosensitive emulsion. However, excessive sensitization degrades the improved image reproducibility.

This involves using a solid disperse dye for the protective layer,
It also occurs when a treatment such as applying a filter to an exposure apparatus, and it has been a long-standing problem to achieve both sensitivity and image reproduction.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an image forming material which is excellent in image quality such as sharpness and resolution, and has good reproducibility of Mincho and Gothic characters and a wide halftone reproduction range. To provide a silver halide photographic light-sensitive material.

[0011]

SUMMARY OF THE INVENTION The object of the present invention is to provide: (1) In a silver halide photographic material having at least one silver halide emulsion layer, a compound which exhibits an inhibitory power when changed by an oxidizing developing agent is used. Contains at least one kind,
And at least one of the anionic surfactants is
A silver halide photographic material characterized by containing 1000 mg / m ² . (2) The silver halide photographic light-sensitive material as described in (1) above, wherein the compound which is changed by the oxidized developing agent and shows an inhibitory power is a compound represented by the following general formula (1).

[0012]

Embedded image [In the formula, R, R 'and R "represent a hydrogen atom or a monovalent substituent.] (3) In the general formula (1), R and R' each represent at least one or more electron donating groups. A monovalent aromatic ring group, a heteroaromatic ring group, or a monovalent group in which these groups are substituted, and R ″ is a monovalent aromatic ring group, a heteroaromatic ring group, The silver halide photographic material as described in (2) above, wherein the group is a substituted monovalent group. (4) The halogen according to the above (2) or (3), wherein in the general formula (1), R ″ is a water-soluble group or a monovalent group having a water-soluble group as a substituent. (5) The silver halide photographic material described in any one of (1) to (4) above, which contains a hydrazine derivative. (6) An amine derivative, an onium salt, a disulfide derivative, and a hydroxy compound (1) to (1), which contain at least one compound selected from methyl derivatives.
The silver halide photographic material according to (5). (7) The compound of the above (1) to (1), wherein the compound represented by the general formula (1) is added to a layer other than the emulsion layer.
(6) The silver halide photographic material as described in any of (6) above. (8) The silver halide photographic light-sensitive material according to any one of the above (1) to (7), comprising a solid disperse dye. (9) The silver halide photographic light-sensitive material according to any one of the above (1) to (8), after imagewise exposure, is developed with a developer having a pH of 7.5 to 10.5. A method for processing a silver halide photographic material. Is achieved by

Hereinafter, the present invention will be described in detail.

First, a compound which exhibits an inhibitory power when changed by an oxidized developing agent will be described.

As the compound which changes depending on the oxidized developing agent and exhibits an inhibitory power, a compound represented by the following general formula (1):
Further, compounds represented by the following general formulas (2) to (4) are preferably used.

[0016]

Embedded image [In the formula, R, R 'and R "represent a hydrogen atom or a monovalent substituent.]

[0017]

Embedded image [Wherein, Y, Y ′ and Y ″ represent monovalent substituents.
m and n represent the integer of 0-5. ]

[0018]

Embedded image [In the formula, R, R 'and R "represent a hydrogen atom or a monovalent substituent, provided that at least one of the monovalent substituents represented by R, R' and R" represents It has an adsorptive group. ]

[0019]

Embedded image [Wherein, Y, Y ′ and Y ″ represent monovalent substituents.
m and n represent the integer of 0-5. However, at least one of the monovalent substituents represented by Y, Y 'and Y "has an adsorptive group to silver halide.] A compound represented by the general formula (1): The compound represented by the general formula (2), the compound represented by the general formula (3) and the compound represented by the general formula (4) will be sequentially described.

In the general formula (1), examples of the monovalent substituent represented by R, R ′ and R ″ include an aromatic ring group, a heterocyclic group, a carboxyl group, a sulfo group, a nitro group, a halogen, Examples thereof include an alkyl group, an alkoxy group, and a cyano group, which may be further substituted.

Preferred as the monovalent substituent are an optionally substituted aromatic or heterocyclic group.

Examples of the aromatic ring or hetero ring include a phenyl group, a pyridine residue, a quinoline residue, a thiazole residue, a pyrrole residue, a pyrazole residue and an imidazole residue. Examples of the substituent which the aromatic or heterocyclic group may have include halogen (fluorine, chlorine, bromine, iodine) and alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group). , An alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group), a cyano group, a homoaromatic group (for example,
Phenyl group, naphthyl group) or heteroaromatic group (for example, pyridine residue, quinoline residue, isoquinoline residue,
Pyrrole residue, pyrazole residue, imidazole residue, indole residue).

In the compound represented by the general formula (1),
The monovalent substituent represented by R or R 'is a monovalent aromatic ring residue or a heterocyclic residue, and at least one of them has an electron donating group; The compound in which the monovalent substituent represented by is a monovalent aromatic ring residue or a heterocyclic residue is preferable.

The electron donating group is a group having a negative σp value in Hammett's rule. Examples of the electron donating group include an alkoxy group (for example, methoxy group, ethoxy group, propoxy group and butoxy group) and an amino group. (For example, dimethylamino group, methylethylamino group) and the like.

In the compound represented by the general formula (1),
At least one of the monovalent substituents represented by R, R 'and R ";
When one has an adsorptive group to silver halide, the general formula (1)
The probability that the compound represented by the formula (1) is present in the vicinity of the silver halide is increased, and the reaction with the oxidized developing agent and the power for suppressing the development are improved, which is preferable.

The atomic group having an adsorptive group to silver halide includes an atomic group having a mercapto group (for example, mercaptooxadiazole, mercaptotetrazole,
Mercaptotriazole, mercaptodiazole, mercaptothiazole, mercaptothiadiazole, mercaptooxazole, mercaptoimidazole, mercaptobenzothiazole, mercaptobenzoxazole,
Mercaptobenzimidazole, mercaptotetrazaindene, mercaptopyridyl, mercaptoquinolyl, 2
-Groups having a thione group (e.g., thiazoline-2-thione, oxazoline-2-thione, imidazoline-2-thione, benzothiazoline-2);
Each group such as -thione, benzimidazoline-2-thione, thiazolidine-2-thione, etc.) and an atom group forming imino silver (for example, each group such as triazole, tetrazole, benzotriazole, hydroxyazaindene, benzimidazole, indazole, etc.) ), An atom group having an acetylene group (for example, 2- [N- (2-propynyl) amino]
Atoms such as benzothiazole and N- (2-propynyl) carbazole), an atom group having a thioether group (eg, each group such as 2-methylthioethyl, cyclohexylthiomethyl, cyclohexylthiomethylcarboxyl), and an atom having a ureido group Group, an atom group having a thioureido group, an atom group having a mesoionic structure, and the like.

The atomic group having a mesoionic structure is described in W. Ba.
ker and WDOllis perform quarterly review (Quart.Re
v.) 11, 15 (1957), Advances in
Heterocyclic chemistry (Advances in Hete
rocyclik Chemistry) 19, 1 (1976), which is a "5- or 6-membered heterocyclic compound, which cannot be satisfactorily represented by one covalent structural formula or local structural formula, In addition, compounds that have a pi-electron hexaploid associated with all the atoms that make up the ring and that the ring is partially positively charged and balanced with an equal negative charge on the exocyclic atom or group of atoms '' Represent.

As a mesoionic ring having a mesoionic structure,
Examples include an imidazolium ring, a pyrazolium ring, an oxazolium ring, a thiazolium ring, a triazolium ring, a tetrazolium ring, a thiadiazolium ring, an oxadiazolium ring, a thiatriazorim ring, and an oxatriazolium ring.

It is preferable that the group adsorbing group capable of adsorbing on silver halide is an adsorbing group having a thioether structure.

In the compound represented by the general formula (1), at least one of the monovalent substituents represented by R, R, and R ″
On the other hand, it is preferable to have a water-soluble group or a water-soluble group as a substituent, since the reaction at the time of development becomes faster and the residual color on the photosensitive material after the development is reduced. The water-soluble group referred to above is
A group that can be anionized in a developer, specifically,
Examples include a sulfonamide group, a sulfamoyl group, a phenolic hydroxyl group, a carboxyl group, a sulfo group, and salts thereof. Preferred water-soluble groups are carboxyl groups,
It is a sulfo group.

In the general formula (2), examples of the monovalent substituent represented by Y, Y 'and Y "include, for example, halogen (fluorine, chlorine, bromine, iodine) and alkyl group (for example, methyl group). , Ethyl, propyl, isopropyl), alkoxy (for example, methoxy, ethoxy, propoxy, butoxy), cyano, homoaromatic (for example, phenyl, naphthyl) or heteroaromatic Groups (for example, pyridine residue, quinoline residue, isoquinoline residue, pyrrole residue, pyrazole residue, imidazole residue, indole residue) and the like.

When there are a plurality of monovalent substituents represented by Y, Y 'and Y ", the monovalent substituents may be the same or different.

In the compound represented by the general formula (2),
At least one of the monovalent substituents represented by Y, Y 'and Y ";
When one has an adsorptive group to silver halide, the general formula (2)
The probability that the compound represented by the formula (1) is present in the vicinity of the silver halide is increased, and the reaction with the oxidized developing agent and the power for suppressing the development are improved, which is preferable.

The atom group having an adsorptive group to silver halide includes silver atoms described in the description of monovalent substituents represented by R, R 'and R "in formula (1). Atoms having an adsorptive group of

In the compound represented by the general formula (2), at least one of the monovalent substituents represented by Y, Y 'and Y "has a water-soluble group or a water-soluble group as a substituent. Then, the reaction at the time of development is accelerated, and the residual color on the photosensitive material after the development is preferably reduced, and the water-soluble group referred to above is a group that can be anionized in a developing solution. For example, a sulfonamide group, a sulfamoyl group,
Examples include phenolic hydroxyl groups, carboxyl groups, sulfo groups, and salts thereof. Preferred water-soluble groups are a carboxyl group and a sulfo group.

In the general formula (3), the monovalent substituent represented by R, R ', R "is the same as the one represented by R, R', R" in the general formula (1). Examples of the monovalent substituent described in the description of the monovalent substituent include the adsorbing group for silver halide which the monovalent substituent has, such as R, R ′, and R ″ in the general formula (1). And the adsorptive group to silver halide described in the description of the monovalent substituent represented by

A water-soluble group of the monovalent substituent,
Alternatively, as the substituent having a water-soluble group as a substituent, the water-soluble group described in the description of the monovalent substituent represented by R, R ′, and R ″ in the general formula (1), or
Examples include a substituent having a water-soluble group as a substituent.

In the general formula (4), examples of the monovalent substituent represented by Y, Y ′, Y ″ are the same as those represented by Y, Y ′, Y ″ in the general formula (2). The monovalent substituents described in the description of the monovalent substituent are exemplified. Examples of the adsorbing group for silver halide possessed by the monovalent substituent include Y, Y ′, and Y ″ in the general formula (2). And the adsorptive group to silver halide described in the description of the monovalent substituent represented by

When there are a plurality of monovalent substituents represented by Y, Y 'and Y ", the monovalent substituents may be the same or different.

A water-soluble group of the monovalent substituent,
Alternatively, as the substituent having a water-soluble group as a substituent, the water-soluble group described in the description of the monovalent substituent represented by Y, Y ′, or Y ″ in the general formula (2), or
Examples include a substituent having a water-soluble group as a substituent.

Specific examples of the compound represented by the general formula (1) and the compound represented by the general formula (2) include Che
m. Rev .. , 55 355 (1955), and synthesis can also be performed with reference to the method described in the same book.

The specific examples of the compounds represented by formulas (1) to (4) are shown below. The compounds represented by formulas (1) to (4) which can be used in the present invention include However, the present invention is not limited to this.

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Embedded image <Synthesis of Compound A-8>

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A compound (3) is synthesized by diazotizing 3.1 g of the compound (2) by a conventional method.

2.0 g of the compound (1) is dissolved in 10 ml of ice water, and the compound (3) is added. Next, 10 g of sodium acetate is added and stirred for 30 hours. Thereafter, the precipitate is collected by filtration, washed with water and dried. The crystals were recrystallized from ethanol to obtain 2.8 g of red crystals (A-8). (Melting point: 125 ° C.) <Synthesis of Compound A-51>

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35 g of the compound (1) is dissolved in 200 ml of water, and the compound (2) is added under ice cooling. The mixture is stirred for 1 hour while cooling with ice, and potassium chloride is added. The precipitate is collected by filtration to obtain 21 g of compound (3).

7 g of the compound (3) are suspended in 100 ml of water and 50 ml of methanol. Under ice-cooling, an aqueous solution of compound (4) synthesized by a conventional method was added dropwise. After stirring for 1 hour, potassium chloride was added, and the precipitate was collected by filtration. Recrystallized from ethanol,
5 g of compound (5) are obtained.

5 g of the compound (5) is dissolved in 200 ml of water, and 1.7 g of the compound (6) is added dropwise under ice-cooling. After stirring for 1 hour, extraction was performed using ethyl acetate. After evaporating the ethyl acetate under reduced pressure, the residue was recrystallized from ethyl acetate to give Compound A-514.5.
g.

The structure of Compound A-51 was confirmed from its NMR spectrum and mass spectrum. (Melting point: 14
3 ° C.) <Synthesis of Exemplified Compound A-122>

[0072]

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According to the above reaction formula, the compound was synthesized in the same manner as the above compound. (Melting point: 133 ° C.) In the present invention, the compound represented by the general formula (1) and the compound represented by the general formula (2) are contained in any layer provided on the side having the emulsion layer. For example, in the emulsion layer, in a hydrophilic colloid layer adjacent to the emulsion layer, can be contained in a hydrophilic colloid layer provided via an intermediate layer,
Particularly preferred layers containing the compound represented by the general formula (1) and the compound represented by the general formula (2) are an emulsion layer and / or a hydrophilic colloid layer adjacent to the emulsion layer. Providing a hydrophilic colloid layer between the emulsion layer closest to the support and the support, and adding the hydrophilic colloid layer to the hydrophilic colloid layer.

The compounds represented by formulas (1) to (4) of the present invention may be contained in a plurality of different layers.

The compounds represented by the general formulas (1) to (4) of the present invention include alcohols such as methanol and ethanol,
It can be added after dissolving in glycols such as ethylene glycol, triethylene glycol and propylene glycol, ethers, esters such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran and ethyl acetate, and ketones such as acetone and methyl ethyl ketone. In addition, those that are hardly soluble in water or organic solvents,
Average particle size 0.01 μm to 6 μm by high-speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion, etc.
Can be added in such a manner as to be dispersed. For dispersion of the compounds represented by the general formulas (1) to (4), an anionic or nonionic surfactant, a thickener, a latex, or the like can be used.

The compounds represented by formulas (1) to (4) are preferably used in an amount of 10 ^-6 mol to 10 ^-1 mol, more preferably 10 ^-4 mol to 1 ^-1 mol, per mol of silver halide.
It is used in the range of 0 ^-2 mol.

The silver halide emulsion layer containing the compounds represented by the general formulas (1) to (4) has a silver weight of 0.01 g to 5 g / m ² and a gelatin weight of 0.01 g / m ^2.
５5 g, and the value of silver weight / gelatin weight is preferably in the range of 0.01-20.

Next, the hydrazine derivative used in the present invention will be described.

The hydrazine derivative used in the present invention is, for example, a compound represented by the following general formula (H).

[0080]

Embedded image [In the formula, E represents an aryl group, a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents-(CO) n ¹
— Group, sulfonyl group, sulfoxy group, —P (＝ O) R ²²
And R ²² represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group,
Represents a substituent such as an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, an amino group, and the like, and n ¹ represents an integer of 1 or 2. E ¹ and E 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 acyl group. R ²¹ is a hydrogen atom,
Alternatively, it represents a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group, carbamoyl group, and oxycarbonyl group. ]

Among the compounds represented by the general formula (H), compounds having the following formula (Ha) are preferable as those having sufficient contrast even at a low pH (less than pH 10.5).

[0082]

Embedded image In the general formula (Ha), R ²³ represents an aliphatic group (eg, octyl group, decyl group), an aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group), a heterocyclic group (eg, pyridyl group) Group, thienyl group, furyl group). These groups are preferably further substituted with a suitable substituent, and R ²³ preferably contains at least one diffusion-resistant group or a silver halide adsorption promoting group.

As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable.
For example, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, phenyl groups, phenoxy groups, alkylphenoxy groups, etc., which are relatively inert to the above photographic properties.

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), Xa represents a group that can be substituted with a phenyl group. ma represents an integer of 0 to 4, and when ma is 2 or more, each Xa may be the same or different.

In the general formula (Ha), E ³ and E ⁴ have the same meanings as E ¹ and E ² in the general formula (H), and E ³ and E ⁴
Are preferably both 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 general formula (Ha), R ²⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group, a carbamoyl group or an oxycarbonyl group. Most preferred R ²⁴ include —COOR ²⁵ group and —CON (R ²⁶ )
A (R ²⁷ ) group (R ²⁵ represents an alkynyl group or a saturated heterocyclic group; R ²⁶ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; and R ²⁷ represents an alkenyl group or an alkynyl group. Group, saturated heterocyclic group, hydroxy group,
Represents an alkoxy group. ).

Hereinafter, specific examples of the hydrazine derivative will be shown, but the hydrazine derivative which can be used in the present invention is not limited thereto.

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Specific examples of other preferred hydrazine derivatives are described in US Pat. No. 5,229,248, columns 4 to 60, (1) to (2).
52).

The hydrazine derivative according to the present invention can be synthesized by a known method, for example, by the method described in US Pat. No. 5,229,248, column 59 to column 80. can do.

In the present invention, the hydrazine derivative can be used in any layer on the side of the silver halide emulsion layer, but is preferably added to the silver halide emulsion layer and / or an adjacent layer.

It is preferable that at least one hydrazine derivative is contained in the layer having the largest silver weight / gelatin weight ratio contained in the emulsion layer. The silver weight of the layer having the highest silver weight / gelatin weight ratio is preferably 1.5 to 10 times the gelatin weight. Further, it is preferable that the layer having the largest silver weight / gelatin weight ratio is the emulsion layer closest to the support.

The hydrazine derivative may be added in an amount which makes it harder (a higher contrast amount).

[0103] The optimum amount of added hydrazine derivatives, grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, but varies depending on the type of inhibitor, generally 1 mol of silver halide per 10 ^- The range is from ⁶ to 10 ^-1 mol, preferably from 10 ^-5 to 10 ^-2 mol.

In the present invention, two or more hydrazine derivatives can be used, and these can be contained in an arbitrary layer in an arbitrary state.

Next, the amine derivative used in the present invention,
The onium salt, the disulfide derivative and the hydroxymethyl derivative will be described.

The amine derivative, onium salt, disulfide derivative and hydroxymethyl derivative used in the present invention function as a release accelerator.

As the amine derivatives, for example, those described in
Nos. 0-140340, 62-50829,
JP-A-62-222241, JP-A-62-250439, JP-A-62-280733, JP-A-63-1240
No. 45, 63-133145, 63-2
Compounds described in 86840 and the like can be mentioned. More preferred amine derivatives are described in JP-A-63-124.
Nos. 045 and 63-133145, 63-133
Compounds having a group adsorbing to silver halide described in JP-A-286840, etc .;
Compounds having a total number of carbon atoms of 20 or more described in Japanese Patent Application Publication No.

The onium salt is preferably an ammonium salt or a phosphonium salt. Examples of preferred ammonium salts are described in JP-A-62-250439 and JP-A-6-250439.
Compounds described in, for example, JP-A-2-280733 can be exemplified. Examples of preferred phosphonium salts include JP-A-61-167939 and JP-A-62-167939.
Compounds described in 280733 and the like can be mentioned.

As the disulfide derivative, for example, there can be mentioned the compounds described in JP-A-61-198147.

Examples of the hydroxymethyl derivative include, for example, those described in US Pat.
777,118, EP231,850, JP-A-62-50829, and the like. Preferred hydroxymethyl derivatives are diarylmethanol derivatives.

The following are specific examples of the amine derivative, onium salt, disulfide derivative and hydroxymethyl derivative used in the present invention. The amine derivative, onium salt, disulfide derivative and hydroxymethyl derivative which can be used in the present invention are as follows. It is not limited to these.

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The optimum addition amount of these compounds differs depending on the kind thereof, but is 1.0 × 10 5 per mol of silver halide.
^-6 mol to 1.0 × 10 ⁻¹ mol, preferably 1.0 × ¹ mol
It is desirable to use it in the range of 0 ^-5 mol to 1.0 × 10 ^-2 mol.

These compounds can be used in a suitable solvent (for example,
Water, alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellosolve, etc.)
And added to the coating solution. These compounds may be used in combination of two or more.

Next, the anionic surfactant used in the present invention will be described.

Examples of the anionic surfactant include alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfates, alkyl phosphates, N
Carboxy groups, sulfo groups, such as -acyl-N-alkyltaurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, and the like.
Anionic surfactants containing an acidic group such as a phospho group, a sulfate group, and a phosphate group are exemplified.

Hereinafter, specific examples of the anionic surfactant used in the present invention will be shown, but the anionic surfactant which can be used in the present invention is not limited thereto.

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Embedded image

[0127]

Embedded image The anionic surfactant is preferably used at 10 to 1000 mg / m ² , more preferably 30 to 500 m / m ^2.
g / m ² . The amount of anionic surfactant used is 10
mg / m ² or less, the effect is small.
If it is more than / m ² , the coatability will be deteriorated.

In the silver halide photographic light-sensitive material of the present invention, it is preferable that at least two silver halide emulsion layers are provided on one side of the support in order to remarkably exert the effects of the present invention. The sensitivities of these two or more silver halide emulsion layers may be the same or different. These silver halide emulsion layers may be provided adjacent to each other, or one or more intermediate layers may be provided between the respective emulsion layers.

The composition of the silver halide in the silver halide emulsion layer is not particularly limited.
When the development is to be performed in less than a second, a silver halide emulsion composed of silver chloride, a silver halide emulsion composed of silver chlorobromide containing 60 mol% or more of silver chloride, or a silver halide emulsion composed of 60 mol% or more of silver chloride is used. A silver halide emulsion comprising silver chloroiodobromide is particularly preferable, and an image having a super-high contrast is obtained.

The average grain size of the silver halide is preferably 0.7 μm or less, particularly preferably 0.5 to 0.1 μm, from the viewpoint of expanding the halftone reproduction range. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood.

In the case where the silver halide grains are spherical or sphere-like grains, the grain diameter is the grain size of the silver halide. When the grains are cubic, they are converted into spheres of the same volume, and the diameter of the converted sphere is the grain size of silver halide.

Details of the method for determining the average particle size are described in Mies,
James: The Theory of the Photographic Process (CEMees & THJames: The theory o
f the photographic process), 3rd edition, pages 36 to 43 (1966 (published by Macmillan "Mcmillan")), and the average particle size can be determined by referring to the description.

There are no restrictions on the shape of the silver halide grains.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, the grain size distribution of the silver halide grains is preferably narrow, and in particular, 90%, preferably 95% of the total number of silver halide grains fall within a grain size range of ± 40% of the average grain size. Emulsions, so-called monodisperse emulsions, are preferred.

As a method for producing silver halide grains, any of a one-sided mixing method, a double-sided mixing method, a combination thereof and the like may be used. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, a so-called controlled double jet method, can be used. A silver halide emulsion having a nearly uniform grain size is obtained.

In at least one of the steps of forming or growing the silver halide grains, cadmium salts, zinc salts, lead salts, thallium salts, ruthenium salts, osmium salts, iridium salts or rhodium salts, or silver salts thereof are used. It is preferable to add a complex salt containing the following element.

The silver halide emulsion and its preparation method are described in detail in Research Disclosure (Resear
ch Disclosure) No. 176, 17643, pp. 22-23 (December 1978) and the literature cited therein.

The silver halide emulsion may or may not be chemically sensitized.

As a method of chemical sensitization, a sulfur sensitization method, a reduction sensitization method and a noble metal sensitization method are known, and any of these sensitization methods can be used alone or in combination for chemical sensitization. Can be used. A preferred chemical sensitization method is a sulfur sensitization method. As the sulfur sensitizer, various sulfur compounds other than the sulfur compound contained in gelatin, for example, thiosulfate,
Thioureas, rhodanines, polysulfide compounds and the like can be used.

A typical noble metal sensitization method is a gold sensitization method, and a gold compound, for example, a gold complex salt is used in the gold sensitization method. Noble metals other than gold, for example, complex salts such as platinum, palladium, and rhodium may be contained.

The reduction sensitizer used in the reduction sensitization method includes stannous salts, amines, formamidinesulfinic acid, silane compounds and the like.

The silver halide emulsion may be spectrally sensitized to a desired wavelength with a sensitizing dye. Sensitizing dyes that can be used for spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.

As these dyes, any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of, i.e., indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus,
Benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidine-2,4-nucleus
5 such as dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus
A 6-membered heterocyclic ring can be applied.

More specifically, Research Disclosure Vol. 176, RD-17643 (December, 1978)
Page 2, page 3, U.S. Pat. No. 4,425,425,
No. 4,425,426, compounds represented by the general formula [1] described in Japanese Patent Application No. 5-129157, page 3 (specific examples include, for example,
Compounds represented by general formula [2] described on pages 17 to 22) and compounds described on page 4 (specific examples include, for example, 2 described on pages 23 to 34). -1 to 2-4
8), compounds represented by the general formula [3] on pages 4 to 5 (as specific examples, for example, 3-1 to 3-48 on pages 35 to 48), Compounds represented by the general formula [1] described on page 3 of JP-A-129158 (specific examples include, for example, 1-1 to 1- on page 14 to 16).
14), a compound represented by the general formula [2] described on page 4 (for example, the compound represented by
-1 to 2-6), the compound represented by the general formula [3] described on page 5 (as specific examples, for example, 3-1 to 3-4 on page 19) and page 6 (Specific examples include, for example, 4-1 to 4-14 described on pages 20 to 22), and Japanese Patent Application No. 5-2077984.
Compounds represented by the general formula [I] on pages 4 to 5 (specific examples include, for example, [I] -1 to [I] -37 on pages 12 to 24), 5-2-1265
Compounds represented by the general formula [1] described on page 4 of the specification (specific examples include, for example, 1
-1 to 1-26), compounds represented by the general formula [2] described on page 5 (specific examples include, for example, 2-1 to 2-14 described on pages 20 to 22) and 5 Compounds represented by the general formula [3] on pages 6 to 6 (for example, 3- (1) to 3- (14) on pages 27 to 29), 6
Compounds represented by the general formula [4] described on pages 7 to 7 (for example, 4-1 to 4-4 described on pages 41 to 42).
-6) can be used.

Preferred sensitizing dyes are described in Research Disclosure 176, 1978 (176).
43) Pages 23 to 24 and 346, published in 1993 (34
685) can be used.

Sensitizing dyes are disclosed in US Pat. No. 3,485,634.
It may be dissolved and used by using ultrasonic vibration described in the specification. Other methods for dissolving or dispersing the sensitizing dye include those described in U.S. Pat. Nos. 3,482,981, 3,585,195 and 3,4.
No. 69,987, No. 3,425,835, No. 3,342,605, British Patent No. 1,
Nos. 271,329, 1,038,029, 1,121,174, U.S. Pat. No. 3,660,101, and 3,658,546.
There is a method described in the specification. These sensitizing dyes may be used alone or in combination. In addition, a combination of sensitizing dyes is often used especially for supersensitization. Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure 176, 17
643 (issued December 1978), page 23, IV, section J.

In the silver halide photographic light-sensitive material of the present invention,
Various compounds can be contained for the purpose of preventing fogging during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. For example, azoles, for example, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole)
Mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3,3).
3a, 7-tetrazaindenes), pentazaindenes and the like; benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers, such as benzenesulfonamide, can be included.

In the present invention, the silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer may contain an inorganic or organic hardener. Examples of the hardener include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2, Active vinyl compounds (1,3,5-triacryloyl-hexahydro-)
s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide] and the like, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine and the like) ), Mucohalic acids (mucochloric acid, phenoxymucochloric acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination. Compounds represented by formulas (1) to (7) described in JP-A-5-289219, pages 3 to 5, are preferred. Specific examples thereof include, for example, H-1 to H-39 described on pages 6 to 14 of the same specification.

In the silver halide photographic light-sensitive material of the present invention, it can react with a hardening agent which acts by activating a carboxyl group, ie, a free carboxyl group of a protein-like binder (eg, gelatin or the like), Preference is given to those containing a hardener which can thereby react with free amino groups to form peptide bonds and consequently form crosslinks in the binder.

In the present invention, the photosensitive emulsion layer and / or the non-photosensitive hydrophilic colloid layer may have various purposes such as a coating aid, an antistatic property, an improvement in slipperiness, an emulsification and dispersion, an adhesion prevention and an improvement in photographic properties. Various known surfactants may be added.

It is advantageous to use gelatin for the binder or protective colloid layer or other hydrophilic colloid layer of the silver halide emulsion, but other hydrophilic colloids can also be used. Examples of these hydrophilic colloids include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose,
Cellulose derivatives such as cellulose sulfates;
Sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
Examples thereof include various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole.

As the gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin, gelatin hydrolyzate, and gelatin enzyme hydrolyzate can also be used.

In the present invention, when the hydrophilic colloid of the layer containing the compound that releases a photographically useful compound by being oxidized is gelatin, in order to make the compound oxidized, 1.0 g / m of gelatin
It is preferably set to ² or less. When the amount of gelatin is in this range, the diffusion of the oxidized developing agent which should act imagewise in the direction parallel to the support is not unnecessarily large in the layer, which is preferable. More preferably, the amount of gelatin in the layer is 0.5 g / m ² or less.

In the present invention, a 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. Dispersions of these water-insoluble or poorly soluble synthetic polymers include, for example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate,
(Meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination, or acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, A polymer dispersion containing a combination of a sulfoalkyl (meth) acrylate, styrene sulfonic acid, or the like as a monomer component can be used.

In the silver halide photographic light-sensitive material of the present invention,
Various other additives can be used. These various additives include, for example, desensitizers, plasticizers, slip agents, development accelerators, oils, dyes and the like.

These various additives are specifically described in Research Disclosure 176 (supra),
The compounds are described on pages 22 to 31 and the like, and the compounds described therein can be used.

In the silver halide photographic light-sensitive material of the present invention, a protective layer can be provided. The protective layer may be a single layer or a multilayer composed of two or more layers.

In the silver halide photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are formed by coating on one or both sides of a flexible support usually used for a silver halide photographic light-sensitive material. Useful as flexible supports are
Cellulose acetate, cellulose acetate butyrate, polystyrene,
A film made of a synthetic polymer of polyethylene terephthalate.

The silver halide photographic light-sensitive material of the present invention is imagewise exposed and then processed with a developing solution to form an image. After being processed with a developing solution, a fixing solution process for removing undeveloped silver halide is performed.

The light source used for exposure is not particularly limited, and examples thereof include a laser, a light emitting diode, a xenon flash lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, and a tungsten lamp.

Examples of the developing agent or auxiliary developing agent that can be used in the developer include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 5-dimethylhydroquinone, etc.), 3
-Pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3- Pyrazolidone, 1
-Phenyl-5-methyl-3-pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-
Aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), pyrogallol, ascorbic acid,
Erythorbic acid, 1-aryl-3-pyrazolines (eg, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p- Aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline, etc.), transition metal complexes (T
i, V, Cr, Mn, Fe, Co, Ni, Cu, etc. These are complex salts of transition metals such as those having a reducing power to be used as a developer. For example, transition metal complexes are It takes the form of a complex salt such as Ti ³⁺ , V ²⁺ , Cr ²⁺ , Fe ²⁺ , and the ligand is ethylenediaminetetraacetic acid (EDT
A), aminopolycarboxylic acids and salts thereof such as diethylenetriaminepentaacetic acid (DTPA), and phosphoric acids and salts thereof such as hexametapolyphosphoric acid and tetrapolyphosphoric acid. ) Etc. can be used alone or in combination.

In the developing solution, a combination of a 3-pyrazolidone and a dihydroxybenzene, a combination of an aminophenol and a dihydroxybenzene, a combination of a 3-pyrazolidone and ascorbic acid, and a combination of an aminophenol and ascorbic acid are used. It is preferable to use a combination, a combination of a 3-pyrazolidone and a transition metal complex, or a combination of an aminophenol and a transition metal complex, particularly, a combination of erythorbic acid and 4,4-dimethyl-3-pyrazolidone. It is preferred to use.

The developing agent is usually preferably used in an amount of 0.01 to 1.4 mol / l.

In order to prevent the generation of silver sludge, it is preferable to carry out development processing with a developer containing a silver sludge inhibitor. As a silver sludge inhibitor, JP-B-62-47
02, JP-A-3-51844, 4-26
Nos. 838, 4-362942, 1-31
Compounds described in JP-A-9031 are exemplified.

The development waste liquid can be regenerated by turning on electricity. Specifically, the developing waste solution and the electrolyte solution are arranged so as to be in contact with each other via an anion exchange membrane, and a cathode (for example, an electric conductor or a semiconductor such as stainless steel wool) is used for the developing waste solution, and an anode (for example, An insoluble electrical conductor such as carbon, gold, platinum, or titanium) is charged, and electricity is supplied to both poles for regeneration.

Further, the silver halide photographic light-sensitive material can be processed while the developing waste liquid is regenerated by energization. At that time, various additives added to the developer, for example, preservatives, alkali agents, pH buffering agents, sensitizers, antifoggants,
A silver sludge inhibitor may be additionally added. When the developing waste liquid is recycled and used, it is preferable to use a transition metal complex as a developing agent.

Preferably, a preservative is added to the developer. As the preservative, sulfites and metabisulfites can be used. Sulfites and metabisulfites that can be used as preservatives include sodium sulfite,
Potassium sulfite, ammonium sulfite, sodium metabisulfite and the like. In the developer, the sulfite is 0.2%
It is preferable to use 5 mol / liter or more. Particularly preferably, it is at least 0.4 mol / liter.

If necessary, the developing solution may contain an alkali agent (eg, sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.). ), Dissolution aids (eg, polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, Antifoaming agents, antifoggants (for example, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles and the like), chelating agents (for example, Ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetic acid salt, polyphosphate ), Development accelerators (e.g., U.S. Pat. No. 2,304,025, JP-B-47-45
No. 541), hardeners (eg glutaraldehyde or bisulfite adduct thereof),
An antifoaming agent or the like can be added.

The pH of the developer is preferably 11 or less, more preferably pH 9.5 to 11, particularly preferably pH 10.2 to 1
0.8 is preferred, but the silver halide photographic light-sensitive material of the present invention can sufficiently achieve the intended purpose even if the pH of the developer is 7.5 or more and less than 10.5.

The developer may be a mixture of solid components, an organic aqueous solution containing glycol or amine, or a viscous liquid in a semi-kneaded state having a high viscosity. These may be used after dilution at the time of use, or may be used as they are.

In the development processing in the present invention, the development temperature can be set in a normal temperature range of 20 to 30 ° C., or can be set in a high temperature range of 30 to 40 ° C.

As a special type of development processing, there is an activator processing in which a developing agent is contained in a silver halide photographic light-sensitive material, for example, in an emulsion layer, and processed in an aqueous alkaline solution to perform development. Such development processing is often used as one of the rapid processing methods of silver halide photographic materials in combination with silver salt stabilization processing using thiocyanate. The silver halide photographic light-sensitive material of the present invention can be used for such a development process. In the case of such rapid processing, the effect of the present invention is particularly large.

As the fixing solution, those having a commonly used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and other components, and has a pH of usually 3.8 to 5.8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate; thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate; and organic sulfur that can form a soluble stable silver complex salt. Compounds known as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, for example, aluminum chloride, aluminum sulfate, potassium alum and the like.

The fixing solution may contain, if desired, a preservative (for example, sulfite or bisulfite), a pH buffer (for example, acetic acid), a pH adjuster (for example, sulfuric acid), a chelating agent capable of softening hard water. A compound such as an agent can be included.

The silver halide photographic light-sensitive material of the present invention is preferably processed using an automatic processor. At this time, the processing is performed while replenishing a fixed amount of a developing solution proportional to the area of the silver halide photographic material. The replenishment amount of the developer is set to 300 ml or less per 1 m ² in order to reduce the amount of waste liquid. Preferably 75 to ²⁰⁰ per m ²
Milliliters.

In the present invention, when processing is performed using an automatic developing machine, the total processing time (from dry to dry zone) after the leading edge of the film is inserted into the automatic developing machine until it comes out of the drying zone due to a demand for reduction of the developing time. Dry) for 10 to 60 seconds. The term “total processing time” as used herein includes the entire process time required to process a black-and-white photosensitive material, and specifically, necessary for processing, for example, development, fixing, bleaching, washing, stabilizing processing,
The time including all the time of the process such as drying, that is, Dry t
o It's Dry time. If the total processing time is less than 10 seconds, desensitization, softening and the like occur, and satisfactory photographic performance cannot be obtained.
The preferred total processing time (Dry to Dry) is 15 to 50 seconds.

The automatic developing machine may be a heat transfer material at 90 ° C. or higher (for example, a heat roller at 90 to 130 ° C.) or 150 ° C.
C. or higher radiating object (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc., and direct heat generation and radiation, or heat energy from a resistance heating element to copper, stainless steel, nickel, (Emission of infrared rays by transmitting heat to various radiators such as ceramics) and drying.

[0179]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 (Preparation of silver halide emulsion A-1)
The solution was adjusted to a silver potential (EAg) of 120 mV, pH 3.0, 35.
Under the condition of ° C., the mixture was added to the following solution C for 7 minutes by the simultaneous mixing method, and 0.09 μm of AgCl 70 mol%, AgBr 30
A nucleus was formed which is mol%. Thereafter, the silver potential was adjusted to 100 mV with NaCl, and the following solution D and solution E were added again over 15 minutes, and the average particle size was 0.20 μm and the variation coefficient was 15
%, 70 mol% of AgCl, and 30 mol% of AgBr. Thereafter, the pH was adjusted to 5.6 with a 1N-NaOH solution, and S-1 was added at 2 × 10 ⁻⁴ mol per mol of silver, followed by aging at 50 ° C. for 10 minutes. Thereafter, denatured gelatin treated with phenyl isocyanate was added, and p
The floc was washed with water at H4.2, and after washing with water, 15 g of gelatin per mol of silver was added to adjust the pH to 5.7, and 55 ° C.
For 30 minutes.

After dispersion, chloramine T was added at 4 × per mole of silver.
10 ^-4 mol was added. The silver potential of the resulting emulsion was 19
0 mV (40 ° C.).

Liquid A: Silver nitrate 16 g Nitric acid 5% 5.3 ml Ion exchange water 48 ml Liquid B: NaCl 3.8 g KBr 3.5 g ossein gelatin 1.7 g Ion exchange water 48 ml C liquid: NaCl 1.4 g Oce in gelatin 7g of nitric acid 5% 6.5 ml _{K 2 RhCl 5 (H 2 O} ) 0.06mg deionized water 700 ml solution D Silver nitrate 154g nitric acid 5% 4.5 ml ion-exchanged water 200 ml solution E: NaCl 37 g KBr 33 g ossein gelatin 6 g K ₂ RhCl ₅ (H ₂ O) 0.04 mg ion-exchanged water 200 ml

In the obtained emulsion, 1.5 × 10 ^-3 mol of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 8.5 × potassium bromide were used per mol of silver. 1
The pH was adjusted to 5.6 and the EAg to 123 mV by adding 0 ^-4 mol. Next, 2 × 10 ⁻⁵ mol and 1.5 × 10 ⁻⁵ mol of chloroauric acid were added as sulfur atoms to the sulfur dispersed in the form of fine particles and chemically ripened at a temperature of 60 ° C. for 80 minutes.
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene per mol of silver is 2 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole is 3 × 10 ^-4 mol and potassium iodide Was added in an amount of 1.5 × 10 ⁻³ mol. 40
C., and then sensitizing dye S-2 was added in an amount of 2 per mole of silver.
× 10 ^-4 mol was added.

(Preparation of silver halide emulsion A-2) Silver halide emulsion A-A was prepared except that the amount of K ₂ RhCl ₅ (H ₂ O) in solution C was 0.10 mg and the mixing temperature was 40 ° C. A silver halide emulsion was prepared in the same manner as in Example 1, and the average grain size was 0.25.
μm, coefficient of variation 15%, 70 mol% of AgCl, AgBr
A silver halide emulsion of 30 mol% was obtained. Thereafter, chemical sensitization and color sensitization were performed in the same manner as in the silver halide emulsion A-1.

<< Preparation of silver halide photographic light-sensitive material sample 101 >> An undercoat layer, a solid disperse dye layer, and a silver halide emulsion layer each having the following composition are formed on one side of the undercoated support from the support side. , An intermediate layer and an emulsion protective layer are simultaneously coated in multiple layers, cooled and set, and then on the opposite side of the undercoated support, a backing layer composed of the following formula from the support opposite side,
A backing protective layer was simultaneously applied in multiple layers, cooled and set at −1 ° C., and both sides were simultaneously dried to prepare Sample 101.

<Undercoat Layer> Silver halide emulsion A-2 Ag amount 0.3 g / m ² Gelatin 0.3 g / m ² Saponin 60 mg / m ² Compound T-1 50 mg / m ²

<Solid Disperse Dye Layer> Gelatin 1.0 g / m ² Solid Disperse Dye AD-1 15 mg / m ² Water-soluble Dye F-1 5 mg / m ² Latex L-2 (average particle size 0.25 μm) 3 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² <Silver halide emulsion layer> Silver halide emulsion A-1 Ag amount 3.3 g / m ² Gelatin 1.5 g / m ² Hydrazine derivative H-37 10 mg / m ² Polymer latex L-1 (average particle size 0.10 μm) 0.5 g / m ² Suspension polymer of 75% by weight of colloidal silica, 12.5% by weight of vinyl acetate and 12.5% by weight of vinyl pivalinate 1.0g / m ² saponin 20 mg / m ² 2-mercapto-6-hydroxy-purine 2 mg / m ² of ascorbic acid ^{20mg / m 2 EDTA · 2Na 25mg} / m 2 of polystyrene scan Sodium acid (average molecular weight 500,000) 15 mg / m ² coating solution pH was 5.2.

<Intermediate layer> Gelatin 0.32 g / m ² compound AM-46 12.9 mg / m ² Polymer latex L-1 (average particle size 0.10 μm) 0.3 g / m ² sodium polystyrene sulfonate (average molecular weight 500,000) 10 mg / m ² activator SA-1 5 mg / m ²

<Emulsion protective layer> Gelatin 0.48 g / m ² Water-soluble dye F-2 50 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 2 mg / m ² Surfactant SA 0.6 mg / m ² Matting agent: irregular silica having an average particle size of 3 μm 22.5 mg / m ² propyl garlic acid ester 15 mg / m ² dimethylsiloxane (average molecular weight 100,000) dispersion (average particle size 0.2 μm) 12 mg / m ² hard film Agent K-1 30 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Disinfectant Z 0.5 mg / m ² <Backing layer> Gelatin 3.0 g / m ² Sodium-iso-amyl-n-decyl sulfosuccinate 5 mg / m ² compound D 50 mg / m ² polymer latex L-3 0.3 g / m ² colloidal silica (average particle size 0.05 μm) 0.5 g / m ² Sodium polystyrene sulfonate 10 mg / m ² Dye F-3 120 mg / m ² Dye F-4 15 mg / m ² Dye F-5 37 mg / m ² 1-Phenyl-5-mercaptotetrazole 3 mg / m ² Compound D 50 mg / m ² Hardener K-2 100mg / m ²

<Backing Protective Layer> Gelatin 1.1 g / m ² Matting agent: monodispersed polymethyl methacrylate having an average particle diameter of 3 μm 45 mg / m ² sodium-di (2-ethylhexyl) sulfosuccinate 10 mg / m ²

<< Silver halide photographic light-sensitive material sample 102-
Preparation of Compound 120> Table 1 shows the compound T-1 (comparative) of the undercoat layer.
And the compound A-46 of the intermediate layer was changed to the compound AM shown in Table 1, and the activator SA of the intermediate layer was changed.
Samples 102 to 120 were prepared in the same manner as Sample 101 except that -1 was changed to the activator shown in Table 1 and the additive of the activator was changed to the amount shown in Table 1.

[0192]

[Table 1]

[0193]

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[0194]

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[0195]

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[0196]

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<< Evaluation of Sample >> Samples 101 to 12 Obtained
For 0, the sensitivity and γ were measured by:
The eye-drawing performance was evaluated. Table 2 shows the obtained results.

In the measurement of sensitivity and γ and evaluation of the elongation performance, processing was performed under the following processing conditions.

(Processing conditions) (Step) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Rinse at room temperature 20 seconds Squeeze / Dry 45 ° C. 30 seconds Total 100 seconds

(Developer 1) Pure water 224 mL DTPA · 5Na 1.0 g Potassium sulfite 12.54 g Sodium sulfite 42.58 g KBr 4 g H ₃ BO ₃ 8 g Potassium carbonate 55 g Diethylene glycol 40 g 5-methylbenzotriazole 0.21 g 1- Phenyl-5-mercaptotetrazole 0.03 g Dimezone S 0.85 g Hydroquinone 20 g KOH 18 g According to the above-mentioned formula, it was dissolved and finished to 400 ml.

In use, 600 ml of pure water was mixed to make 1 liter. Use liquid p
H was 10.40.

(Developing solution 2) The developing solution was adjusted in the same manner as the developing solution 1 except that the amount of KOH was changed so that the pH of the working solution became 11.00.

In use, 600 ml of pure water was mixed to make 1 liter.

(Fixing solution) Pure water 216 ml Ammonium thiosulfate 140 g Sodium sulfite 22 g Boric acid 10 g Tartaric acid 3 g Sodium acetate trihydrate 37.8 g Acetic acid (90% aqueous solution) 13.5 g Aluminum sulfate 18 hydrate 18 g It was dissolved and made up to 400 ml with pure water.

When using the above-mentioned concentrated liquid, the concentrated water
It was mixed with 00 ml and made up to 1 liter. The pH of the working solution was 4.83.

<Measurement of Sensitivity and γ> A sample was stuck to a step wedge, exposed to tungsten light at 3200 ° K. for 3 seconds, and processed under the above conditions using an automatic developing machine GR-27 (manufactured by Konica Corporation). .

The blackening density of the obtained developed sample was
-65 (Digital densitometer manufactured by Konica Corporation)
The reciprocal of the exposure amount giving a blackening density of 1.0 was defined as the sensitivity, and the sensitivity of each sample was determined by relative sensitivity with the sensitivity of the sample 101 being 100.

Further, an exposure amount giving a density of 0.05 and an exposure amount giving a density of 2.5 were obtained, and γ was obtained by the following equation.

Γ = 2.45 / (E (0.05) −E (2.5)) E (0.05); logarithmic value of the reciprocal of the exposure amount giving the density of 0.05 E (2.5) The logarithm of the reciprocal of the exposure giving a density of 2.5

<Evaluation of enlargement performance> H made by Konica Corporation
5% and 9% at 400 L using SG747 manufactured by Dainippon Screen Co., Ltd. using the scanner film SH-2 for e-Ne.
A 5% halftone dot is output, and this is used as an original. Using a fine zoom C-880F manufactured by Dainippon Screen Co., Ltd., the enlargement magnification is set to 120%, and 95% of the original is 5%. Exposure is performed by changing the exposure amount so that
Processing was performed under the above conditions using an automatic processor GR-27 (manufactured by Konica Corporation).

The dot percentage of the obtained developed sample was determined by X-Ri
The measurement was carried out at te361T, and at the exposure amount (appropriate exposure) at which 95% of the original became 5%, the collapse of halftone dots of the 5% of the original was visually evaluated.

[0212] The completely crushed one is defined as the first rank.
The leveling performance was evaluated in a five-point scale, with the last level being practically determined not to be crushed as the third rank, and the level that is considered to be reproducing the original being the fifth rank.

[0213]

[Table 2]

From the results shown in Table 2, it can be seen that the sample using the compound of the present invention has high sensitivity, high γ, and good enlargement performance even when developed using a developer having a pH of 10.5 or less. It turns out that it became favorable. The introduction of the adsorptive group improves the enlargement performance. In particular, when the adsorptive group is a thioether group, it is understood that the enlargement performance is improved while maintaining high sensitivity.

In addition, since the eye-drawing performance is improved, the reproducibility of Mincho / Gothic characters is also improved.

Example 2 (Preparation of silver halide emulsion B-1) Using a double jet method, silver chloride had an average diameter of 70 mol%, and the balance was silver bromide.
09 μm silver chlorobromide core particles were prepared. The preparation of the core particles by the double jet method is carried out by adding K ₃ Rh
(NO) ₄ (H ₂ O) ₂ was added at 7 × 10 ⁻⁸ mol per mol of silver at the end of grain formation, and K ₃ OsCl ₆ was added at 8 × 10 ⁻⁶ mol per mol of silver at the end of grain formation. 40 ° C, pH3.
0, while keeping the silver potential (EAg) at 165 mV.

EAg was added to the obtained core particles with salt.
The shell was attached using a double jet method at 5 mV. At that time, K ₂ IrCl ₆ was added to the halide solution at 3 × per mole of silver.
10 ^-7 mol of K ₃ RhCl ₆ was added in an amount of 9 × 10 ^-8 per mol of silver.
Mole was added. Further, KI conversion was performed using silver iodide fine particles. The resulting emulsion had an average particle size of 0.1
5 μm core / shell type monodispersed (coefficient of variation: 10%) silver chloroiodobromide (70 mol% of silver chloride, 0.2 mol% of silver iodide, balance being silver bromide) cubic silver halide It was an emulsion having grains. Then, a modified gelatin described in JP-A-2-280139 (in which an amino group in gelatin is substituted with phenylcarbamyl, for example, as described in JP-A-2-280139).
Illustrative compound G- on page 287 (3) of JP-A-280139.
Desalting was performed using 8). EAg after desalting is 190 at 50 ° C.
mV.

The obtained emulsion was mixed with 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene at 1.5 × 10 ^-3 mol per mol of silver and potassium bromide at 8.5 × 10 ³ mol.
^-4 mol, and citric acid was added to adjust the pH to 5.6.
EAg was adjusted to 123 mV, and p-toluenesulfonylchloramide sodium trihydrate (chloramine T) was added to 1 ×
After adding and reacting 10 ^-3 mol, an inorganic sulfur (S8) compound dispersed in a solid (Seishin Enterprise Co., Ltd .; PM-1
200, saponin was added and dispersed to an average of 0.5 μm), and 1.5 × 10 ⁻⁵ mol of chloroauric acid was added, and the mixture was chemically ripened at a temperature of 55 ° C. until the maximum sensitivity was obtained. Next, 100 mg of sensitizing dye d-1 and 5 mg of trihexylamine were added at 50 ° C. After cooling to 40 ° C, 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was used in an amount of 2 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole was used in an amount of 3 × 10 ^-4 mol, and potassium iodide was used in an amount of 5 mol per mol of silver. × 10 ^-3 mol was added, and citric acid was added to adjust the pH to 5.1.

(Preparation of Silver Halide Emulsion B-2) In the preparation of silver halide emulsion B-1, the core grain conditioning temperature was raised to 50 ° C., and K ₃ RhCl ₆ in the shell portion was changed to 6 × 10 6 per mole of silver. ^A silver halide emulsion B-2 having an average grain size of 0.19 μm was prepared in exactly the same manner except that the amount was changed to ^-8 mol.

When the same chemical sensitization was performed, silver halide emulsion B-2 was 40% higher in sensitivity than silver halide emulsion B-1.

<< Preparation of Silver Halide Photographic Material Sample 201 >> On one side of the support, a gelatin undercoat layer of the following formula 1 and a silver halide emulsion layer 1 of the following formula 2 were formed from the support side.
A silver halide emulsion layer 2 of the following formula 3 and an emulsion protective layer of the following formula 4 were simultaneously coated by a curtain coating method at a speed of 200 m / min, and cooled and set. At that time, the amount of gelatin in the gelatin undercoat layer was 0.45 g / m ² ,
The silver halide emulsion layer 1 has a silver content of 1.5 g / m ² and the silver halide emulsion layer 2 has a silver content of 1.5 g / m 2.
² , the amount of gelatin in the protective layer is 0.6 g / m ^2.
I tried to be. Next, a backing layer of the following formulation 5 and a backing protective layer of the following formulation 6 were simultaneously coated on the undercoat layer on the opposite side of the support from the support side, and cooled and set at -1 ° C. At that time, the amount of gelatin in the backing layer was adjusted to 0.6 g / m ^2, and the amount of gelatin in the backing protective layer was adjusted to 0.4 g / m ² .

After cooling and setting, both sides were dried at the same time.
Sample 201 was manufactured.

Formulation 1 (Gelatin undercoat layer) Gelatin 0.45 g / m ² Saponin 56.5 mg / m ² Compound T-1 (Dissolved in ethyl acetate and dispersed in a gelatin solution, and then ethyl acetate was removed under reduced pressure. 25 mg / m ² solid disperse dye AD-1 50 mg / m ² sodium polystyrene sulfonate (average molecular weight 500000) 15 mg / m ² fungicide Z 0.5 mg / m ²

Formulation 2 (Silver Halide Emulsion Layer 1) Silver Halide Emulsion B-1 Silver equivalent 1.5 g / m ² equivalent Sensitizing dye S-3 150 mg / Ag 1 mol Hydrazine compound H-37 2 × 10 ^-3 Mol / Ag 1 mol Compound AM-46 15 mg / m ² Compound J 100 mg / m ² 2-pyridinol 1 mg / m ² Polymer latex L-2 (average particle size 0.25 μm) 0.25 g / m ² Hardener K-2 5 mg / m ² sodium-iso-amyl-n-decylsulfosuccinate 0.7 mg / m ² sodium naphthalenesulfonate 0.5 mg / m ² saponin 20 mg / m ² hydroquinone 20 mg / m ² 2-mercapto-6-hydroxypurine 2 mg / m ² 2-mercaptopyridine 1 mg / m ² colloidal silica (average particle size 0.05μm) 150mg / m ² of ascorbic ^{20mg / m 2 EDTA 25mg / m} 2 Sodium polystyrenesulfonate 15 mg / m ² active agent SA-1 5mg / m ² coating solution pH was 5.2.

Formulation 3 (Silver Halide Emulsion Layer 2) Silver Halide Emulsion B-2 Amount of silver 1.5 g / m ² equivalent Sensitizing dye S-4 100 mg / Ag 1 mol Hydrazine compound H-37 4 × 10 ^-3 Mol / Ag 1 mol sodium-iso-amyl-n-decylsulfosuccinate 0.7 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / m ² nicotinamide 1 mg / m ² gallic acid n-propyl ester 50 mg / m ² Mercaptopyrimidine 1 mg / m ² EDTA 50 mg / m ² Styrene-maleic acid copolymer (molecular weight 70,000) 10 mg / m ² Polymer latex L-6 (JP-A-5-66512) Example 3 Type Lx-3 Composition (9)) 0.25g / m ² colloidal silica (average particle size 0.05μm) 150mg / m ² gelatin phthalated gelatin There pH of the coating solution was 4.8.

Formulation 4 (Emulsion protective layer) Gelatin 0.6 g / m ² amino compound Na-3 14 mg / m ² sodium-iso-amyl-n-decylsulfosuccinate 2 mg / m ² Matting agent: average particle size 3. 5 μm spherical polymethyl methacrylate 25 mg / m ² matting agent: average particle size 8 μm irregular silica 12.5 mg / m ² surfactant SA 26.5 mg / m ² slip agent (silicone oil) 4 mg / m ² compound J 50 mg / m ² polymer latex L-7 (average particle diameter 0.10 .mu.m) 0.25 g / m ² colloidal silica (average particle size 0.05 .mu.m) 500 mg / m ² dye F-6 20mg / m ² 1,3- vinylsulfonyl - 2-propanol 40 mg / m ² Hardener K-1 30 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Disinfectant Z 0.5 mg / m ²

Formulation 5 (Backing Layer) Gelatin 0.6 g / m ² Sodium-iso-amyl-n-decylsulfosuccinate 5 mg / m ² Polymer Latex L-3 0.3 g / m ² colloidal silica (average particle size) 0.05 μm) 100 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Dye F-6 65 mg / m ² Dye F-4 15 mg / m ² Dye F-7 100 mg / m ² 1-phenyl-5-mercaptotetrazole 10 mg / m ² hardener K-1 100 mg / m ² zinc hydroxide 50 mg / m ² EDTA 50 mg / m ²

Formulation 6 (Backing protective layer) Gelatin 0.4 g / m ² matting agent: monodispersed polymethyl methacrylate having an average particle size of 5 μm 50 mg / m ² matting agent: amorphous silica having an average particle size of 3 μm 12.5 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant SA 1 mg / m ² Dye F-6 65 mg / m ² Dye F-4 15 mg / m ² Dye F-7 100 mg / m ² Dye AD-1 (solid dispersion) 20 mg / m ² Compound J 50 mg / m ² Hardener K-1 20 mg / m ² Sodium polystyrene sulfonate 10 mg / m ²

<< Silver halide photographic light-sensitive material sample 202-
Preparation of 220> Compound T-1 (comparative) of gelatin undercoat layer was changed to compound A shown in Table 3, compound AM-46 of silver halide emulsion layer 1 was changed to compound AM shown in Table 3, and halogen was changed. Table 3 shows activator SA-1 of silver halide emulsion layer 1.
Sample 2 was prepared in the same manner as in Sample 201 except that the activator shown in Table 2 was changed and the additive of the activator was changed to the amount shown in Table 3.
Nos. 02 to 220 were produced.

[0230]

[Table 3]

[0231]

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[0232]

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<< Evaluation of Samples >> Samples 201 to 22 Obtained
For 0, the sensitivity and γ were measured by:
The halftone was evaluated. Table 4 shows the obtained results.

In the measurement of sensitivity and γ and the evaluation of halftone, processing was performed under the following processing conditions.

(Processing conditions) (Step) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Rinse at room temperature 20 seconds Squeeze / Dry 50 ° C. 30 seconds Total 100 seconds

(Developer) Per liter of working solution diethyltriamine pentaacetic acid / pentasodium salt 1 g sodium sulfite 42.5 g potassium sulfite 17.5 g potassium carbonate 55 g hydroquinone 20 g 1-phenyl-4-methyl-4-hydroxymethyl-3 -Pyrazolidone 0.85 g Potassium bromide 4 g 5-Methylbenzotriazole 0.2 g Boric acid 8 g Diethylene glycol 40 g 8-Mercaptoadenine 0.3 g KOH was added in an amount to bring the pH of the working solution to pH 10.4.

(Fixing solution composition) Ammonium thiosulfate (70% aqueous solution) per liter of used 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 Sulfuric acid was used to adjust the pH of the working solution to 4.9.

<Measurement of Sensitivity and γ> Exposure was performed by a laser sensitometer using a He-Ne laser having a wavelength of 633 nm as a light source, and step exposure was performed while changing the amount of light in 1.5 × 10 ⁻⁷ seconds. Using GR-27 (manufactured by Konica Corporation) under the above conditions, a photographic characteristic curve was obtained and the density was determined to be 2.5.
The reciprocal of the amount of exposure that gives the sensitivity was defined as the sensitivity, and the sensitivity of each sample was determined as a relative sensitivity with the sensitivity of the sample 201 as 100.

The tangent of a straight line connecting the point of density 0.1 and the point of density 3.0 of the photographic characteristic curve was defined as γ.

When the gamma value (γ) is 10 or more, it indicates that a super-high contrast image can be obtained.

<Evaluation of halftone gradation> Halftone gradation was determined by the following equation.

Halftone = log E (95%) − log E (5%) E (95%); exposure amount giving 95% halftone area E (5%); exposure amount giving 5% halftone area The larger the halftone value, the better the halftone.

[0243]

[Table 4]

From the results shown in Table 4, it can be seen that the sample using the compound of the present invention exhibited high sensitivity, high γ and halftone gradation even when developed using a developing solution having a pH of 10.5 or less. It can be seen that an image with a wide reproduction range can be obtained. By introducing an adsorbing group, the halftone reproduction range has been improved.
It can be seen that when the adsorptive group is a thioether group, the halftone reproduction range is improved while maintaining high sensitivity.

[0245]

The silver halide photographic light-sensitive material of the present invention comprises:
Even when developing with a developer having a pH of 10.5 or less, high sensitivity can be obtained, high γ can be obtained, an image with a wide halftone reproduction range can be obtained, and Mincho and Gothic characters can be reproduced. Is good.

Claims (9)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer, comprising at least one compound which exhibits an inhibitory power by being changed by an oxidized developing agent, and which comprises an anionic surfactant. the silver halide photographic material, which comprises 10 to 1000 mg / m ² contains at least one. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the compound which is changed by an oxidized developing agent and exhibits an inhibitory power is a compound represented by the following general formula (1). Embedded image [In the formula, R, R 'and R "represent a hydrogen atom or a monovalent substituent.] 3. In the general formula (1), R and R 'each represent a monovalent aromatic or heteroaromatic group having at least one or more electron donating groups, or these groups are substituted. 3. The monovalent group according to claim 2, wherein R ″ is a monovalent aromatic ring group, a heteroaromatic ring group, or a monovalent group in which these groups are substituted. Silver halide photographic material. 4. In the general formula (1), R ″ is a water-soluble group,
4. The silver halide photographic material according to claim 2, wherein the photographic material is a monovalent group having a water-soluble group as a substituent. 5. The silver halide photographic light-sensitive material according to claim 1, which further comprises a hydrazine derivative. 6. The method according to claim 1, wherein the compound contains at least one compound selected from an amine derivative, an onium salt, a disulfide derivative and a hydroxymethyl derivative.
6. The silver halide photographic light-sensitive material according to any one of items 1 to 5. 7. The method according to claim 1, wherein the compound represented by the general formula (1) is added to a layer other than the emulsion layer.
7. The silver halide photographic light-sensitive material according to any one of items 1 to 6, 8. The silver halide photographic light-sensitive material according to claim 1, further comprising a solid disperse dye. 9. A halogen, which comprises subjecting the silver halide photographic material according to any one of claims 1 to 8 to imagewise exposure and developing with a developer having a pH of 7.5 to 10.5. Processing method of silver halide photographic light-sensitive material.